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Current World Environment

Vol. 7(1), 01-06 (2012)

Air Pollution Estimation from Traffic Flows in Tehran Highways KEIVAN SAEB¹, MARYAM MALEKZADEH¹ and SAEED KARDAR² ¹Department of Environment, Tonekabon Branch, Islamic Azad University, Tonekabon (Iran). ²Department of Environment, Damavand Branch, Islamic Azad University, Damavand (Iran). (Received: January 01, 2012; Accepted: February 19, 2012) ABSTRACT Urban areas confront with increases in air pollution because of increasing urbanization, expanding the use of vehicles and development of economic activities. In this research carbon monoxide concentration as a pollutant analyzed and modeled within highways in Tehran. In this regards factors affecting the concentration of atmospheric pollutants analyzed on the basis of geometric, atmospheric and traffic data at five stations in Tehran and finally models runs based on existing methods. The model predictions results are match well with field data.

Key words: Air Pollution, Traffic Flows, Tehran Highways.

INTRODUCTION Motor vehicles emit nitrogen oxides (NOx), carbon monoxide (CO), volatile organic compounds (VOC) and particulate matter (PM), which constitute a major source of air pollution in large cities. To achieve sustainable development and a sustainable transport we need a tool to evaluate projects related to transportation, with good accuracy and in numerical form. With increasing traffic and the increases in pollutants, Human will be in risk from environmental issues that impacts of that on physical health, psychological and economic losses are evident. Heavy traffic in large cities by thousands of car passage has increased the air pollution. Today, air pollution is one of the main human issues and become more important each day. In Iran, according to land use, topography, traffic behavior, and traffic it is a very important problem. To identify and fix this problem in urban streets, factors such as computation of pollutants level and their compatibility with standards are important and finally set up the executive works to reduce air pollution, are effective steps is to resolve this problem. To achieve environmental goals, and determine the environmental issues for planners,

environmental impact studies in traffic management plans and in the road design is considered and the purpose is to determine the transportation request in condition that the negative environmental effects of that not be more than standards. Analysis of carbon monoxide pollution levels in places where traffic is the main source of air pollution is selected as the main target of research. It must be mentioned that the issue of air quality is essential in urban design and planning urban transportation. Although these analysis is not only limits to predict concentrations of pollutants caused by traffic in urban streets but it is so important in these areas because this problem is more significant in urban streets. In summary, in this study the effective factors on concentration of pollutants in the atmosphere surveyed in the vicinity of highways of Tehran, near the surface and sidewalk based on field data in 32 points on 5 stations. Calculations have been done in short-term (one hour) and usual traffic conditions in these areas. The final purpose of the research is to provide a model for estimation carbon monoxide

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SAEB et al., Curr. World Environ., Vol. 7(1), 1-6 (2012)

concentration in urban highways with good accuracy and set the acceptable amount of traffic and other features in the system by investigate the causes of these pollutants and prediction of that. Literature Review Understanding the characteristics of the air flows besides and upper of streets is necessary for understanding the transmission and distribution performance of pollutants in urban highways. There are three main methods for this problem: all dimensions measurement, reduce field measurements by using of physical models and mathematical models1. Many studies about the Highways confirm that the vortex flow in the streets will expand when the wind that blows in roof surface is perpendicular to the direction of the wind spread. The result of this vortex flow is transmission of the pollutants in upstream and in the direction of the wind and then transfer it back to the wind and finally increasing the pollutants levels in the back side of wind2. Jacko et al., Study the transmission parameters of a point pollutant source at the center of town using a wind tunnel model. They found that with increasing two times in average height of building, buildings with equal density, the concentration of pollutants at ground level in urban areas will double too. There are accurate studies about measurements of the wind profile in real urban highway by Oke & Nunez in 1977, Sheih in 1986, and Nakamura in 1988. Generally, these studies show a form of a vortex in street, but this cannot be true in all cases (especially at low wind speeds). Physically, studies of the wind tunnel model are simpler from study of all dimensions from the viewpoint of guidance and control. However inaccurate boundary conditions and incorrect scaling may cause errors. Studies of Hoydysh in 1988 and 1991 show the pollutants concentration pattern depends on the path symmetry and apparent ratio of the block size. And concentration of pollutants in the vertical direction is reduced exponentially. Also the concentration of pollutants is more in the back of wind toward the face of wind3. Numerical models used for the issue of urban highways can be in several forms: some of

them simulate the fluid flow and contaminant transmission and some are empirical models based on observational data. Advances in computer hardware technology have provided new opportunities for the simulation of environmental aspects. Johnson et al.,, in 1990 and Shuzo et al.,, in 1992 investigate the wind flow as the fluid in urban highways and approved a number of wind tunnel results, such as the wind vortex rotation when the roof-level wind flow is perpendicular to street3. In 1973 Johnson et al.,, made an empirical model based on observed data in all dimensions in the State of California. The model predicates the decrease of concentration from a linear source against the wind and linear decreases of concentration toward height level on the opposite side of the wind. They found that the wind direction in roof-level controls the levels of CO concentration pattern. Concentration of CO near the street surface in the backside of wind is significantly higher toward the opposite side4. Lin and Niemeier (1998) used observed traffic data to estimate hourly allocation factors and disaggregated traffic volume into hourly values. These indirect methods inevitably lead to inaccuracies in emission modeling. In theory, numerical modeling of traffic flow on road can provide every detail required for the calculation of traffic emissions. Unfortunately, previous efforts failed to do this because of road network complexity5. L. Xia, Y. Shao (2005) used a Lagrangian traffic flow model. According to their study the traffic flow model is simple, but has been found to be quite efficient. With the specification of travel behavior, their model was capable of simulating traffic flow on a road network. The model applied successfully to Hong Kong Island. The simulated traffic flows in three cross-harbour tunnels and at three counting stations on the island for weekdays and weekends were compared with observations. The temporal variations of traffic flow in the crossharbour tunnels and at the counting stations were reproduced by the model at satisfactory level6.

SAEB et al., Curr. World Environ., Vol. 7(1), 1-6 (2012)

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is complicated and requires high cost. Also comparison of laboratory data and field data is difficult and using wind tunnel simulation models requires extensive laboratory facilities.

METHODS There are three appropriate methods for study of factors affecting the traffic pollutants levels [1]: 1Developing the two-stage models (diffusion - distribution) that Distribution mechanism simulates with the Navier-Stokes equations and appropriate boundary conditions are considered (numerical modeling). 2Developing experimental models based on wind tunnel and field observations (simulation wind tunnel using a small-scale model). 3Developing empirical models based on true understanding of all factors influencing the concentration of pollutants and also the data collected at different sites with a wide range of traffic and atmospheric conditions.

According to the purpose of this study and the available facilities the first and second methods are not recognized suitable. Therefore the third method that apply the effective factors and field data are used and relationships between geometric, atmospheric and traffic conditions are analyzed. This method has advantages over other methods as follows [7] 1. Because analyzing the levels of pollutants and effective parameters are with each others, expanding the relations based on equal weights in the distribution and emission becomes possible. 2. In terms of costs these models that based on field observations are the best option. 3. Empirical relationships are simple and not required powerful computer to estimate concentrations of pollutants for purposes of transportation planning. 4. When empirical relationships for evaluating

Methods 1 and 2 require accurate models to predict emission rates of pollutions based on traffic parameters. Because there is not prepared accurate diffusion models in Iran, two stages modeling is not applicable. Furthermore accurate measurements of parameters in emission models

Table 1: Results of modeling Model No. 1 2 3 4

A

B

.189 -.000027 -.00015 -.000065

21.111 1.22 1.47 1.35

C

D

E

-2.144 . . -3.97 .2438 . -3.78 .0091 . -4.46 .222 .33

Rsqr

MSR

MSE

F

F a,k,n-k-1

.763 .745 .762 .757

4935. 4928 4935 4933

21.59 23.2 21.7 22.12

228.6 212.4 227.4 223

2.64 2.64 2.64 2.64

Table 2: Results of models variation

  Co  Co  4

Model

Rsqr

k

Max Res

1

i

Std.

Std.

Std.

1

No.

1 2 3 4

.763 .745 .762 .757

3 4 3 5

+

-

7.6 7.6 7.4 7.0

-7.9 -8.8 -7.9 -9.9

Deviation (28)

0.6 1.1 0.9 1.0

4.287 4.441 4.297 4.339

Error Deviation of (4) Mean (4) .346 .664 .547 .652

.693 1.329 1.095 1.305

4

SAEB et al., Curr. World Environ., Vol. 7(1), 1-6 (2012) and selecting transportation projects are used less input data are require to other modeling methods. Also these data are available in the planning of transportation and are easily accessible. Furthermore the experimental models run just with a small part of inputs that the two-stage models are required.

Data collecting Generally the factors affect the pollution concentration in urban highways are divided into four groups. 1. Traffic parameters 2. Geometric design 3. Atmospheric condition 4. Surroundings (background) concentration

There are define methods for measurement in methods 1 through 3 and there is general agreement about their digitizing. But surroundings concentration seems to be some complicated. The surroundings concentrations are the amount of pollutant that exists in the air without traffic there. Distribution of residential and industrial areas near the areas under study will impact of this issue7. About the first three methods there are distinct measurements methods and general agreement to digitize it. But the Surrounding concentrations seem to be some complex. The background concentrations are the pollutants that exist in the air without traffic condition. Distribution of residential and industrial areas near the areas under study, affects this issue7.

Fig. 1: Positive and good correlating between Co concentration and hourly traffic

Fig. 2: Negative and good correlating between Co concentration and wind normal speed

SAEB et al., Curr. World Environ., Vol. 7(1), 1-6 (2012) The main focus of this research will be on the first three groups of variables because the reason as follow: ´ First, traffic is effective in pollution concentration on the ground surface and near the urban streets and at low altitude areas. ´ Second, it is due to studies about the role of traffic in the concentration of CO in Tehran City. According to studies, more than 90% of the CO gas production is arising from transportation in Tehran. ´ The third reason is related to the stations selection. It is tried that the selected station be in commercial and residential areas, and away from industrial areas that produce CO gas. The main problem with field data in this study is requirement of taking the traffic, air pollution and the atmospheric data in the same time. The locations of existing measurement stations of “Tehran air pollution control” and “environmental protection organization” have been checked first. Because more of existing stations were besides the crossroad and squares and some others were set in wide area generally there were no suitable stations that show the pollution conditions of urban streets.

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Meteorological variables In this study three variables analyzed that includes: wind speed, wind direction and environment temperature. This information has been taken from meteorological stations of Resalat highway. Meteorological variables at different hours and days of the week were existed and in which time the data are collected the desired meteorological data is extracted too. Model development In order to develop a model to predict and estimate well, firstly correlated pairs of variables were analyzed. Based on this analysis, traffic volume and wind normal speeds were identified as the most effective variables. Figures (1) and (2) shows the correlation between these variables and hourly concentrations of carbon monoxide. Correlation between traffic volume and the carbon monoxide concentration is +0.814 and between the wind normal speed and the concentration of carbon monoxide is -0.655. The calibration of the previous models shows good agreement for SRI and Crompton & Gilbert models. In this stage through the following analysis and using SPSS software four combine forms were define and calibrated.

So used from portable samples. Furthermore portable samplings have some advantages because some parameters like station situation and the height level of samples are controllable. High amount of traffic and highways condition takes into consider in sampling as well as the other foresaid important conditions. Therefore Modares and Resalat highways selected for data measurement. Geometric variables Geometric variables in stations were measured in three dimensions: elevation, longitudinal and transverse. Data measurements have taken at adjacent stations in different parts of the two highways. Geometric variables in these stations are very close together, so the main focus is on the relationship between pollution levels, traffic parameters and meteorological conditions.

Traffic : the rate of traffic (vehicles of hours) W.Sinα: wind normal speed (m/s) Wt: total road width (m) Temp: temperature To select the final model the ability of models checked. As it can be seen from table (1) and (2) model No.1 suggested as the best models according to prediction ability and computational error.

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SAEB et al., Curr. World Environ., Vol. 7(1), 1-6 (2012) CONCLUSION

In order to determine a viable method for quantifying the contribution of traffic emission to regional air quality, all methods analyzed and according to the analyses developing empirical models that apply the effective factors and field data has advantages over other methods. The correlation between the variables and hourly concentrations of carbon monoxide shows that the main parameters influencing the distribution of carbon monoxide concentration in the city streets are traffic volumes and normal speed and the study shows

that the calibrated models SRI and Crompton & Gilbert are good in existing traffic, geometric and atmospheric conditions of Tehran. In addition four integrated traffic emission model developed and good agreement has been found between them and field data therefore can accurately predict carbon monoxide concentrations due to traffic and atmospheric conditions of Tehran. Finally the study shows that these models have good ability and can be use as a technique by traffic managers to reduce air pollution in polluted cities in Iran, to control the volume of traffic with environmental standards.

REFERENCES 1.

2.

3.

4.

Environmental Protection Agency, Appendix W to part 51 – Guideline on Air Quality Models (1995). Shiran, G. R. “Area–Wide Environmental Capacity Based on Air Pollution Criteria, Ph.D. Thesis , University of New South Wales, Sydney , Australia (1997). A.A.Hassan and J.M.Crowther, Modeling of fluid flow and pollutant dispersion in a street canyon, Environmental Monitoring and Assessment 52: pp 281-297 (1998). C.M.N Riain, B.Fisher, C.J.Martin, and J.Littler, Flow field and dispersion in a central London street, Environmental Monitoring

5.

6.

7.

and Assessment 52: 299-314 (1998). Lin, K., Niemeier, D., Using multivariate multiple regression models to improve the link between air quality and travel demand models. Transportation Research 3(6), 375– 387 (1998). L. Xia, Y. Shao, Modeling of traffic flow and air pollution emission with application to Hong Kong Island, Environmental Modeling & Software 20: 1175-1188 (2005). Linaritakis, Factors affecting traffic – related air pollutant levels in urban streets, Ph.D. Thesis, University of London, United Kingdom (1987).

Current World Environment

Vol. 7(1), 07-12 (2012)

Effect of Temperature and Humidity on the Population Abundance of Spotted Oriental Cucumber Beetle Epilachna chrysomelina (F.) (Coccinellidae : Coleoptera) In Al - Qunfudah Western Saudi Arabia SALEH A. AL-DIGAIL, AHMA I ASSAGAF and JAZEM A. MAHYOUB Department of Biological Science, King Abdul-Aziz University, Jeddah (KSA). (Received: May 18, 2012; Accepted: June 18, 2012) ABSTRACT The Melon Ladybird Beetle, Epilachna chrysomelina (Coleoptera: Coccinellidae) Fabricius, is one of the major phytophagous insects that feed on cucurbit plants. E. chrysomelina which is considered an economic pest in agriculture is a multi-habitat insect widely distributed throughout the world .It is also endemic along the Southern and the Western coast of Saudi Arabia due to the abundance of cucurbit plants (wild and domesticated) where it passes through all four developmental stages . In this research it was found that temperature and humidity affect the insect biological activities through their effect on insect reproduction and development. During some parts of the year the insect is more abundant due to the favorable conditions of temperature and humidity for reproduction. The month of March was more favorable than February while January was the least favorable.

Key words: Epilachna chrysomelina (F.), The Melon Ladybird Beetle, Biological activities.

INTRODUCTION The spotted oriental cucumber beetle E. chrysomelina (F.) is a notorious pest feeding on many vegetable crops and attacks its most preferred plants specially members of the family Cucurbitaceae like pumpkin, sweet gourd, bitter gourd, cucumber, Cucumis mello, Cucurbita pepo and Citrullus lanatus ( Talhoq, 1982 ). The pest damages in adult and larval stages during all vegetation of host plants. It damages mainly melons, cucumbers, pumpkins, and vegetable marrows. Watermelon is damaged in a lesser degree (Papointe and Shapiro, 1999 ; Lapointe , 2000).

gourd fruits keep badly, decaying in 30-40 days (Shirai and Yara, 2001; Hiiesaar et al., 2005; Taylor and Schrader 2010 ) . In Saudi Arabia, E. chrysomelina is one of the most injurious cucurbit attacking pests.The beetle is distributed throughout the country specially the South Western region( Abo-Thoria, 1982 ; Omaker et al., 2009). The present work was planned to evaluate the effect of temperature and humidity on the population abundance of spotted oriental Cucumber beetle E. chrysomelina in Al- Qunfudah province Kingdom of Saudi Arabia. MATERIALS AND METHODS

The pest sometimes entirely consumes seedlings of the melons and gourds of late sowings, Beetles are more gluttonous during reproduction time (Al-Allan et al., 2008). Damaged melon and

Study area Al- Qunfudah province located on the west coast of the Kingdom of Saudi Arabia is one of

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Al-Digail et al., Curr. World Environ., Vol. 7(1), 7-12 (2012)

the largest cities of Makka Al Mukarrama Region in Saudi Arabia, overlooking the Red Sea on the west, and away from the holy city of Mecca 350 km to the south, and away from Jeddah, 360 km (Fig. 1). Its geographic coordinates are 19 07 42. 18" N and 41 05 11. 75" E level. Data collection The Cucurbit plant Momordia charantia was chosen to study the abundance of E. chrysomelina L. throughout the year . The plant grows naturally depending on the environmental conditions including soil moisture ,however the beetles were observed congregating on this 4 preferred cucurbit plant feeding on its foliage , specially when there is no cucurbit plants growing in the vicinity The choice on M. charantia was based upon the following criteria : 1. The continued abundant availability of the host plant throughout the year. 2. The plant tolerates environmental fluctuations in (temperature, humidity and dryness of soil ). 3. The beetles thrive and nourish best on this plant throughout the year as considered it preferred host . Method of calculating abundance of E. chrysomelina . The study started January 2009 up to December 2009 . Fifteen plants of Momordia charatia , having the same size were chosen . The plants were separated from each other at distances of approximately 15 meters , giving a total study area of 150 meter squared , and each plant was marked by given a serial number . The plants were visited monthly , recording number of insects present then, insects were collected by hand , during two periods , from 6. a.m. to 10. a.m. in the morning , and from 10. a.m. noon time . The monthly field visits took place during the middle of the month , and the temperature and RH% were registered using a digital metrological instrument , and also temperature and RH data were obtained from the Metrology and Environment Protection Department. Data analysis Data were analyzed using SAS statistics software (version 6). Data were analyzed in order to find relationship & correlation between climatic factors, and the population numbers of the cucurbit

beetle E. chrysomelina Al- Qunfudah province. RESULTS The results showed a pronounced effect of the environmental factors as seen from the daily mean values of the temperature and R.H. on the daily emergence of the insect for feeding, and its behavioral activities. The level of activity was observed as related to the differences in insect numbers during certain periods of the year, hence the maximum numbers were recorded in March then February and April respectively with an average temperature of 22.72, 21.95, 25.21ºC and R.H. of 64, 66, 64.5% respectively, which represents the optimum values for the beetles breeding and reproduction. The minimum population density of the insects was recorded during August, September and October where the average temperature and R.H. reached 31.39, 29.02, 27.28ºC and RH 49, 57, 57.5% respectively (Table 1). During the rest of the year the average population density fall between the average range. The E. chrysomelina beetles were affected by variation in the environmental conditions as regards to their activity and the different plant growth stages throughout the year. Moreover they thrive well in temperatures ranging between 23ºC and 35ºC ,

Table 1: Mean temp. and Humidity during the months of (Jan. - Dec. 2009) Month

January February March April May June July August September October November December

Mean Temperature(C°)

Humidity(%)

23.17 21.95 22.72 25.21 28.06 31.23 30.32 31.39 29.02 27.28 27.51 24.10

62.5 66 64 64.5 65.5 58 54.5 49 57 57.5 61 62

Al-Digail et al., Curr. World Environ., Vol. 7(1), 7-12 (2012)

between different climatic factors & abundance of E. chrysomelina population in time & space using data collected at 6AM-12AM and 6AM-12AM. Pearson’s Correlation coefficient values suggest positive correlation and highly significant relationship between E. chrysomelina population and temperature, negative correlation significant relationship between E. chrysomelina population and relative humidity (Table. 2).

and R.H. between 30 and 70%. Out of these ranges there was pronounced reduction in growth and reproduction rate, and increase in mortality and inhibition in egg hatching. Generally, E. chrysomelina beetles were abundant during January- May period, then their population numbers starts decreasing from June till October where it reached the minimum population numbers (Fig 2 & 3).

The analysis of variance (Table 2) indicated a highly significant difference ( p<0.01) between temperature and number of eggs, and a significant difference (p<0.05) between R.H.% and number of beetles at periods 6-10 a.m. and noon time.

The beetle population was abundant during the morning period 6 a.m. to 10 am., and their numbers drop sharply from 10 to noon time with a complete absence of the beetles after 12 Oclock. The beetles were not 6 abundant after 10 a.m. during July to October due to the sharp rise in temperature after this time .

This might give an indication that the feeding activities of the beetle E. chrysomelina on leaves of the host plants is affected by temperature and R.H. and the beetles were actively feeding early

In the following analysis of results, correlations were used to explain the relationship

Table 2: Pearsonâ&#x20AC;&#x2122;s correlation values between climatic factors and E. chrysomelina density Time Parameters Temperature Relative Humidity

9

6AM-12AM

6AM-12AM

r-value

p-value

r-value

p-value

-0.76444 0.63476

0.0038** 0.0266*

-0.76816 0.60005

0.0035** 0.0391*

* Significant ** high Significant

Fig. 1: Location of the study area in Al- Qunfudah City Kingdom of Saudi Arabia

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Al-Digail et al., Curr. World Environ., Vol. 7(1), 7-12 (2012)

in the morning and their numbers decreased with increase in temperature and when R.H. starts decreasing . The beetles disappear completely after 12 oclock (Table 2), which illustrates the

relationship between the beetle numbers on plants and temperature degrees and R.H. throughout the year .It is clear evident that the most suitable time for the beetles feeding lies between 6 to 10 a.m.

Fig. 2: The graph showing the relationship between abundance of E. chrysomelin & temperature

Fig. 3: The graph showing the relationship between abundance of E. chrysomelin & humidity 8

Al-Digail et al., Curr. World Environ., Vol. 7(1), 7-12 (2012) during March , April and February , and least present during October . Indicated ( Table 1 ) to averages of temperature and humidity during the year 2009. DISCUSSION It was clearly evident that E. chrysomelina is active during early morning hours and gradually disappears with rise in temperature as was mentioned earlier by Habeek et al., (1990) who reported marked effects of the environmental variations of the beetle population and our results were in agreement with these findings. Such effects are obvious from the influence of the daily mean temperature and R.H. on the presence of these beetles during their daily feeding in the field. The maximum number of the beetle present was during February , March and April, where the temperature and R.H. were at their optimum values 23°C and 70% , and the minimum density was during August ,September and October with a rise of temperature to 36°C and the reduction of R.H. to35%. Abdelrahman ( 2005 ) mentioned that fixed temperature affects growth and reproduction of Coccinella undecimpunctata , suggesting that the optimum temperature for this carnivorous insect and its development ranges between 25 to 30°C. Taghizadah, ( 2008 ) repor ted that increasing temperature up to 40°C did not improve the insect development .There are significant differences between the rates of temperature decrease and the increase in the development and growth of the beetle , a fact which plays a vital role in the reproduction rate of the beetle and manifested in the increase in their numbers during certain periods of the year. The beetles appear feeding during day on different parts of the plant . In the early morning were observed on the upper surface of the leaf ,and later when temperature starts rising hiding under the lower surfaces of the leaves , and at noon observed congregating below the plant between branches and on the soil near the bases of their host plant. It has been observed that the beetles prefer moist humid habitats in most agricultural fields, however the second best preferred host plant was bitter gourd in the absence of 11 cucumber, as an alternative host plant where

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they complete their life cycle..This plant emits volatile odors which probably attracted these beetles. Moreover E. chrysomelina beetles can differentiate between the different cucurbit plants because they were never observed feeding on , bitter melon plants . Al-Allam , ( 2008 ) reported significant differences in egg hatching periods during temperature ranges between 28-30ºC , and no significant differences in the adult life span periods at temperature 32°C. This might probably explain the reduction in beetle population density as a result of reproduction with increase in temperature. The results indicated the absence of a significant correlation between egg numbers produced and R.H. , while the correlation is strongly significant with the number of eggs produced and temperature . These results are in agreement with some authors findings (Lapointe 2000; AbdelRahman 2005 ; Papointe and Shapiro 1999 ; Shirai and Yara 2001; Yunis et al., 2004). CONCLUSION In general, as evident from the results the activity of the pest is at its peak in the month of March; therefore it is recommended that the crop must be sprayed by insecticides during the month of January and February to control the activity of adult insects. ACKNOWLEDGMENTS The authors wish to extend their profound gratitude and appreciation to Sayed Mohammad Al Laithy for welcoming the conduction of this field study at his farm and thanks also goes to his 11 fellow workers who have contributed in the manual work near Al-Qunfotha town. Also deep thanks and appreciations were conveyed to the technical staff of the biological Science Department. Faculty of Science .King Abdul Aziz University for their appreciated efforts by giving a helping hand during data collection and the preparation of this manuscript.

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Al-Digail et al., Curr. World Environ., Vol. 7(1), 7-12 (2012) REFERENCES

1.

2.

3.

4.

5.

6.

Abdel-Rahman, M. ( 2005 ) . Influence of constant temperature on the development , and reproductive potential of the ladybird beetle , Coccinella undecimpunctata L. ( Coleoptera : Coccinellidae ). 3rd International Conf. on IPM role in Integrated Crop Management and Impacts on Envi. And Agr. Products , 26-29 (2005), Geiza ,Egypt. Abo – Thoria , N. General account of agricultural pests in the King dom of Saudi Arabia .Agricultural Research and Water Management . Riyadh , Saudi Arabia , 268 (1982). Al-Allan et al, Coccinella septempunctata L. (Coleoptera: Coccinellidae) Arab Scientist Organization, ArabScinetist.org. (2008). Habeek , D. H. ,Bennett, F. D. andJ.H.Frank. Classical biological control in the southern United States. Southern Cooperative Serier Bull. No. 355 , IFAS Ed. ,Univ. Florida , Gainesville ,FL. 197 (1990). Hiiesaar , K. ,Metspalu, L. , Joudu, J. Jogar , K. ( 2005 ). Influence of low temperatures on development of preimaginals of Colorado potato beetles , Leptinotarsa decemlineata ( Coleoptera : Chrysomelidae) 3rd International Conf. on IPM role in Integrated Crop Management and Impacts on Envi. And Agr. Products, 26-29 (2005), Geza ,Egypt. Lapointe, S. L. ( 2000 ) . Thermal requirements for development of Diaprepes abbrivatus (Coleoptera :Curculionidae). Environ.

7.

8.

9.

10.

11.

12.

13.

Entomol. 29: 150-156 (2000). Papointe ,S. L. and J. P. Shapiro. Effect of soil moisture on development of Diaprepes abbrivatus ( Coleoptera : Curculionidae ). Florida . Entomol. 82: 291-299 (1999). Omakar C. ; S. Rastogi ; P. Pandey. Effect of temperature on reproductive attributes of the Mexican beetle Zygogramma bicolorata ( Coleoptera: Chrysomelidae ). Inter. Jour. of Tropical Insect Sci. 29: 48-52 (2009). Shirai , Y. and Yara , K. Potential distribution area of the Mexican bean beetle , Epilachna varivestis ( Coleoptera : Coccinellidae ) in Japan , estimated from its high – temperature tolerance . Appl. Entomol. Zool. 36(4): 409417(2001). Taghizaden , R., Y. Fathipour , and K. Kamali. Temperature-dependent development of Acarophagous ladybird, Stethorus gilvifrons ( Coleoptera : Coccinellidae ). J. Asia –Pasific Entomol., 11(3): 145-148 (2008). Talhoq , A.S. Applied Zoology in Saudi Arabia , Anote on the Entomophagous Insects . Fnuna and Saudi Arabia , 4: 525531 (1982). Taylor, F. and R. Schrader ( 2010 ). Transient effects of photoperiod or reproduction in the Mexican bean beetle .Physio. Ento. 9(4): 459464 (2010). Yunis , L. H. ; K. F. Azzawi ; A. F. Khalifa . Applied insect science . First Ed. ,Faculty of Agriculture , Iraq , 281– 290 (2004).

Current World Environment

Vol. 7(1), 13-22 (2012)

Shading Nets Usefulness for Water Saving on Citrus Orchards under Different Irrigation Doses A. ABOUATALLAH1, R. SALGHI1* A. EL FADL2, B. HAMMOUTI3, A. ZARROUK 3, A. ATRAOUI2 and Y. GHNIZAR4 1

Equipe de Génie de l’Environnement et Biotechnologie, ENSA, Université Ibn Zohr, BP1136 Agadir, Morocco. 2 Institut Agronomique et Vétérinaire Hassan II, IAVCHA, BP 121 Ait Melloul, Morocco. 3 LCAE-URAC18, Département de Chimie, Faculté des Sciences, Université Mohammed Premier, BP 4808, Oujda, Morocco. 4 GPA Group, 325, Av Hassan II Agadir, Morocco. (Received: March 12, 2012; Accepted: April 14, 2012) ABSTRACT This work treats a comparative study of deficit irrigation and shading nets impacts on the citrus growth and fruit dropping, in order to save water without affecting physiological status and trees performances. The first dose (100%) is calculated using reference evapotranspiration (ETo - calculated using weather station), and crop coefficient (Kc) which varies according to physiological stage; the second is a double-dose (200%) and the third is a half-dose (50%); This study has shown that the application of half-dose using shade screens meets trees needs without causing adverse effect on crop performances; the soil water content and root hairs are well distributed laterally, the bulb’s depth and 90% of roots are located at 0-50 cm horizons. Shading net enhanced fruit growth and has mitigated fruit dropping phenomena by H≈50% for the treatment F50%.

Key words: Water saving, Shade screens, Dose, Irrigation, Citrus.

INTRODUCTION Water uptake for agriculture is very intensive in Souss Massa region (521Mm3 per year), where irrigation waters are almost exclusively pumped from the water table which is being depleted by 2 to 3 meter per year 1. The climate is very arid with rainfall of about 150-200 mm/year concentrated in winter and Evapotranspiration (ETo) of 1800 mm/year with more than 7 mm/day in the Summer, average winter temperatures can reach 5-7°C whereas average summer temperatures can be as high as 32-36 °C 2-3 . Adding the effect of the foreseen climate change, the available water volumes are expected to shrink by 10-15% of the actual volumes in 2020 due to the falling groundwater levels and the reduction of the storage capacity of dammed lakes by siltation 4. The citrus sector in the Souss region occupies about 33 000 ha which represents about 40% of the

whole citrus plantings in Morocco, and employing quasi permanent irrigation with very limited water resources. This has led to the use of low volume irrigation systems (i.e.; drip, microsprinklers etc.) by more than 80% of the citrus orchards 5. To sustain agriculture, it is particularly important to optimize crop yields by minimizing inputs, mainly water and nutrient application 6; Irrigation practices for water saving need to be adopted in intensive horticulture of Souss Massa region, where there is strong competition for scarce water supplies. While, Water efficiency is a key concept to solve water-shortage problems in semiarid areas 7, Shading nets structures in semiarid and arid environments can be considered as an intermediate solution for increasing water use efficiency and reducing plant water stress 8. It offer many advantages and environmental benefits 9-12, this is why an increasing area of crops, including

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citrus, is being grown under shading materials of various types, and growers need to know how these influence yield. Some authors reported that shading nets are helping to reduce wind speed within the foliage by about 40% 13, keep lower values of maximum daily shrinkage 14, maintain high leaf water content and better LAI - Leaf Area Index 15, reduce irradiance at the Earth’s surface 16, decrease crop transpiration by increasing stomatal diffusive resistance in leaves 17 and reduce the daily sap flow 17-18 . However the photosynthesis and integrated daily net CO2 uptake is maintained at high levels in shaded plants with respect to exposed trees 20, The shade provided by the net do not affect yield and internal fruit quality (ratio of sugar to acid) but may increase fruit average weight and diameter 14,21 . Another common practice is the Improve of water-use efficiency by reducing the amount of water supply 25-27,31. Plants have developed various mechanisms to withstand water stress, such as higher root-shoot ratios, fewer and smaller leaves, concentrated solutes or increased activity of oxidative stress enzymes in leaf cells 22 , nevertheless, rootstock characteristics are important factors influencing plant responses to water deficit 23. It is well known that water stress in citrus reduces stomatal conductance, transpiration rate and net assimilation of CO2 24-27; Some authors suggest that the Deficit Irrigation (DI) and regulated deficit irrigation (RDI) strategies can be applied in commercial orchards not only in case of water scarcity, but also as a tool to control vegetative growth improving fruit composition and reducing costs associated with the crop management 22. It was possible to save up to 18% of water, applying DI strategy, without any significant reduction in yield and fruit weight 28 , Mid-summer RDI strategy allowed 20% water savings, with a reduction in tree growth but without any significant reduction in yield, fruit size nor in the economic return, and helped to improve water use efficiency 29. Another author did find that RDI with 50% of the crop ETc decreased the yield by 10% but wasn’t statistically significant 30 , it is important to draw attention to the fact that fruit growth and flowering stages are the most sensitive periods in relation to irrigation water deficit and yield loss 31, a loss of water takes place from fruit to transpiring leaves during water stress32, fruit dropping may happen as a result of this endogen competition 33 or just a natural selection to keep a

limited fruit number balanced to its reserves 34, thus water-sever stress applied during the flowering and fruit-growth phases affect significantly the yield, the growth and reduces fruit size causing important economic losses in orchards 35,39; but when this degree of stress is applied during the maturity phase, it improves mainly fruit-quality parameters (total soluble solids, and titrable acidity in juice) 26,27,32,40 , other authors reported that DI and RDI decrease fruit size by 4% and fresh weight by 10%, but enhance total soluble solids by 10% and titratable acidity by 13% at fruit maturity 41. Although the amount of irrigation water would have a relative importance, but other variables such as the irrigation strategy, would decidedly influence prudent water management in semiarid areas 33, when using low watering frequency, Deficit irrigation reduces water use by 1250m3/ha, with similar yields in comparison to the fully irrigated trees 42. However, when reducing water supply, irrigation water salinity is very important factor that should be managed too, because it increases average crop root zone salinity and may result in a negative effect on crop yield 43. This work aims to compare the impact of three Deficit Irrigation strategies (200%, 100% and 50% doses) on performance and physiological status of “Afourer” mandarin, in order to streamline the water supply without adversely affecting the trees performances; shading nets were then used towards their usefulness when combined with water deficit. EXPERIMENTAL The experiment took place at two plots of 5 years old mandarin (Afourer) over an area of 8.5 ha. Planting density was 833 trees per hectare (2 m between trees and 6 m between rows). While the first parcel has trees in open field, the second parcel was under net. The plot is equipped with various instruments used for applied research and drip irrigation system. Each tree row has a single polyethylene pipe with self compensating online drippers that are placed at 1 meter from one to another on the pipe line and their flow is about 4 l/ hour at a pressure varying within the range of 1 to 4 bars, each tree has 2 drippers. The factor studied is the amount of water applied. All the other production practices (fertilization, protection against pests and diseases, weed control etc.) are optimal and were

ABOUATALLAH et al., Curr. World Environ., Vol. 7(1), 13-22 (2012) similar for the whole experimental plot. The three water regimes corresponding to the three treatments studied are defined based on Penman–Monteith evapotranspiration (ET) equation that predicts the rate of total evaporation and transpiration from the earth’s surface using commonly measured weather data (solar radiation, air temperature, vapor content, and wind speed) 44. Citrus water requirement was then estimated using proposed FAO crop coefficient (Kc) which varies according to physiological stage45. ETc (mm/day) = Kc x ETo (mm/day)

...(1)

The first dose is taken 100% of crop ETc, the second is a double-dose (200%) and the third is a half-dose (50%). The 100% dose computing is a function of the crop evapotranspiration lost during the day before, it was varying from 2.75 to 4 mm/ day because of ETo variations en Kc changes (0.5 during May and 0.6 from June). Thus, our different treatments were: ´ Control with trees irrigated based on 100% dose at open field (F100%) ´ Treatment which received 200% dose at open field (F200%) ´ Treatment undergoing 50% dose at open field (F50%) ´ Control with trees irrigated based on 100% dose under shading net (S100%) ´ Treatment which received 200% dose shading net (S200%) ´ Treatment undergoing 50% dose shading net (S50%) Variety characteristics The mandarin variety called ‘Nadorcott is well known under the names “Afourer” in Morocco and Europ and under the name “W. Murcott’ and ‘Delite’ in the United States. It is a Moroccan selection identified during 1981-82, among 18 years old Murcott mandarins grafted on Troyer citrange. These trees were planted at the Experimental Station of INRA in Afourer - Beni Mellal (Morocco). Afourer is a very attractive, easy to peel midlate season mandarin (peak maturity January - February) which, when grown in isolated conditions, can be virtually seedless. Production is excellent with very little alternate bearing when grown under commercial conditions 46. The variety, known worldwide for its high quality, has been

15

widely planted over the past decade as consumer demand for internal and external highquality of fruit (flavor, aroma, appearance and profile templates), lowseeded, easy to peel mandarins has increased, its high productivity (30-60 t / ha), and early entry into production (15 to 20 t / ha the third year after planting) and ease of peeling 47 . Rootstock characteristics Citrus macrophylla rootstock is sensitive to cold and wet soils. However, it supports high levels of chlorides and adapts to limestone soils. It’s tolerant to phytophthora, gummosis and responds well to other root attacks Diaprepes abbreviature especially due to its ability to rapidly regenerate damaged roots. It tolerates exocortis, but is sensitive to tristiza and the cachexiaxyloporose. Citrus macrophylla gives a good fruit set and a strong affinity with the lemon and lime trees. It tends to reduce the soluble sugar content of oranges, mandarins and their hybrids 48. Measurements and observations Characterization of soil water retention using Richards’s apparatus: soil sampling was done in the first 70 cm profile and samples were taken at intervals of 20 cm of depth. Metal cylinders of 4.2 cm in diameter and 4 cm in depth were used for in situ samplings. Characterization of the root profile in the soil: it allows architectural visualization of the roots in the soil, in relation to the relative distance to the drippers and to the tree trunk. A square-shaped screen (1 m in each side) composed of elementary openings of 10 cm × 10 cm is placed against the vertical wall of the profile; roots located in each opening were counted after their classification according to their diameter ( Ø < 3 mm ; Ø ≥ 3 mm). Soil water content: Soil samples were used for this purpose; sampling was performed at 15 day intervals. A single sample is the mixture of 6 samplings done at the same depth for each one of the six treatments. These profiles allow comparison between treatments by comparing vertical and horizontal distribution of water. Samples of soil were taken using rings in order to determine the bulk density and soil characteristics at the Laboratory of Soil Science at Agronomic and veterinary Institute Hassan II; the water content was calculated by

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ABOUATALLAH et al., Curr. World Environ., Vol. 7(1), 13-22 (2012)

Fig. 1: Water retention curves (pF curves) at different depths of the soil (30, 50 and 70 cm) for the experimental orchard

Fig . 2: Spatial distribution of the soil water content on the open field treatments F200%, F100% and F50%

Fig. 3: Soil moisture distribution on treatments under shade S200%, S100% and S50% Root profiles

ABOUATALLAH et al., Curr. World Environ., Vol. 7(1), 13-22 (2012)

17

Fig. 4: Roots spatial distribution in the soil profile (Ø <3mm) made at 20 cm from tree trunk and just underneath the irrigation pipeline for open field treatments F200%, F100% and F50%; the placement of the 2 drippers coincides with horizontal distances (small triangles ±30cm).

Fig. 5: Roots spatial distribution in the soil profile (Ø <3mm) made at 20 cm from tree trunk and just underneath the irrigation pipeline for treatments under shade S200%, S100% and S50%; the placement of the 2 drippers coincides with horizontal distances (±30cm). measuring the fresh weight and dry weight (after drying at 105 ° C for 24 hours). Fruit growth: we randomly selected four trees per treatment; each one was marked with eight fruits for which the equatorial diameter was measured weekly. Fruit dropping intensity: the number of dropped fruits has been counted three times a week during the month of May to compare its intensity for the three treatments applied (200% x 50%) in the two plots under nets and on open field. Repetitions and trees concerned were the same as those from fruit growth measurements.

RESULTS AND DISCUSSION Water retention curve or pF curve Values in Fig. 1 are relative to different soil depths. The observed difference concerns water retention capacity between the three soil depths because of variations in soil micro porosity and soil texture, which varies between the three horizons. The average curve of 50cm binding soil water pressure potential with soil volumetric water content has a polynomial form: y = -0.746x2 – 1.146x + 34.21 Soil moisture is calculated from trends using equations at field capacity (HFC=pF2) and at permanent wilting point (HPWP=pF4.2) 49-50,41 (Table 1). Available soil moisture is determined as

18

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the interval between the water content at field capacity and permanent wilting point 51. Treatments at open field We note a good water distribution into the soil for the open field treatments F200% and F100% (Fig. 2); soil moisture never approaches the HPWP, but water have been lost until 70cm and 90cm of soil depth for treatments F100% and F200% respectively due to the high amount of water applied in both two cases. A better lateral distribution took place on treatment F50%, however soil moisture was below HPWP at the horizons of 40-60cm depth (Figure 2), indeed, deficit irrigation significantly reduces the wetted soil volume 52; this can strongly prevent the development of roots at these levels; we observed 95% of root hairs at only 30 cm of soil depth; the F50% dose seems to be insufficient for citrus crops grown on open field.

Fig. 6: Fruit size growth for all treatments under shade and on open field. Fruit dropping intensity

Treatments under shade We note, again, a good water distribution into the soil for the treatments under shade S200% and S100% (Fig. 3); but with high soil moisture at deep horizons below 70 cm. similar soil flooding causes less root hydraulic conductance in citrus, so a reduction in transpiration by 56% 53 . The soil water content is well distributed laterally on treatment S50% (Fig. 3), the bulbâ&#x20AC;&#x2122;s depth is about 50 cm where the majority of roots are located; it seems that the shade screens helped to reduce evapotranpiration and to keep water into the soil. This result is in concordance with some other authors who founded sap flow in shaded trees is lower than in exposed trees almost every day 18,19. Root profiles. In this report, we are only presenting results for the root hairs with diameter < 3 mm.

Fig. 7: Fruits cut number per tree for all treatments under shade and on open field

ABOUATALLAH et al., Curr. World Environ., Vol. 7(1), 13-22 (2012)

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by Hâ&#x20AC;?73% because of the continuous deficit irrigated 55; this root reaction is to be explained by the restricted water supply which brings superficial soil moisture; however, a good horizontal distribution of these roots is observed, which proves that soil humid bulbs overlap under the emitters which is also in relation with the loamy nature of the soil.

Treatments at open field The greatest number of roots was counted on the open field treatment F200% (3293/m 2), almost 90% of the feeder roots are concentrated at less than 60 cm depth; nevertheless, we could found some active roots until 100cm due to the very deep soil water bulb (Fig. 4). Roots were better distributed for the open field treatment F100% (2333/m2), the last roots are found at 80 cm depth. These results confirm what other authors say that the root system architecture is largely affected by irrigation 54. Trees from treatment F50% developed very few root hairs (1625/m2) at superficial horizons only (95% at 30cm depth); it means 50% compared to the F200%; other author have found that root length density is reduced

Treatments under shade The trees from the treatment S200% developed deep roots until 90cm with a total number of 3267/m2; nevertheless, almost 90% of the feeder roots are concentrated at less than 70 cm depth. With a total of 2652/m2, roots were better

Table 1: Soil water retention, for the three studied horizons Depths (cm)

HFC (%)

HPWP (%)

RU (mm/cm)

Da

30

20,06

11,3

13,86

1,58

50

18,67

10,5

12,7

1,55

70 Average

17,05 18,59

8,5 10,10

12,52 13,03

1,47 1,53

Soil water content

Table. 2: Root counts in the soil profile (Ă&#x2DC; <3mm) made at 20 cm from tree trunk and just underneath the irrigation pipeline for the open field treatment F50% Depth (cm)

Horizontal distribution

Counts%

0-10 10-20 20-30(*) 30-40 40-50 50-60 60-70 70-80 80-90(*)90-100 0-10 10-20 20-30 30-40 40-50 50-60 60-70 70-80 80-90 90100 Total

30 42 35 12 0 0 0 0 0 0

48 58 29 8 0 0 0 0 0 0

113 74 28 11 0 0 0 0 0 0

58 43 14 4 0 0 0 0 0 0

62 39 22 0 0 0 0 0 0 0

85 68 16 3 0 0 0 0 0 0

73 67 19 10 0 0 0 0 0 0

65 68 22 13 0 0 0 0 0 0

75 75 38 16 0 0 0 0 0 0

57 87 38 0 0 0 0 0 0 0

666 621 261 77 0 0 0 0 0 0

41 38 16 5 0 0 0 0 0 0

119 %

143 7

226 9

119 14

123 7

172 8

169 11

168 10

204 10

182 13

1625 11

100 100

(*): Approximate placement of the 2 emitters.

20

ABOUATALLAH et al., Curr. World Environ., Vol. 7(1), 13-22 (2012) Table. 3: Root counts in the soil profile (Ø <3mm) made at 20 cm from tree trunk and just underneath the irrigation pipeline for the treatment S50% under shade

Depth (cm)

Horizontal distribution

Counts%

0-10 10-20 20-30(*) 30-40 40-50 50-60 60-70 70-80 80-90(*)90-100 0-10 87 10-20 83 20-30 53 30-40 24 40-50 8 50-60 22 60-70 12 70-80 3 80-90 0 90-100 0 Total 292 % 12

62 65 37 22 14 13 15 5 0 0 233 9

83 79 42 14 23 15 18 6 0 0 280 11

89 43 27 16 13 5 8 2 0 0 203 8

67 73 38 12 27 19 11 0 0 0 247 10

58 72 64 23 32 25 7 0 0 0 281 11

87 63 49 29 22 10 9 5 0 0 274 11

92 77 30 33 22 5 3 3 0 0 265 11

67 111 40 27 14 8 0 4 0 0 271 11

64 63 18 5 8 6 6 0 0 0 170 7

756 729 398 205 183 128 89 28 0 0 2516 100

30 29 16 8 7 5 4 1 0 0 100 -

(*): Approximate placement of the 2 emitters.

distributed for the treatment S100% horizontally as well as vertically, the last roots are found at 85 cm depth (Fig. 5). Trees from treatment S50%, growing under shelter, developed good number of root hairs (2516/m2); almost 90% of them are at 50cm depth and very well distributed horizontally (Fig. 5). The comparison between open field trees and those under shade brings to say ´ Roots number and distribution are almost the same for treatments 200% with deeper water bulbs. ´ Roots are very well distributed for treatments receiving 100% of their water requirements; ´ For treatments under 50% of water stress, the difference on root profiles is notable. The roots number is greeter under shade (2516/ m2 against 1625/m2) and well distributed; this might be explained by a better distribution of the soil moisture in the different horizons thanks to the less crop water requirement under shade (Table 2 and 3). Fruit size The Fig. 6 and statistical analysis indicates no significant difference between the three doses. In addition, the use of the shade screens coupled with treatment 200% and 100% does not affect the

growth of fruit trees. But, when using the dose of 50%, the fruit growth is enhanced under shade compared to the open field; some authors reported that the best integrated daily water-use efficiency corresponded to the shaded citrus treatments 56 . Fruit dropping intensity Fig. 7 shows that fruit drop is higher for the dose of F200% with a total of 341 fruit dropped while, for treatment F50%; this value is only 176 (≈50% less); however, other author found that a partial drying do not induce excessive fruit drop and crop yield is kept unaffected 57; Also, for all treatments it was evident that fruit dropping phenomena depends a lot on the use or not of the shade screens that seems to reduce considerably the rate of fruit drop especially for the treatments 100% and 50%. CONCLUSION Better water use efficiency is no longer an aim of citrus growers but necessity for sustainability of agriculture in the Souss-Massa region. The use of the shading net helped to decrease fruit dropping, but had no effect on the fruit size growth. Roots distribution and soil moisture measurements showed that the 100% and 200% doses provided

ABOUATALLAH et al., Curr. World Environ., Vol. 7(1), 13-22 (2012) the plant with excess water percolating into deeper horizons, which was behind the establishment of roots beyond 60 cm; in contrast, those ones confined in the upper layers of 50 cm depth when trees are under shade and irrigated using 50%

21

dose. We may conclude that adopting 50% of tree’s water requirements using net are a good way to maximize irrigation water efficiency without affecting the tree growth and their physiological state.

REFERENCES 1.

2. 3. 4.

5.

6. 7. 8.

9.

10. 11.

12. 13. 14.

Agence du Bassin Hydraulique du Souss Massa (ABHSM), Etude de révision du plan directeur d’aménagement intégré des ressources en eau des bassins du souss massa, Document interne, (2006). Le Houerou H. N., Ecologia Mediterranea., 15: 95 (1989). Driouech F., Déqué M., Sánchez-Gómez E., Global. Planet. Change., 72: 1 (2010). Ministère de l’Aménagement du Territoire, de l’Urbanisme, de l’Habitat et de l’Environnement du Maroc (MATUHE), First National Communication, United Nations Framework Convention on Climate change, 99 (2001). Office régional de mise en valeur agricole du Souss Massa (ORMVASM), Etude de gestion intégrée des ressources en eau dans le Souss Massa., Document interne, (2007). Edwards C. A., Agric. Ecosyst. Environ., 27 : 25 (1989). Tejero I. G., Zuazo V. H. D., Bocanegra J. A. J., Fernández J. L. M., Sci. Hort., 128: 274 (2011). Nicolás E., Barradas V. L., Ortuño M. F., Navarro A., Torrecillas A., Alarcón J., Environ. Exp. Bot., 63: 200 (2008). Castellano S., Scarascia G. M., Russo G., Briassoulis D., Mistriotis A., Hemming S., Waaijenberg D., Appl. Eng. Agric., 24: 799 (2008). Medany A. M., Hassanein M. K., Farag A. A., Acta Hortic., 807: 121 (2009). Hemming S., Swinkels G. L. A. M., Castellano S., Russo G., Scarascia G. M., Agricultural and Biosystems Engineering for a Sustainable World., 42: 23 (2008). Briassoulis D., Mistriotis A., Eleftherakis D., Polym. Test., 20: 970 (2007). Tanny J., Cohen S., Biosystems Eng., 84: 57 (2003). Nicolás E ., Torrecillas A., Dell’Amico J.,

15. 16. 17. 18.

19.

20.

21. 22. 23.

24.

25.

26. 27.

28. 29. 30.

Alarcón J. J., J. Plant Physiol., 162: 439 (2005). Cohen S., Raveh E., Li Y., Grava A., Goldschmidt E. E., Sci. Hort., 107: 25 (2005). Stanhill G., Cohen S., Agric. Forest Meteorol., 107: 255 (2001). Muthuchelian K., Paliwal K.,Gnanam A., Plant. Sci., 99: 539 (1989). Alarcón J. J., Ortuño M. .F, Nicolás E., Navarro A., Torrecillas A., Agric. Water Manage., 82: 387 (2006). Nicolás E., Torrecillas A., Dell’Amico J., Alarcón J. J., J. Plant Physiol., 162: 439 (2005). Medina L. C., Souza P. R., Machado C. E., Ribeiro V. R., Silva A. B. J., Sci. Hort., 96: 115 (2002). Talamini do Amarante C. V., Steffens C. A., Argenta L. C., Sci. Hort., 129: 79 (2011). Lei Y. B., Yin C. Y., Li C. Y. Physiol Plant., 127: 182 (2006). Rodríguez-Gamir J., Ancillo G., Aparicio ., Bordas M., Primo-Millo E. , Plant Soil., 347: 91 (2011). Arbona V., Iglesias D. J., Jacas J., Primo-Millo E., Talon M., Gomez-Cadenas A., Plant Soil., 270: 73 (2005). Garcia-Sanchez F., Syvertsen J. P., Gimeno V., Botia P., Perez-Perez J. G., Physiol. Plantarum., 130: 532 (2007). Perez-Perez J. G., Syvertsen J. P., Botia P., Garcia-Sanchez F., Ann. Bot., 100: 335 (2007). Gomez-Cadenas A., Tadeo F. R., Talon M., Primo-Millo E., Plant Physiol., 112: 401 (1996). Velez J. E., Intrigliolo D. S., Castel J. R., Agric. Water Manage., 90: 197 (2007). Ballester C., Castel J., Intrigliolo D. S., Castel J. R., Agric. Water Manage., 98: 1027 (2011). García-Tejero I., Jiménez-Bocanegra J. A., Martínez G., Romero R., Durán-Zuazo V. H., Muriel-Fernández J. L., Agric. Water

22

31.

32. 33. 34. 35.

36.

37. 38. 39. 40.

41.

42.

43.

ABOUATALLAH et al., Curr. World Environ., Vol. 7(1), 13-22 (2012) Manage., 97: 614 (2010). García-Tejero I., Durán-Zuazo V. H., ArriagaSevilla J. and Muriel-Fernández J. L., Agron. Sustainable Dev., 31: 779 (2011). Xu-Ming H., Hui-Bai H., Fei-Fei G., Sci. Hort., 83: 227 (2000). Agusti M., Garcia-Mari F., Guardiola J. L., Sci. Hortic., 17: 257 (1982). Goldschmidt E. E., Monselise S. P., Proc. Int. Soc. Citriculture., 2: 668 (1977). García-Tejero I., Romero-Vicente R., Jiménez-Bocanegra J. A., Martínez-García G., Durán-Zuazo V. H., Muriel-Fernández J. L., Agric. Water Manage., 97: 689 (2010). Romero P., Navarro J. M., Perez-Perez J., Garcia-Sanchez F., Gomez-Gomez A., Porras I., Martinez V., Botia P., Tree Physio., 26: 1537 (2006). Gonzalez-Altozano P., Castel J. R., J. Hortic. Sci. Biotechnol., 74: 706 (1999). Gonzalez-Altozano P., Castel J. R., J. Hortic. Sci. Biotechnol., 75: 388 (2000). Ginestar C., Castel J. R., J. Hortic. Sci., 71: 551 (1996). Treeby M. T., Henriod R. E., Bevington K. B., Milne D. J., Storey R., Agric. Water Manage., 91: 24 (2007). Treeby M. T., Henriod R. E., Bevington K. B., Milne D. J., Storey , Agric. Water Manage., 91: (2007). García-Tejero I., Durán-Zuazo V. H., JiménezBocanegra J. A., Muriel-Fernández J. L., Sci. Hortic., 128: 274 (2011). Abu-Awwad A. M., Agric. Water Manage., 52: 53 (2001).

44. 45.

46. 47. 48. 49. 50. 51. 52. 53.

54.

55.

56.

57.

Fares A., Safeeq M., Jenkins D. M., Pedosphere., 19: 588 (2009). Allen R. G., Periera L. S., Raes D., Smith M., Crop evapotranspiration: guideline for computing crop water requirement. FAO, Rome, Italy, 301 (1998). Milind S., Ladaniya A., Academic Press., 1: 13 (2008). Nadori E. B., Revue HTE., 132: 15 (2005). Hanson R. B., Orloff S., Peters D., Calif Agric., 54: 47 (2000). Jabro J. D., Evans R. G., Kim Y., Iversen W. M., Irrig Sci., 27, 223 (2010). Ratliff L. F., Ritchie J. T., Cassel D. K., Soil Sci Soc Am J., 47 : 770 (1983). Castel J. R., Buj A., Irrig. Sci., 11: 121 (1990). Hutton R. J., Loveys B. R., Agric. Water Manage., 98: 1485 (2011). Rodríguez-Gamir J., Ancillo G., GonzálezMas M. C., Primo-Millo E., Iglesias D. J., Forner-Giner M. A., Plant Physiol. Biochem., 49: 636 (2011). Sokalska D. I., Haman D. Z., Szewczuk A., Sobota J., Dereñ D., Agric. Water Manage., 96: 917 (2009). Abrisqueta J. M., Mounzer O., Álvarez S., Conejero W., García-Orellana Y., Tapia L. M., Vera J., Abrisqueta I., Ruiz-Sánchez M. C., Agric. Water Manage., 95: 959 (2008). Alarcón J. J., Ortuño M. F., Nicolás E., Navarro A., Torrecillas A., Agric. Water Manage., 82: 387 (2006). Hutton R. J., Loveys .B R., Agric. Water Manage., 98: 1485 (2011).

Current World Environment

Vol. 7(1), 23-32 (2012)

Reverse Osmosis Pretreatment: Removal of Iron in Groundwater Desalination Plant in Shupramant-Giza - A Case Study AL-SAYED M. ALY¹, MAHMOUD M. KAMEL², A. HAMDY¹*, KHALED Z. MOHAMMED¹ and MOHAMED A. ABBAS¹ ¹Egyptian Petroleum Research Institute (EPRI), Nasr City, Cairo (Egypt). ²Chemistry Department, Al-Azhar University (Assuit Branch) (Egypt). (Received: March 18, 2012; Accepted: May 20, 2012)

ABSTRACT Reverse osmosis (RO) is being increasingly utilized throughout the world for desalination due to the latest improvements in RO membrane performance and its reduced cost compared to thermal desalination. In this paper, Different media and chemicals have been used for Iron removal to prevent membrane fouling of groundwater reverse osmosis plant located in Shupramant-Giza. The objective is to present field results of the reverse osmosis plant operation in order to evaluate the reliability of this technology. The operating pressure and pressure drop increased significantly without an increase in the production capacity. Frequent shutdowns of the plant were observed due to severe membrane fouling. The membrane was cleaned with different chemical solutions to dissolve the deposits from the membrane surface. To achieve high cleaning efficiency, the flow rate of desalinated water and total dissolved salts (TDS) were studied.

Key Words: Reverse osmosis (RO); desalination; groundwater; fouling.

INTRODUCTION Due to recent developments in membrane technology, the trend in the desalination industry is to use reverse osmosis (RO) for desalting seawater. Brackish water (BW) desalination using membrane technology is also expanding as the salinity of groundwater increases. Selecting an appropriate process to meet specific needs at specific locations is essential though the biggest challenge remains in the capability to successfully operate these plants once installed due to peculiarities of sea and brackish waters in the region1. Membrane filtration in general and reverse osmosis (RO) in particular is applied in a wide range of fields, such as chemical, medical, textile, petrochemical, electrochemical, water treatment, biotechnology and environmental industries2. Fouling and scaling are the most serious problems in membrane processes. In sea/brackish water applications, pretreatment of RO feed water

is the key step in designing the plants to avoid membrane fouling and scaling1. At the present time, pretreatment technology is divided into conventional pre-treatment and non-conventional pre-treatment. Conventional RO pre-treatment has been widely applied for sea and ground water RO plants to achieve the expected quality of feed water to the RO membrane. But with the deterioration of feed waters and the consideration of the less efficient conventional system, an increasing number of plant owners were considering the use of membrane based pretreatments3. Iron is found in surface and ground waters at varying concentration levels, usually up to 3–4 mg/l and in some cases up to 15 mg/l4. Sharma ; et al., found that when present, even at low concentrations it can be linked to aesthetic and operational problems such as bad taste and color, staining, as well as deposition in the water distribution system leading to incidence of high turbidity5. Also, iron promotes the growth of certain

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ALY et al., Curr. World Environ., Vol. 7(1), 23-32 (2012)

types of chlorine-tolerant microorganisms in water distribution systems, thus causing increased costs for cleaning and sterilizing systems in addition to odor and taste problems. The highest permitted limit of iron concentration for drinking water is 0.2 mg/l6. Chemical cleaning of membrane means removing impurities by means of chemical agents. The first step of chemical washing is finding appropriate materials as cleaning agents. This depends on feed composition and precipitated layers on the membrane surface and in most cases is performed using a trial and error method7. The cleaning agents must be able to dissolve most of the precipitated materials and remove them from the surface of membrane with no surface damage8. The FilmTec Cor poration was established in 1977 with the introduction of the FILMTEC FT30 reverse osmosis membranes which was the first commercially viable thin-film composite polyamide membrane for brackish water treatment. The FilmTec Corporation was purchased by the Dow chemical company in 1985, a move that merged Dow’s sales and marketing strength and expertise in polymer and membrane research with FilmTec’s membrane research, manufacturing and technical service resources9. This paper includes evaluation to compare performance results during operation and operating cost of conventional media filtration, which is one of the most important decision-making bases for choosing feasible pretreatment methods. Raw Water Characteristics The raw water coming from two wells contains ca. 2 g/l total dissolved solids, predominantly chloride and sodium ions. The increase in the salinity represents only dissolved salts. Iron and manganese often occur together in groundwater but manganese usually occurs in much lower concentration than iron. Both iron and manganese are readily apparent in drinking water supplies. The highest permitted limit of iron concentration for drinking water is 0.2 mg/l6. The feed water temperature is almost ranged in all seasons between 20 and 42°C. Raw water analysis by an Atomic Absorption Spectrometer (Perkine Elmer Flame AAS 3110) is presented in Table1.

RO Plant Characteristics The feed water is supplied with two feed pumps with a specification: stainless steel 304, 20 m3/h – 5 bar max, kw 5.5, IP 55, class F. Feed water pumps are followed by dual media filter vessel. This vessel constructed of a fiberglass reinforced polyester resin for standard water conditioning use with specific size (diameter 13 inches (330 mm) and height 54 inches (1372 mm)), maximum operating pressure 150psi (10.34 bars), maximum operating temperature 120o F (48o C), bed capacity in liters is 105 and the top opening of this vessel is 2½ inches. Dual media filter vessel has two layers of filtration media – typical design includes anthracite10, with effective size: 0.6-0.8 mm, sand11, 0.45-0.55 mm, and/or gravel, 2.0-3.0 mm, Table 2. The vessel which used as media filter is controlled by automatic head conditioning controller that is a simple mechanical design, two valve body designs, one for downflow regeneration and one for upflow. Head controller has a choice of 7 or 12day time clock or demand regeneration with either mechanical or electronic meter. The continues flow rate up to 20 gpm with regeneration time available up to 120 minutes and mounting base 2½ inches. The high pressure pump with a specification: stainless steel 304, 20 m3/h – 17 bar max, k w15, IP 55, HP 20 and class F, supplies the pretreated water to the three membrane pressure vessels (housings) of the RO plant. Each housing contains one spiral wound polyamide membranes (Filmtec BW30-4040), Table 3. The membrane nominal active surface area is 7.6 m2; its permeate flow rate is 9.1 m3/d and the minimum salt rejection is 99.5%. Two flow meters are present to measure the in-and-out water of RO plant. Finally, the RO plant was controlled by electrical control panel. Pretreatment Methods Granular Media Filtration Direct filtration, using mono, dual-media or mixed-media filtration, is the most common technology used for the filtration of seawater prior to the RO system. Filtration depends primarily on a combination of complex physical and chemical mechanisms, the most important being adsorption. As water passes through the filter bed, the

ALY et al., Curr. World Environ., Vol. 7(1), 23-32 (2012) suspended particles contact and adsorb (stick) onto the surface of the individual media grains or onto previously deposited material 13 . To reach the expected quality of filtrate, the size, surface charge, and geometry of both suspended solids and filter media are the most important parameters that need to be well designed. Water Desalination Technical Manual (WDTM), Department of the U.S. Army 14, gave the following design parameters for single, dual and mixed-media filtration: 1. Single-media filtration. Single-media filtration consists of one media. This media is often small-grained silica sand; however, anthracite may be used after lime and lime-soda softening. Some desalination pretreatment systems use an alternate media such as greensand to remove iron and manganese compounds. Diatomaceous earth media is not recommended for primary filtration because of its characteristic high head loss and short run times. 2. Dual media filtration. Dual media filtration consists of two media with different specific gravities. The difference creates a two-layer separation effect: The use of silica sand or greensand for one layer; or the use of anthracite for the other layer. The use of dual media will allow larger quantities of material to be filtered and will reduce head loss during operation. The use of two media types will provide a good coarseto-fine filtration process for desalination facilities. 3. Mixed-media filtration. When three media are used in filters, a better coarse-to-fine filtration pattern can be obtained. High density silica sand, garnet, and anthracite are commonly used to provide the filter bed. The different media do not stratify completely. Instead, there is a small amount of intermixing among the different layers. This gradual change in media size provides a gradient from coarse to fine and creates a media flow pattern necessary to achieve a very low silt density index. In this case, Dual media filter have two layers of filtration media – typical design includes anthracite, sand and/or gravel, Table3. The depth of the filter bed is typically a function of the media size and follows the general rule-of-thumb that the ratio between the depth of the filter bed (l - in millimeters) and the effective size of the filter media (de - in millimeters), l/de, should be higher than 1500. For example, if the effective size of the anthracite

25

media is selected to be 0.6 to 0.8 mm, the depth of the anthracite bed should be at least (0.6 mm × 1500= 900 mm to 0.8 mm × 1500= 1200 mm, i.e., 0.9-1.2 m)15. In comparison to single sand filter media, dual filter media with anthracite over sand permit more penetration of the suspended matter into the filter bed, thus resulting in more efficient filtration and longer runs between cleaning. Periodically, when the differential pressure increase between the inlet and outlet of the pressure filter is 0.3–0.6 bar, and about 1.4 m for the gravity filter, the filter is backwashed and rinsed to carry away the deposited matter. Backwash time is normally about 10-120 min. Before a backwashed filter is placed back into service, it must be rinsed to drain until the filtrate meets the specification16. Last, to protect the RO membrane from the breakthrough particles from media filtration, cartridge filters are usually recommended in the last step of a pre-treatment sequence. The pore size from 1 to 20 µm can be used based on different produced water quality from media filtration14. In this case, we used cartridge filter with pore size 5 µm and length 20 inches. After filtration through these filters, the turbidity reduced from 3.87 NTU to 0.24 NTU. Scale Inhibition Scale inhibitors (antiscalants) can be used to prevent or control scaling. There are generally three different types of scale inhibitors: sodium hexametaphosphate (SHMP), organophosphonates and polyacrylates. According to FILMTEC Reverse Osmosis Membranes Technical Manual 17, SHMP is inexpensive but unstable compared to polymeric organic scale inhibitors. Hydrolysis of SHMP will not only decrease the scale inhibition efficiency, but also create a calcium phosphate scaling risk. Therefore, SHMP is generally not recommended. Organo-phosphonates are more effective and stable than SHMP. They act as anti- foulants for insoluble iron, keeping them in solution. Polyacrylates (high molecular weight) are generally known for reducing silica scale formation via a dispersion mechanism. Dosage rates on all antiscalants should be based on the antiscalant manufacturers. Overdosing should be avoided to

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make certain that no significant amounts of cationic polymers are present when adding an anionic scale inhibitor18. In this case study, injection of antiscalant has done by chemical dosing pump (5 liters/7bars). Feed water pH was reduced from 6.78 to 6.52 by the effect of Permatreat 510 antiscalant which is a mixture of polymers and phosphonates. This antiscalant is specifically developed for groundwater with a high content of silica, and it is also effective with respect to precipitation of calcium salts (carbonate, sulfate and fluoride) and the fouling of iron (iron reduced from 3.8 mg/l to 3.12 mg/l). pH Adjustment Acidity (pH) adjustment is an efficient way to control scaling. By adding H + as acid, the equilibrium can be shifted to keep salts dissolved. Adjustment chemicals to the pH include carbon dioxide, sulfuric acid, and hydrochloric acid. Carbon dioxide should not be used for pH adjustment of lime addition systems due to scaling problem associated with lime pretreatment. Sulfuric acid is easier to handle and in many countries more readily available than hydrochloric acid; however, additional sulfate is added to the feed stream, potentially causing sulfate scaling13. In this case, it should be known that the pH is always changed significantly and the pH must be returned to a neutral state for the final produced water. At the beginning of the study, sulfuric acid is used. However, membrane fouling was observed. In order to stopping this fouling, the acid was then switched to hydrochloric for the remainder of the study. After the switch from sulfuric to hydrochloric acid, the plant worked very well, and the fouling is not observed according to standard permeate flow rate (27.3 m3/d) and TDS (50 mg/l). Iron Removal Strategies Iron, usually presents in groundwater as divalent ion (Fe2+) and is considered as source of membrane scaling. The main target in our case study is the removal of iron in groundwater before passing through reverse osmosis membranes as pretreatment technique to avoid membrane fouling. Take in account that the antiscalant feeding before membranes is effective with respect to precipitation. It reduces iron concentration from 3.8 mg/l to 3.12

mg/l, but this iron level is still the main source of membrane problems. In this case, various treatment methods have been employed to enhance water quality by removing iron. Oxidation Processes Alternative processes have been proposed in order to facilitate the operation and to allow the removal of high amounts of iron in the presence, or absence, of dissolved organic matter. In both cases, a pH adjustment is necessary to maintain iron in the dissolved state to avoid membrane fouling.Ferrous iron is oxidized in air according to the following reaction: Fe2+ + (1/4) O2 + H+ â&#x20AC;?! Fe3+ + (1/2) H2O

...(1)

Potassium Permanganate and Depth Filtration Conventional treatment for iron removal from groundwater consists of oxidation and depth filtration. Oxygen or stronger oxidants, such as potassium permanganate (KMnO4), are generally used for Fe 2+ oxidation. The solid products of oxidation (FeOOH.H2O) are then filtered through a granular bed, commonly green sand 19 . The potassium permanganate dose applied must be carefully controlled to minimize any excess passing into supply which could give a pink color to the water. Potassium permanganate oxidation tends to form a colloidal precipitates which may not be well retained by the filters. Chlorine and Depth Filtration The removal of iron along with chlorination step and appropriate dose of chlorine will be discussed. In particular membrane fouling caused by oxidized particles, was assessed in depth with visualization of the membrane surfaces. As shown in Fig.1, the removal efficiency of dissolved iron increased very rapidly and reached nearly 100% within 20 minutes with the appropriate dose of chlorine, 2.75 mg/L. With a higher dosage of chlorine 2.75 mg/L, there was no significant increase in the removal of metal ions but more serious membrane fouling occurred. The use of chlorine may be inadvisable when treating waters containing organic substances due to the possibility of disinfection byproducts (DBPs) formation.

ALY et al., Curr. World Environ., Vol. 7(1), 23-32 (2012) Manganese Greensand An alternative filter media is manganese greensand 20 , formed by treating greensand (glauconite), which is a sodium zeolite, with manganous sulphate followed by potassium permanganate. Mn-greensand removes soluble iron by a process of ion exchange, frequently with the release of hydrogen ions. The process is therefore pH dependent, being virtually ineffective

Table 1. Groundwater Composition Ca++, mg/l Mg++, mg/l Na+ , mg/l K+, mg/l Mn++, mg/l Fe++, mg/l SiO2, mg/l HCO3, mg/l Cl–, mg/l SO42–, mg/l NO3–, mg/l F–, mg/l pH Turbidity, NTU Temperature, ºC Conductivity, µS/cm TDS, mg/l

107 72 406 8 0.62 3.8 8.33 199 737 297 7.66 0.04 6.78 3.87 20-42 2677 1938

27

below pH 6.0 and very rapid at pH values above 7.5. When the Mn-greensand is saturated it is regenerated by soaking the filter bed with weak potassium permanganate solution. This procedure oxidizes iron on the surface of Mn-greensand thereby reactivating the exchange sites. It is reported that the exchange capacity is 1.45 g of Fe /l of Mn-greensand and that 2.9 g of potassium permanganate (as a 1% w/v solution) per liter of Mn-greensand is required for regeneration 21 . Alternatively, potassium permanganate is continuously applied to the bed by dosing it at the filter inlet, which maintains Mn-greensand active and catalyses the oxidation reaction. Mn-greensand then acts as a filter medium in addition to catalytic oxidation of any residual soluble manganese and is usually capped with a layer of anthracite to achieve longer filter runs. Operating the bed after oxidation capacity is exhausted will reduce its service life and may cause stain. Oxidation and Microfiltration This treatment is similar to the conventional one except that depth filtration is replaced by microfiltration (MF). The expected advantage of this treatment is to have a compact separation unit which produces high quality water from a wide range of raw water quality. In the present study the MF of iron oxide suspensions is removed22,23.

Table 2. Pretreatment Media Specifications Color

Mesh size Effective size, mm Bulk Density, lbs./cu. Ft. Bed depth, inch Freeboard of bed depth,% Backwash flow rate, gpm/sq. ft. Backwash bed xpansion of bed depth, % Service flow rate, gpm/sq.ft.

Sand and gravel Light tan to reddish brown

Anthracite Black

Activated carbon Black

Manganese greensand Black

18x35 0.45-0.55 100 18-30 50 15-20

14x30 0.6-0.8 50 24-36 50 12-18

12x40 0.55-0.75 31 26-30 50 10-12

16x60 0.30-0.35 85 30 50 10-12

20

20-40

30-40

40

1.5-2

5

5

3-5

28

ALY et al., Curr. World Environ., Vol. 7(1), 23-32 (2012) Table 3. Filmtec BW30-4040 Specifications 12. Membrane type Max. operating temperature, oF (oC) Max. operating pressure, psi (bar) Max. feed flow rate, gpm (m3/h) Active area, ft2 (m2) Applied pressure, psig (bar) Permeate flow rate, gpd (m3/d) Stabilized salt rejection, % Pressure vessel diameter, inch Pressure vessel length, inch Free Chlorine Tolerance, ppm

Polyamide thin film composite 113 (45) 600 (41) 16 (3.6) 82 (7.6) 225 (15.5) 2400 (9.1) 99.5 4 40 <0.1

Table 4. Amberlite IR120Na Data Sheet 25. Matrix Functional groups Ionic form Total exchange capacity Harmonic mean size Minimum bed depth Service flow rate Regenerant Level (g/L) Concentration (%) Minimum contact time

Styrene divinylbenzene copolymer Sulphonates Na+ â&#x2030;Ľ 2.0 eq/L 600-800 Âľm 700 mm 5 to 40 BV/h NaCl 80-250 10 30 minutes

Fig. 1. Removal efficiency of iron through 60 min. at different chlorine dosages.

ALY et al., Curr. World Environ., Vol. 7(1), 23-32 (2012) Finally, under certain conditions, the presence of free chlorine and other oxidizing agents, in the oxidation processes, will cause premature membrane failure. Since oxidation damage is not covered under warranty, FilmTec recommends removing residual free chlorine and other oxidizing agents by another suitable pretreatment prior to membrane exposure24. Ion exchange resin Ion exchange resins are able to remove many inorganic metal ions from groundwater including iron. In this case, Amberlite IR120Na, strong acid cation exchanger was used, Table 4. Ion exchanger was carried out in a vessel constructed of a fiberglass reinforced vinylester resin for standard water de-ionizing use with specific size (diameter 13 inches and height 54 inches), maximum operating pressure 150psi (10.34 bars), maximum operating temperature 150o F (66oC), bed capacity in liters is 105 and the top opening of this vessel is 2½ inches. The total hardness concentration averaging 528 mg/L was passed through sodium charged strong acid cation exchange resin to reduce the hardness to less than 5 mg/L. Amberlite IR120Na, also treat with other metal ions like iron and so, the total exchange capacity is become smaller. The resin was then regenerated using commercially available extra coarse water-softening salt (NaCl). This process was repeated several times to demonstrate that no irreversible fouling had occurred to resin. Granular activated carbon Activated carbon 26 is prepared from a char form material such as almond, coconut, and walnut hulls, other woods, and coal. Activated carbon has the strongest physical adsorption forces or the highest volume of adsorbing porosity of any material known to mankind. It is a highly porous material; therefore, it has an extremely high surface area for contaminant adsorption27. The objective of this topic was to determine the effectiveness of granular activated carbon (GAC) in removing iron from the groundwater. From these advantages for granular activated carbon, in this case study, we used a single-media filter, Table3. The depth of the GAC media is estimated based on the average contact time in this media, which is recommended

29

to be 10 to 12 min. For example, if a filter is designed for a surface loading rate of 4 m3/m2 h, the depth of the GAC media should be at least 0.66 m (4 m3/m2 h Ă&#x2014;10 min/60 min per h=0.66 m to 4 m3/m2 h Ă&#x2014;12 min/60 min per h=0.8 m, i.e., 0.66 0.8 m)15. For the following reasons28, we used the granular activated carbon in the adsorption of ferrous. The van der Waals force that forms multilayer adsorption was overcome by the adsorbate due to the high ambient temperature 29. With relatively high room temperature of about 30oC where the adsorption process occurs, the chemisorption was more dominant as compared to the physisorption. The relatively high room temperature cause the chemical bond to occurs between the metal ions. Furthermore desorption will also occur between adsorbate and activated carbon at high temperature which physically bonded by the van der Waals force. Adsorbates which are physically adsorbed onto activated carbon receive sufficient energy from such high temperature to overcome the van der Waals force. Activated carbon has high adsorption capacity for Fe(II) as compared to others. This may relate to adsorbate characteristics in terms of electronegativity. The electronegativity of Fe(II) is 1.8 . In fact, electronegativity is a measure of strength for element to attract electron. In this case, it would measure the strength of Fe(II) attach to negative charge at activated carbon surface. According to previous literature 30, higher electronegativities corresponded to the higher adsorption levels of metal ions onto the GAC. Another factor that contributes to different GAC adsorption capacity on metal ion is ionic radius. Fe(II) has relatively smaller ionic radius than that of the others since Fe(II) has the higher attractive charge in nucleus on the electron orbital 29. The smaller ionic radius of Fe(II) makes it easier to penetrate into the micropores of the GAC. There were four major functional groups on the surface of activated carbon which are carboxyl, carbonyl, hydroxyl, and lactonized carboxyl31. All these four functional groups were promoted to attract cation to it and ion exchange would occur. Therefore, the Fe(II) which has positive

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charge would react and attach onto GAC surface’s functional groups with chemically bonded. However, the actual chemical reaction between the metal ion and functional groups on the activated carbon surface was complex and difficult to understand. In the case of iron, oxidation is followed by settling and filtration or filtration alone, depending on the concentration of iron in the water. In the presence of turbidity (and color) and when the Fe(II) concentration is greater than about 5 mg/ l, settling or flotation would be assisted by a coagulant and/or a coagulant aid. Direct filtration is used when the iron concentration is less than about 5 mg/l 32. Post-treatment strategies Post-treatment1 is limited to injection of lime to increase the pH from 6.52 to 8.0 and chlorine for disinfection. Lime Post-treatment Lime has been added to neutralize the final produced water. For excess lime injection, it is necessary to raise pH to approximately 8. The high pH level produces good disinfection as a by-product and thus chlorination might be unnecessary after such injection except for a small dose to provide residual chlorine in the distribution system. Carbonation is necessary to remove the excess lime and reduce the pH after treatment. Disinfection Groundwater may be contains microorganisms such as bacteria, algae, fungi, and viruses, which can cause serious biological fouling. There are various methods to prevent and control biological fouling such as the addition of chemical oxidants (chlorine, bromine, iodine, or ozone), ultraviolet irradiation, biofiltration to remove nutrients, and the addition of biocide. Because of the risk of oxidation of the membrane, the use of oxidants must be monitored carefully to keep the chlorine well below 0.1 mg/L of free chlorine residual. Sometime dechlorination upstream of the membranes is required through sulfite compound addition or passage through granular-activated carbon 18. World Health Organization (WHO) 33

considers: ‘it has been demonstrated that virus-free water can be obtained from faecally polluted source waters’ if the following chlorine disinfection conditions are met. The water has a turbidity of 1 Nephelometric turbidity unit ( NTU) or less, Its pH is below 8.0, A contact period of at least 30 minutes is given; and, The chlorine dose applied is sufficient to achieve at least 0.5 mg/l free residual chlorine during the whole contact period. Sodium hypochlorite (NaOCl) was used in our case study and the injection of hypochlorite has done by chemical dosing pump (5 liters/7bars) in dosage 1 mg/l. Typically iron should be less than 0.2 mg/l. If at the point of chlorine application, their levels are too low to justify disinfection, the dose must take their demand into account. Membrane cleaning The fouling of RO elements is unavoidable with long-term operation. They can be fouled by biological matter, colloidal particles, mineral scale, and insoluble organic constituents. Deposits build up on the membrane surfaces during operation until they are causing loss in normalized permeate flow (product flow rate) and/or loss of normalized salt rejection [total dissolved salts (TDS)]. Elements should be cleaned whenever the normalized permeate flow drops by ≥10%, or the normalized salt passage increases by ≥10%, or the normalized differential pressure (feed pressure minus concentrate pressure) increases by ≥15% from the reference condition established during the first 48 h of operation. Cleaning procedures are usually given by the membrane manufacturers17. In this case, the maximum operating pressure required is 15.5 bar and maximum pressure drop is 1 bar increased to 16.5 and 1.5bar, respectively, without an increase in the standard permeate (flow rate 27.3 m3/d and TDS 50 mg/l). Frequent shutdowns of the plant were observed due to membrane fouling (permeate flow rate is 18.7 m3/d and TDS is 580 mg/l). In this case, both acidic and alkaline cleaners can be used. Acid cleaning to remove mineral scale was done at pH 2 or lower with 0.2%

ALY et al., Curr. World Environ., Vol. 7(1), 23-32 (2012)

31

(W) hydrochloric. Citric acid can also be used in the same concentration. Alkaline cleaning to remove organic fouling was done at pH 12, generally done with 0.1% (W) sodium hydroxide 24,34. After resolving the fouling problem, membranes are cleaned with the first option given by the manufacturer every six months and the cartridge filters are replaced every three months1.

conventional and specific pre-treatment methods, we concluded that, every applied method has advantages and disadvantages in application. The most suitable pretreatment technique for iron removal (concentration less than 5 mg/l) is a granular activated carbon (GAC) filter which has higher adsorption capacity and leads to low operating cost.

CONCLUSIONS

ACKNOWLEDGMENTS

In our case study iron was removed in groundwater before passing through reverse osmosis membranes as pretreatment technique to avoid membrane fouling. Different pretreatment techniques are done to remove iron and save the membrane.

The authors express their appreciation to Prof. Dr. Naglaa Ali and Prof. Dr. Yasser Moustafa, Egyptian Petroleum Research Institute (EPRI), for their assistance and revision of this paper. Also, the authors wish to acknowledge the assistance and support of this study by Eng. Mohamed Amer, General Manager of Water Engineering Technology Co. (WETCO), which agent for each products of Jacobi Carbon, Clack and DOW.

Many processes affecting the iron removal from the groundwater are applied in this case study. From the performance comparison between

REFERENCES

1. 2.

3. 4. 5.

6.

7.

8. 9. 10.

Arras W., Ghaffour N., Hamou A., Desalination 235: 170, (2009). Bodalo-Santoyo A., Gomez-Carrasco J.L., Gomez-Gomez E. and Montesinos A.M., , Desalination ,160 : 151, (2004). Wolf P.H., Siverns S.and Monti S., Desalination, 182: 293, (2005). Ellis D., Bouchard C. and Lantagne G., Desalination . 130: 255, (2000). Sharma S.K., Kappelhof J., Groenendijk M.and Schippers J.C., J. Water Supply Res. Technol., 50: 187, (2001). EC-Official Journal of the European Communities Council Directive 98/83/EC L. 330: 32, (1998). Madaeni S.S., Mohammadi T. and Moghadam M.K., Desalination 134: 77, (2001). Lindau J.and Jonsson A.S., J. of Membrane Science 87: 71, (1994). Redondo J.A. and Lomax I., Desalination, 110 : 167, (1997). Clack Corporation, Anthracite data sheet

11.

12.

13. 14.

15. 16.

17.

form no. 2354, replaces form 1785, Part no. A8029, 3 (2011). Clack Corporation, Filter sand and gravel data sheet form no. 2352, replaces form 1824, Part no. A8071, 3 (2011). Filmtec Reverse Osmosis Membranes, BW30-4040, Technical bulletin 609-00350804 Chua K.T., Hawlader M.N.A. and Malek A., Desalination , 159: 225, (2003). Headquarters, Department of the Army, Washington, D.C., Water Desalination Technical Manual, (1986). Voutchkov N., Desalination , 261: 354, (2010). Voutchkov N.and Dietrich J., Pilot testing alternative pretreatment systems for seawater desalination in Carlsbad, California, Proceedings of World Congress in Desalination and Reuse, International Desalination Association, SP05-095, Singapore, 11-16, (2005). Filmtec Reverse Osmosis Membranes

32

18. 19. 20.

21.

22.

23.

24. 25. 26.

27.

ALY et al., Curr. World Environ., Vol. 7(1), 23-32 (2012) Technical Manual,( 2004). Prihasto N., Liu Qi. and Hyun Kim S., Desalination, 249: 308, (2009). Lessard C., Ellis D., J. S &odes and C. Bouchard, Environment, 32, (1999). Clack Corporation, manganese greensand data sheet form no. 2349, replaces form 1564, Part no. A8041, 3, (2011). Benefield, L. D. and Judkins, J. F. ,Process Chemistry for Water and Wastewater Treatment. Prentice-Hall (1982). Mourato D. and Smith C., Proc., 6th Workshop on Drinking Water, AQTE, Montr6al, 705-716, ( 1994). Cote P., Mourato D. , C.Gungerich, Russell J. and Houghton E., ISWA Conference, Membranes in Drinking and Industrial Water Production, Amsterdam ( 1998). Filmtec Reverse Osmosis Membranes Technical bulletin 609-22010/CH172-086-E. Rohm and Haas Amberlite IR120Na, PDS 0210 A.1997. Clack Corporation, Activated carbon data sheet form no. 2348, replaces form 1795 & 1564, Part no. A8009-12, 3, (2011). Cheremisinoff N.P., Handbook of Water and Wastewater Treatment Technologies, Butterworth-Heinemann, Boston, USA, 138:

28.

29.

30. 31.

32.

33. 34.

140, ( 2002). Ahmad bin Jusoh, Cheng W.H., Low W.M. , Ali Noraâ&#x20AC;&#x2122;aini and Megat Mohd Noor M.J., Desalination, 182: 347, (2005) . Tam Y.K., Studying on Removal of Dye Using Granular Activated Carbon, Science Engineering Department, Kolej University of Science and Teknology Malaysia ( 2003). Rockstraw D.A. and Dastgheib S.A., Carbon, 40: 1843 (2002). Keneth E.N. and Chang H.T., Effect of Surface Functional Groups on the Coefficient of Freundlich Isotherm, Depar tment of Chemical and Environmental Engineering, Illinois Institute of Technology, 1999, http:// www.chee.lit.edu/ chang/index.html, Accessed 18 April ( 2004). Ratnayaka Don D., Malcolm J. Brandt and Michael Johnson K., Water Supply (Sixth Edition), CHAPTER 10: Specialized and Advanced Water Treatment Processes, 365: 423, (2009). WHO ,Guidelines for Drinking-Water Quality, Vol. 1, Recommendations. 2nd Edn (1993). Filmtec Reverse Osmosis Membranes Technical bulletin 609-24010/CH172-120E.

Current World Environment

Vol. 7(1), 33-36 (2012)

Multimedia: A Technique in Teaching Process in the Classrooms ASHVINI JOSHI Sri Satya Sai College of Engineering, Bhopal (India). (Received: March 20, 2012; Accepted: May 27, 2012) ABSTRACT One of the techniques to improving the studentsâ&#x20AC;&#x2122; meets the academic needs and helps them developing English language skills is providing multimedia during the process of teaching and learning in the classroom. Multimedia classroom provide the students chances for interacting with diverse texts that give them a solid background in the tasks and content of mainstream college courses. The writing aims to find out some advantages of the use of multimedia in the classroom. Also, the involvement of technology in the classroom can not denied giving positive point to improving the quality of teaching and giving more various techniques in teaching a foreign language. The research uses a qualitative method giving a deeply description using multimedia in the classroom. The difference between a traditional classroom and multimedia classroom has been drawn in this writing. The writing shows that there are some advantages in teaching English using multimedia as a technique in teaching process in the classroom. Through the media the teacher could give more opportunity to students to express their opinions and enjoy during the course. The highly presence and motivation also bring positive aspects to students so that they can improve their skills.

Key words: Multimedia, Technology, Classroom.

INTRODUCTION The population of student learning English as a foreign language has been steadily increasing from year to year. To succeed in college, these students must develop not only linguistics, but also academic skills. These skills involve using English to acquire and articulate knowledge by reading academic texts, writing acceptable academic prose, conducting and reporting research. In Indonesia, English is taught in schools since the students go to Junior high schools. However, many of them do not know how to speak and write English for some reasons. Some people from educational field said that the curriculum need to be changed, including the purpose of teaching them English, the textbook, and the methods. To meet the studentsâ&#x20AC;&#x2122; academic needs and help them develop strong English language skills, there are a number of ways need to be applied. One of the techniques to improving

the students is using multimedia in the process of teaching and learning in the classrooms. Multimedia use in classroom will provide opportunity for interacting with diverse texts that give students a solid background in the tasks and content of mainstream college courses. Furthermore, because educational technology is expected to become an integral part of the curriculum, EFL students must become proficient in accessing and using electronic resources. This article describes the method that could help the students to develop their skills in English through multimedia: print text, film, video, radio, computer, and Internet. As students, they must be dealt with the subject found in resource material; also they are able to choose the resources that best suitable the points they wish to make. However, the courses are not included research skills, making research reports to challenging their English language skills.

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JOSHI, Curr. World Environ., Vol. 7(1), 33-36 (2012)

Multimedia Classroom The time it takes to earn the degree in education today is based on an increasingly outdated model: so many hours in a classroom entitle a student to a receipt in the form of a grade, and so many receipts can be redeemed for a credential in the form of a degree... Education today is just beginning to think of shifting the basis of certification from time served to skills and knowledge obtained. Traditionally classroom situation is teachers stand in front of the students, giving explanations, informing, and instructing. They usually use chalk to write something on the blackboard. These technique needs slightly to be modified regarding with the development of the technology. The using of multimedia in classroom cannot be denied anymore. That will make possible for teachers giving more opportunity to students being happier and more enjoy during the course. Traditional classrooms have different settings from the multimedia classrooms. Students seat in rows and a chalkboard in the front. The teacher is standing in front of the class giving a lecture. Compared with traditional classrooms, multimedia classrooms setting differ greatly from traditional classrooms. Traditional classrooms have the seats in rows and a chalkboard in the front. In the multimedia classrooms, students’ seat can be modified according to the situation needed. Inside the classrooms, all the equipment is available and makes the students feel comfortable to study. They sit at wide tables in comfortable chairs and have plenty of room to spread work. Furthermore, they also have the opportunity to move the furniture around for group discussions. A large teaching station is located at the front and to one side of the room. Inside the station cabinet there are controls for the rooms built – in equipment. The use of multimedia described here makes use of print texts, film and Internet to develop and enhance linguistics and knowledge. Through their interactions with multimedia texts on topic of interest, students become increasingly familiar with academic vocabulary and language structures. As they pursue sustained study of one content area through focus discipline research, the students become actively engaged in the process of meaning construction within and across different media. Working though

the complex intermingling of meanings, embedded within different texts encourages students to make connections as they build a wider range of schemata, which are then available to help them grasp future texts. Using print, film and Internet as resources for studying provides students with opportunities to gather information through stimuli that will stimulate their imaginations, engage their interest and introduce them to the raw materials for analysis and interpretation of both language and context. Students develop solid foundation in several subject areas and become “content experts” in one. Thus they greatly increase their overall knowledge base, as well as their English language and critical literacy skills, facilitating their performance in future college courses. Although various studies support the application of multimedia in the classroom, Liu, Jones and Hem street (1998) point out that the design of multimedia is useful when technology is to have any effect on learning. One of the main purposes of software in writing is to facilitate the development of academic writing skills for students through the use of the objects matter for writing assignments. The program is presented as a simulation game to interest and motivation. Students using the program found themselves in the virtual world of education. The Computer Internet Computer technology has given us Internet, which has various uses. Dealing with education, Internet presents the students a wide range of collection of English language texts in many discipline departments. Before the general use of computers in colleges and universities to teach writing, students met in a traditional classroom and were taught to write standard essay. Instruction was personified commonly by the teachers standing behind a lectern or by the teacher marking errors on student texts (Blair, 1997). With the rapid proliferation of the personal computer, many institutions of higher education created “computerized writing courses” emphasizing word processing skills and collaborative critiquing; believing that using the technology “democratizes the classroom discussion, allowing students to transcend the limits of the traditional Computer technology has given us Internet, which is an electronic medium in which both print and visual resources are invariably bound. At the click of a

JOSHI, Curr. World Environ., Vol. 7(1), 33-36 (2012) mouse, text resources present students with a diverse collection of authentic English language texts dealing with a wide variety of interdisciplinary topics, and at each web page link, students have the advantage of reading print texts with the benefit of immediate visual reinforcement provided by pictures and slide shows, facilitating the collaborative effects of print and visual information processing. Integrating the Internet yields the additional benefit of increased student motivation. Students are eager to begin class and often arrive early at the computer lab, logging on to the Internet and beginning research on their own. They also often stay after class to continue working on the Internet. Overall, students develop greater confidence in their ability to use English because they need to interact with the Internet entirely through reading and writing. Using the Internet for focus discipline research not only teaches higher order thinking skills, but also promotes critical and social literacy as students encounter a variety of information, synthesizing that information through cooperation and collaboration with their peers. Members of focus discipline groups generally form strong multicultural friendship fostered by their collaborative efforts throughout the semester. However, the general uses of computers are rarely found in traditional classroom. For instance, students attend the regular classes that were taught to write the standard essay. With the technology use, the students do not only literate the ability to read and write but also to be able to understand music, video, hypertext and networked communications. Whitaker (1995) points out clearly that technology as something to expand human potential rather than substitute for it and which enhances the thought process rather than cripples it. The Print Text The Print text used in presenting students with sophisticated reading that contains cognitively demanding language and introduces a wide range of vocabulary. However, these texts may be difficult to understand. This is suggested to present in printed and visual text. By reading print texts will the benefit of immediate visual provided by pictures or slide show. In writing class of using multimedia, students watch the selected video novel. After watching students are asked questions about the

35

video and assigned essay topics, then divided into brainstorming groups. They discuss and develop the topics in their group. They then make rough draft before presenting in front of other groups. It is obviously that in the multimedia classroom students are engaged to learn how to brainstorm, how to use groups for draft and how to critique other presentations .However, to benefit from the Internet, the students have to learn to navigate and then evaluate the information found there. The students must know how to use search engines, web browsers, and met sites evaluate information in terms of its validity and reliability, as well as its relevance to the topic (Carlson, 1995). Therefore to guide the students in determining whether an Internet source is reliable and credible, students should consider the source and time frame, as well as the evidence supporting the information provided. As the students become more comfortable surfing the Internet, they discover it can be used to develop not only content area knowledge but also to improve their language skills. They know how to compose an essay, using information from the sources they have found in the Internet; also they learn how to cite references in a bibliography. A study conducted by Kasper (1997) illustrate that teaching English using multimedia such as print, film, video, Internet to students encourage them to write a critical analysis on assignments. Overall, the studentsâ&#x20AC;&#x2122; achievement increased significantly. 92 % of the students passed on departmental reading and writing examinations. In addition, their feedback on discussions is very positive. They express confidence in their ability to use English. They attribute this improvement to the multimedia model that the texts teach them English and provide helpful information in other courses and the film and Internet help them make material easier to understand because they see, hear, and read about the topic. The Film Film can be used to provide a visual material. The students can read a print text and watch the film later, according to Kasper and Singer (1997), the film can clarify comprehension, consolidate concepts and reinforce learning. It is expected to the students to fully understand both visual and verbal comprehension. By watching the

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JOSHI, Curr. World Environ., Vol. 7(1), 33-36 (2012)

complete film the students expected to understand various areas of academic discourse such as psychology, environmental science and others to broaden the verbal and written perspective (Kasper and Singer, 1997). A study case from Florida International University (1994), has examined a multimedia classroom, the students watching the video novels Tom Jones (the new six part A & E version) and The Scarlet Pimpernel (Anthony Andrews and Jane Seymour). After viewing it, the class asked questions about the movie and assigned essay topics, to help them the teacher asked the students to brainstorm. CONCLUSION Through the interaction with multimedia, the students become increasingly familiar with academic vocabulary and language structure. Connecting with the Internet will make the benefit of increased student motivation. Students are eager to begin class and often arrive early at the computer lab, logging on the Internet and beginning research on their own. They also often stay after class to

continue working on the Internet. Overall, students develop greater confidence in their ability to use English because they need to interact with the Internet through reading and writing. Using multimedia provides the students to gather information through media that encourages their imaginations, interests. Also it using this technology combined with the sense of teaching will create a successful teaching method. In our imaginations, we enjoy and value all the benefits of education on-demand. We wish the future was here already because deep down inside, we all are lifelong learners. We just want learning to be easy, personalized. This vision is inviting, yet we must live and work in present time. And today, the reality stays apart from the dream. The challenge to educators is clear. We must also establish rigorous standards of quality in the products, services, and solutions we offer to our youth. We must learn how to prepare all of our students for lives that are becoming more and more complex. We must prepare our students to master change.

REFERENCES

1.

2.

Carlson, Earl R. “Evaluating the Credibility of Sources: A Missing Link in the teaching of Critical Thinking”, Teaching of Psychology, 22(1): 39-41 (1995). City University of New York. (1994), Report of the CUNY ESL Task Force, CUNY: Instructional Resource Center, New York. Kasper, Loretta F. (1997), “The Impact of Content-Based Instructional Programs on the Academic Progress of ESL Students”, English for Specific Purposes, vol. 16. Pp. 309-20. Kasper, Strategies”, PostScript, vol. 16. No. 2, pp. 5-17. ^ Richard Ablation, “Goldstein’s Light Works at Southampton,” Variety, August 10, 1966. Vol. 213, No. 12. Eagle Computer, http://en.wikipedia.org/wiki/ Eagle_Computer#Multi-Image_models,

3.

4.

5. 6.

7. 8.

retrieved 2010-06-27 Multi-Media Becomes Multi-Image, http:// www.avsquad.com/page8/page8.html, retrieved 2010-04-30 Vaughan, Stay, 1993, Multimedia: Making It Work (first edition, ISBN 0-07-881869-9), Osborne/McGraw-Hill, Berkeley, pg. 3. Variety, January 1-7, 1996. Stewart, C and Kowalski, A. 1997, Media: New Ways and Meanings Loretta F and Robert Singer. (1997). “Reading, Language Acquisition, and Film (second edition), JACARANDA, Milton, Queensland, Australia. pp.102. Jennifer Story, from Next Online,2002. Lynch P., Yale University Web Style Manual, Http://info.med.yale.edu/caim/manual/sites/ site_structure.heml

Current World Environment

Vol. 7(1), 37-39 (2012)

Chemical Properties of Drinking Water of Renigunta Near Tirupati, Andhra Pradesh, India and its Impact on Human Health S.V. DORAIRAJU 1, C. NARASIMHA RAO2, M. BUJAGENDRA RAJU2 and P.V. CHALAPATHI1* 1

Department of Chemistry, S. V. Arts Degree and P. G. College, Tirupati - 517 502 (India). 2 Department of Chemistry, S.V. University, Tirupati - 517 502 (India). (Received: January 25, 2012; Accepted: March 12, 2012) ABSTRACT This paper is an attempt to assess the effect of drinking water quality on health of the people living in Renigunta, an industrial area near Tirupati, Andhra Pradesh, India. Drinking water samples were collected from 40 different locations of Renigunta and analyzed for physicochemical parameters such as pH, hard ness, alkalinity, calcium, magnesium, iron, nitrates, chlorides, sulphates, electrical conductivity, total solids (TS), total dissolved solids (TDS), total suspended solids (TSS), dissolved oxygen (DO), chemical oxygen demand (COD) and bio chemical oxygen demand (BOD). The found values of physicochemical parameters were compared with the World Health Organization water quality standards. Study of all these characteristics and correlation studies indicate that in some of the studied areas water was polluted and not suitable for drinking purpose. The drinking water of the area needs some degree of treatment before consumption and prevention steps to be taken from contamination.

Key words: Drinking water, Physicochemical parameters, Electrical conductivity, Total dissolved solids, Hardness.

INTRODUCTION The quality of drinking water is vital concern for mankind since it is directly linked with human health. People of rural areas located around Tirupati are mainly dependent on ground water for drinking and other domestic needs. Thus, in this paper an attempt was made to assess the physico chemical analysis of drinking water in the view of health of human beings living in this area. EXPERIMENTAL Drinking water of different polluted locations at Renigunta area near Tirupati was studied during the period from March 2011 to August 2011. Electrical conductivity values were measured using Elico CM 180 conductivity bridge. Total alkalinity was evaluated by titration with standard 0.1M HCl using methyl orange and phenolphthalein

as indicators1. Standard procedures2-5 involving spectrophotometry, flame photometry and volumetry were used for the determination of water quality parameters. All the chemicals used were of AR grade. RESULTS AND DISCUSSION Most of the waters are slightly alkaline due to presence of carbonates and bicarbonates. pH below 6.5 starts corrosion in pipes, thereby releasing toxic metals such as Zn, Pb, Cd and Cu etc3. All the sampling points showed pH values within the limit prescribed by WHO. Hardness of water depends upon the amount of calcium and magnesium salts. Hardness value in the studied area varied between 423-538 mg/L. 6 sampling points showed higher hardness values than the prescribed limit by WHO.

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DORAIRAJU et al., Curr. World Environ., Vol. 7(1), 37-39 (2012)

Alkalinity is due to the presence of bicarbonate, carbonate and hydroxide compounds of calcium, sodium and potassium. Alkalinity itself

is not harmful to human beings4. Alkalinity value in the studied area varied between 218-580 mg/L. 8 sampling point showed alkalinity value within the

Table 1: Average results of chemical parameters Sampling Point S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 S11 S12 S13 S14 S15 S16 S17 S18 S19 S20 S21 S22 S23 S24 S25 S26 S27 S28 S29 S30 S31 S32 S33 S34 S35 S36 S37 S38 S39 S40 WHO

pH

6.7 6.8 6.9 7.9 8 8.1 8.1 8.4 7.8 8.2 8.3 8.3 8.4 8.4 8.5 6.5 6.6 6.7 6.7 7 7.1 7.2 7.4 7.9 7.7 7.8 7.8 6.9 7 6.6 6.7 6.7 7.9 8 6.8 6.6 6.5 6.5 6.5 8.2 6.5-8.5

Hardness Alkalinity Ca2+ (mg/L) (mg/L) (mg/L) 445 445 445 472 472 483 483 527 467 499 462 517 494 501 483 440 430 445 453 462 445 464 471 447 483 472 527 439 453 448 431 441 524 538 454 445 445 439 441 423 500

304 317 329 432 437 463 490 531 427 519 520 524 543 560 580 233 234 298 304 387 392 397 406 429 416 422 427 329 378 244 245 296 432 437 317 238 231 218 229 501 250

118 124 126 177 179 189 192 294 169 208 219 273 306 319 320 83 84 107 118 144 144 159 162 174 164 164 169 126 137 91 92 106 177 179 124 89 81 78 80 197 75

Mg2+ (mg/L)

Fe2+ (mg/L)

NO3(mg/L)

Cl(mg/L)

SO42(mg/L)

71 68 87 73 62 72 74 54 66 75 77 80 83 84 87 58 60 62 62 67 68 68 69 70 69 70 70 63 66 61 61 62 71 72 63 61 57 54 55 73 50

0.39 0.27 0.45 0.49 0.16 0.7 0.71 0.38 0.52 0.45 0.5 0.48 0.61 0.48 0.5 0.36 0.44 0.42 0.39 0.57 0.21 0.43 0.57 0.62 0.51 0.32 0.52 0.45 0.43 0.29 0.38 0.37 0.49 0.16 0.27 0.31 0.25 0.23 0.31 0.41 0.3

8 14 4.2 10.5 4.8 3.5 13.6 3.8 6.9 9.1 12.5 14.6 11 14.3 20.1 11.5 23 4.8 8.5 11.6 6.3 6.5 11 7.4 10 18.4 16.4 11.5 20.8 22.1 22.5 9.6 10 4.2 14 8.6 21.5 11 16 11 45

231 232 232 243 246 246 249 269 242 262 263 265 269 271 310 215 218 230 231 239 239 240 240 243 240 242 242 232 237 223 227 227 243 246 232 221 214 210 211 251 250

146 157 161 178 154 169 137 175 174 162 136 180 175 182 214 190 208 162 146 163 171 172 182 143 224 170 174 161 159 189 168 171 178 154 157 163 209 210 171 154 200

DORAIRAJU et al., Curr. World Environ., Vol. 7(1), 37-39 (2012) limit prescribed and 32 sampling points showed higher alkalinity values than the prescribed limit by WHO Calcium value in the studied area varied between 78-320 mg/L. All the sampling points showed higher calcium values than the prescribed limit by WHO. If calcium is present beyond the maximum acceptable limit causes incrustation of pipes, poor lathering and deterioration of the quality of clothes. Too high magnesium causes nausea, muscular weakness and paralysis in human body when it reaches a level of about 400mg/L 8 . Magnesium value in the studied area varied between 54-87 mg/L. DO value in the studied area varied between 2.3-5.7 mg/L. 9 sampling points showed higher DO values than the prescribed limit by WHO. High amount of DO imparts good taste to water. BOD value in the studied area varied between 1.43.2 mg/L. All sampling points showed BOD values within the limit prescribed by WHO. Ground water with high value of BOD is due to microbial activities related to the dumpsites.

39

When electrical conductivity value exists at 3000 µ mho/cm, the generation of almost all the crops would be affected and it may result in much reduced yield6. It is considered to be an indication of the total dissolved salt content10. Conductivity value in the studied area varied between 10942400 µS/cm. 9 sampling points showed higher conductivity than the prescribed limit by WHO. CONCLUSION According to WHO, nearly 80% of all the diseases in human beings are caused by water11,12. The water quality parameters of the various areas of Renigunta, near Tirupati indicates that the drinking water samples are contaminated and the quality is poor for drinking purpose. After purification treatment only this water can be used for drinking. The values of correlation coefficients will help in selecting proper treatment to minimize pollution. Drinking water pollution in the studied area should be controlled by the proper environment management plan to maintain proper health conditions of people.

REFERENCES 1.

2.

3.

4. 5. 6.

7.

APHA . Standard methods for the examination of water and waste water (19th ed) (1996). Nagarajan S, Swaminathan M and Sabarathinam PL, Poll. Res., 12(4): 245. (1993). Washington, DC: Public Health Association. M. Hussain, T.V.D.P. Rao, H.A. Khan and M. Satyanarayan. Orient. J. Chem., 27(4): 16791684 (2011). A. Malviya, S.K. Diwakar and S.O.N. Choubey. Orient. J. Chem. 26(1): 319-323 (2010). V. Magarde, S.A. Iqbal, S. Pani and N. Iqbal. Orient. J. Chem. 26(4): 1473-1477 (2010). Trivedy R K and Goel P K, Chemical and Biological Methods for Water Pollution Studies, Environmental Publications, Karad, 7: (1986) Surve P R, Ambore N E and Pulle J S, Eco. Env. and Consv., 8(1): 87-90 (2005).

8. 9.

10.

11.

12.

M.G. Adak, and K.M. Purohit, Poll. Res., 20: 575 (2001). C. H. Srinivas, Ravi Shankar Piska, C. Venkatesan, M. S. Sathya Narayana Rao, and R. Ravinder Reddy, Poll. Res., 19(2): 285 (2000). APHA, “Standard methods for the examination of water and wastewater”, American Public Health Association, Washington D.C.,(1998). G. Dilli Rani, M. Suman, C. Narasimha Rao, P. Reddi Rani, V. G. Prashanth, R. Prathibha and P. Venkateswarlu, Current World Environment, 6 (1): 191-193 (2011) . P. Venkateswarlu, M. suman and C. Narasimha Rao, Research Journal of Pharmaceutical, Biological and Chemical Sciences, 2(2): (2011), 464-469. Biological and Chemical Sciences, 2(2): 464-469 (2011).

Current World Environment

Vol. 7(1), 41-48 (2012)

Mineralogical and Textural Characteristics of Soils from Sangamner Area, Ahmednagar District, Maharashtra, India K. K. DESHMUKH Sangamner Nagarpalika Arts, D.J. Malpani Commerce and B.N. Sarda Science College, Sangamner - 422 605 (India). (Received: May 06, 2012; Accepted: June 12, 2012) ABSTRACT Studies were conducted to know the mineralogical and textural characteristics of soils in relation to soil fertility status of Sangamner area, Ahmednagar district, Maharashtra. For this purpose particle size distribution was determined from 62 surface soil samples collected from the area. Representative ten sample clay fractions were subjected to X-ray diffraction analysis for mineralogical characterization. Clay factions have been found to be dominated by illite which is generally facilitated due to high K2O content in soils. Montmorillonite present in the salt affected soils has the predominance of magnesium. Kaolinite, chlorite, halloysite were also detected. The textural analysis revealed the clay content varies from 9.51 to 53.61%. Clay and clay loam type of soils were found in the downstream part which is possibly attributable to inadequate drainage conditions prevailing in the area. The proportion of silt content was followed by sand and coarse sand. The textural classification of the soils showed 35.48% samples were clay, 22.58% samples were clay loam, 21% sandy clay, 16% sandy and 5 % sandy clay. This indicates that majority of the samples have clay and clay loam category. The present investigation suggested that adequate drainage and leaching, crop rotation, blending of saline water with good quality of water, use of manures and mulching and desiltation of Ojhar weir can be adapted as measures to improve soil fertility of the area. Farmerâ&#x20AC;&#x2122;s participation has been looked as the best means of avoiding further degradation of soils in the area.

Key words: Particle size distribution, Montmorillonite, Clay and clay loam, Textural triangular diagram, XRD diffractogram.

INTRODUCTION Soil is a dynamic and complex system of air, water, decomposing organic matter, living plants and animals. In addition to this, soil consists of rock fragments, clays, sands and silts organized into definite pattern as dictated by environmental conditions. The major factors involved in the process of soil formation are parent material, climate, time, topography and biota1. These factors are influencing the mineralogical, mechanical and chemical properties of soils. The physical properties of the soils greatly influences its uses and behavior towards plant growth. This also influences the chemical and biological properties of the soils and it is of utmost importance in relation to plant growth as well as soil fertility.

The mineral matter is a major component of soil. The mineralogical information of soils is essential for understanding soil genesis and for developing appropriate management practices for the maintenance of soil fertility. The color of the soil is also largely caused by the presence of certain minerals. The interaction of soil clay with nutrient ions, water and organic substances determines the soil fertility, which in turn largely controlled by the quality and nature of minerals 2. Therefore, to understand the utility of soils, it is very essential to know the mineralogy. The mineralogy influences soil fertility through its control on the type and quality of plant nutrients which may be released by weathering. The shape of the particles affects their packing and thus related to soil structure3. The study of minerals is the study of nature of soils. Many

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DESHMUKH, Curr. World Environ., Vol. 7(1), 41-48 (2012)

Researchers4-9 have studied the clay mineralogy of normal and salt affected soils from different parts of the country. Texture is probably the most important of the soil characteristics. Soil texture has profound effect upon the properties of soils including its water supplying power, rate of water intake, aeration, fertility ease of tillage and susceptibility to erosion. It is a guide to the value of land. Land use capability and soil management practices are determined by the texture10. Clays also acts as a major store of plant nutrients and therefore many aspects of soil fertility are ultimately influenced by texture 11. Voluminous research work has been conducted in the area of textural characterization of soils12-15. The soils from the Sangamner area mainly derived from the Deccan basalts. The area is experiencing the problems of salinization, alkalinsation, waterlogging etc due to over irrigation, excess use of chemical fertilizers, intensive cultivation with modern production technology and establishment of sugarcane and allied industries. Therefore attempts have been made to study the mineralogical and textural characteristics of soils in order to know their fertility status from study area. The study area The Sangamner area is located in the Ahmednagar district of Maharashtra. Sangamner is a taluka headquarter which is located at a distance of 150 km from Pune on Pune-Nashik National Highway No. 50 (Fig.1). The area is drained by the Pravara river which is a tributory of Godavari. Pravara river originates in the mountainous region of Western Ghats and flows into low-lying fertile alluvial plain in the downstream part. Several dams and weirs have been constructed across Pravara river. Of these, Bhandardara dam is located in the source region and the Ozar weir is in the downstream direction of Sangamner town. These dams and weirs have been augmenting the irrigational water needs of the area. Over 90% of the study area is practising intensive agriculture. It should be noted that subsequent to the establishment of co-operative sugar-mill at Sangamner in 1967, the agriculture in the area has witnessed rapid changes in the cropping pattern. The industrial units developed in the area generate large volumes of waste water which mixes with

surface and groundwater resources thereby contaminating them. At places, the lagoons used for storage of waste waters have caused degradation of soils as well as water due to infiltration of effluents. Thus, the soil resources are facing severe threat from both irrigation practices as well as from agro-based industry. MATERIAL AND METHODS Selected 62 surface soil samples (0-20cm) were collected (Fig 1) in cloth bags as per the standard procedures16,17. 49 samples are from irrigated and 13 from non –irrigated areas. Quartering technique was used for preparation of soil samples. The samples were dried in air and passed through 2 mm sieve and stored in cloth bags. The textural analysis was done by using International Pipette Method10,18,19. Out of 62 soil samples, representative 10 sample clay fractions obtained by International pipette method were subjected to X-ray diffraction analysis for mineralogical characteristics. Six samples (S.No. S6, S 10, S 11, S 13, and S26) were from irrigated / salt affected zone whereas four (S.No. S29, S49, S56 and S59) were from nonirrigated area (Fig 1). For X ray diffraction analysis samples were powdered to 250 – mesh ASTM sieve. The characteristics of clay samples were recorded on PW172. X – Ray diffractometer using CuKα radiation operated at 30 KV and 30 mA (Cu). The CuKα radiation wavelength was 1.542° A. The scanning speed was maintained at 0.05° 2θ /s and chart speed was 5 mm/2θ starting with 2θ = 10 degrees. For the identification of different peaks, Hanwalt’s method has been used in which peaks are composted with ASTM cards. The typical X-ray diffraction pattern of the clay fractions under investigation is shown in Fig 2. RESULTS AND DISCUSSION Mineralogical characteristics of soils It is observed from the fig 2 that the important clay minerals identified in the clay fractions of the soil samples under investigation are illite, montmorillonite, kaolinite, chlorite and halloysite.

DESHMUKH, Curr. World Environ., Vol. 7(1), 41-48 (2012)

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Table 1: Textural Characteristics of the soils from Sangamner area S.

Particle size distribution (%)

Soil

No.

Coarse sand

Fine sand

Silt

Clay

Class

S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 S11 S12 S13 S14 S15 S16 S17 S18 S19 S20 S21 S22 S23 S24 S25 S26 S27 S28 S29 S30 S31 S32 S33 S34 S35 S36 S37 S38 S39 S40 S41 S42 S43 S44 S45

6.08 8.48 13.28 19.88 14.32 9.48 18.21 16.52 7.29 28.08 5.01 14.62 3.52 9.51 31.65 11.21 6.57 5.48 12.45 2.15 32.68 27.67 15.52 22.02 7.31 5.30 33.31 18.25 21.26 32.78 17.08 6.292 7.127 3.22 10.17 13.28 6.647 11.67 25.104 19.086 19.094 9.935 7.317 11.983 4.143

24.92 29.92 28.4 13.22 10.86 20.88 23.12 17.97 16.17 6.07 14.33 25.54 12.05 22.24 9.81 27.93 14.11 15.52 33.62 15.75 36.81 16.6 42.76 42.79 16.35 15.55 27.67 28.51 40.13 20.06 22.62 19.91 11.35 22.71 19.6 33.29 23.56 34.88 41.25 33.56 31.54 37.28 41.96 32.76 34.75

21.6 15.35 12.2 21.1 25.17 32.15 15 22.07 29.08 20.87 31.15 30.15 26.82 26.37 18.22 33.3 21.17 26.6 15.72 23.42 13.73 19.35 16.65 12.42 20.12 23.35 13.35 19 14.55 12.65 14.52 23.4 20.65 28.15 10.67 24.4 15.57 21.97 12.12 18.35 14.27 23.426 11.87 14.87 11.22

46.75 45.73 40.53 39.48 43.93 31.98 42.18 37.43 41.33 39.83 43.53 28.06 50.23 35.68 37.16 29.51 51.03 44.93 43.18 52.33 13.51 31.71 20.58 18.11 49.71 51.03 21.04 29.09 19.38 29.26 39.31 42.61 53.16 37.56 51.57 32.73 48.06 27.03 17.78 22.91 26.81 24.61 33.11 34.93 41.56

Clay Clay Clay Clay loam Clay Clay loam Clay Clay loam Clay Clay loam Clay Clay loam Clay Clay loam Clay loam Clay loam Clay Clay Clay Clay Sandy loam Sandy clay loam Sandy clay loam Sandy loam Clay Clay Sandy clay loam Sandy clay loam Sandy loam Sandy clay loam Sandy clay Clay Clay Clay loam Clay Clay loam clay Clay loam Sandy loam Sandy clay loam Sandy clay loam Sandy clay loam Sandy clay loam Sandy clay loam Sandy clay

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DESHMUKH, Curr. World Environ., Vol. 7(1), 41-48 (2012) S46 S47 S48 S49 S50 S51 S52 S53 S54 S55 S56 S57 S58 S59 S60 S61 S62

7.559 9.139 6.592 12.846 18.03 4.33 11.28 21.12 10.372 3.696 6.117 4.23 2.199 4.777 19.932 11.266 6.595

53.32 51.83 35.87 36.87 45.97 19.39 50.03 41.34 26.884 29.51 33.33 31.55 28.66 28.35 49.24 34.59 29.1515

22.07 16.15 20.15 16.05 12.95 22.52 16.93 16.1 18.12 23.87 20.27 12.37 13.75 10.87 7.875 10.8 12.2

12.28 18.01 32.11 28.36 19.73 48.58 17.91 17.86 40.36 38.68 33.68 45.26 46.93 46.56 19.51 35.51 44.56

Sandy loam Sandy loam Sandy clay loam Sandy clay loam Sandy loam Clay Sandy loam Sandy loam Clay loam Clay loam Clay loam Clay Clay Clay Sandy loam Sandy clay Clay

Fig. 1: Location map showing soil sampling stations in the study area

Illite The dominance of illite in all samples reflected the alkaline nature of the soils along with high concentration of aluminum and potassium. This is further evidenced by the chemical analysis of soils 20 . Illite is identified by series of basal reflections at 1.99°A, 3.32° 2.57° A and 2.07° A, besides the weaker reflections at 1.52°A, 4.81° A and 3.1° A. The presence of illite in the samples is indicative of the influence of olivence / enstatitic pyroxene dominated parent material. However, the formation of illite is more favoured due to high K2O

content of these soils20. This is possibly due to excessive use of potash fertilizers. Montmorillonite The XRD pattern of salt affected soils in the area revealed the formation of montmorillonite (smectites). This can be attributed to alkaline condition and availability of sodium and magnesium. Such hyper alkaline condition can be developed due to impeded drainage in the area1,21. Montmorillonite presence is seen as 100% reflection at 4.41° A and weaker reflections at 1.53°A

DESHMUKH, Curr. World Environ., Vol. 7(1), 41-48 (2012)

45

drainage condition have accelerated the formation of smectite22. However, the normal soil showed less proportion of montmorillonite indicating adequate drainage and leaching of magnesium from the host rock basalt.

Fig. 2: XRD diffractogram for some clay fractions of representative soil samples

Kaolinite It is a major component in almost all the soil samples from study area. It is represented by basal reflection at 7.13 to 7.24° A and 3.55° A. However, in the presence of chlorite as in the case of present samples, the above reflection interfere and coincide with the chlorite at 7.14 and 3.54°A respectively. The other reflections were identified with the lesser intensity at 2.43°A, 2.86, 2.57 and 2.2°A. In the upland soils the dominance of kaolinite might be attributed to the good internal drainage. The plagioclase feldspar has undergone weathering to kaolinite at low pH. However, it is observed that kaolinite reflection does not show any systematic variation in intensity. Chlorite It is represented by basal reflections at 7.14°A and weak reflection at 1.55°A. However, because of interference and coincidence of reflections of chlorite with reflection of kaolinite, it was rather difficult to distinguish between the peaks of kaolinite and chlorite in the soil samples under study.

Fig. 3: Triangular diagram showing textural classification of soils from study area to 3.48°A. Similarly, weaker reflections were also identified in the range of 1.29° A to 7.73°A. Under alkaline conditions, the pyroxenes from basalt are believed to weather to clay of this type and fine sand. The smectite type of minerals once formed, remain stable under alkaline conditions that can develop impeded drainage. In the low lying area, it appears that slightly weathered parent materials under alkaline conditions, low Mg and poor

Halloysite It is the mineral, which belongs to kandite group21. It is known to occur in two forms with basal spacing 10 ° A and 7 ° A as halloysite and methahalloysite respectively. In the present study, 100% intensity has been detected at 4.43° A and 4.52° A, which indicated the presence of hydrated halloysite in all the samples under study. By and large, it can be inferred that the formation of illite in the area is generally facilitated by the presence of cations like potassium and sodium in sufficiently large quantities. The montmorillonite present in salt affected soils is due to the predominance of magnesium or other alkaline earth cations. Kaolinite, chlorite and halloysite were also detected in the soils samples. However, no remarkable difference was seen in the clay mineral composition in the soils from the area.

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DESHMUKH, Curr. World Environ., Vol. 7(1), 41-48 (2012)

Textural characteristics of soils from the Sangamner area The textural characteristics of the soils are the most important laboratory determinations made in the soil studies. It deals with the process of determining the amount of individual soil separates below 2 mm in diameter i.e. sand, silt and clay. The relative proportions of these soil separates are referred to as soil texture. The various relationships that exist between plant and soil are controlled to a great extent by soil texture1. It is observed from the table 1, that majority of the soils are in the clay and clay loam category. The clay content varies from 9.51 to 53.61 %. However, the clay and clay loam type of soils were reported predominantly from the downstream part and in the catchment of Ojhar weir (S. No. S1, S2, S3, S4, S5, S8, S9, S10, S12, S14, S15, S16 and S33). This is possibly due to inadequate drainage due to unfavorable topography and siltation at Ojhar weir. In addition to this, presence of alluvial deposits showing low permeability has lead to higher clay content. The silt content of the soils ranged from 10.8 to 33% However, higher values of slit were noticed for the soils from irrigated tract and in the areas of lower elevation (S. No. S6, S9, S12, S13, S14 and S16). The fine sand and coarse sand ranged from 6.076 to 59.24% and 3.696 to 33.31% respectively. The higher content of these sands was recorded in the vicinity and downstream part of Ojhar weir (S.No. S21, S23, S24, S29, S39, S43 and S60). However, low values were found in the areas with flat topography (S, No.S5, S10, and S15) and characterized by alluvial lithology. Similar observations were made by the researchers7,14,23,24 for the soils from the area which is in proximity to the present study area. This inference is also supported by cation exchange capacity values20. The distribution of particle size influences the moisture retention and transmission properties of soils. This is to say that, coarse textured soils have low moisture retention and high permeability whereas fine textured soils have high moisture retention and low permeability25. Considering this,

it can be said that the soils having high clay content (S. No. S2, S3, S4, S5, S7, S8, S9, S10, S16 and S20) will have low infiltration rate. The chemical properties of soils are expected to be influenced by clays than silt and sand particles. This is because clay fraction contains larger alumino â&#x20AC;&#x201C; silicates and has higher content of humus. Therefore, they are characterized by a higher charge density per unit surface26. In the study area, high proportion of clay in some parts of study area can be considered as one of the important factors influencing the chemical properties of soils20. Textural classification of the soil Natural field soils are always mixtures of soil separates. The relative percentages of the various soil separates in a field are almost infinite in possible combinations. It is, therefore, necessary to establish limits of variations among the soil sepa-rates so as to group them into textural classes. The determination of the textural class of a soil is based on particle size analysis. The soil samples from study area are separated into three size fractions viz. sand, silt and clay. The quantity of each fraction was measured and expressed as a percentage (by weight) of the soil. The distribution of the different sized particles was used for determining textural class of the soil with the help of textural triangular diagram (Fig 3)10,16. On the basis of this, five tex-tural groups were obtained viz clay, clay loam, sandy loam, sandy clay loam and sandy clay from the study area (Fig 3). Out of 62 soil samples, 22 soil samples (35.48%) were clay, 14 samples (22.58%) were clay loam, 10 samples (16.12%) were sandy loam, 12 samples (20.96%) were sandy clay loam and 3 (4.84%) were sandy clay. Thus, majority of the samples in the area represent clay and clay loam type of textural class. The distribution of various textural classes is depicted in Fig 3. From the Fig, it is observed that the clay and clay loams were located in the central and downstream part in the back-waters of Ojhar weir. (S.No. S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S12, S14, S15, S16, S17, S18, S34, S35, S36, S37, S38, S51, S57, S58, S59 and S62). This particular area is waterlogged due to flat topography and impeded drainage. Similar observations were also

DESHMUKH, Curr. World Environ., Vol. 7(1), 41-48 (2012) reported 7,23,24 from adjoining areas in the same basin. In nutshell, textural classification of soil provides a basis for making judge-ment about various other properties important to overall soil behavior in the area. CONCLUSION The studies carried out to know mineralogical characteristics of the soils from Sangamner area have demonstrated the importance of clay minerals in relation to soil fertility. The clay minerals identified by the XRD studies of the representative soil samples indicated presence of illite followed by montmorillonite, kaolinite and halloysite in the area. The formation of illite in the soil is generally facilitated by the presence of cations like potassium and sodium in sufficiently large quantities. The montmorillonite present in salt affected soils has the predominance of magnesium. However, no remarkable difference was seen in the clay mineral composition in the soils from the area. The textural analysis revealed the predominance of clay to clay loam textural type of soils which are located in the downstream part i.e. in the catchment of Ojhar weir. This is possibly attributable to inadequate drainage conditions prevailing in the area. The five textural groups of

47

soils viz. clay, clay loam, sandy loam, sandy clay loam and sandy clay were identified in the area. Out of these, majority of the samples represent clay and clay loam type, which are located in the downstream part of the river. The percentage distribution of these textural classes is clay (35.48%), clay loam (22.58%), sandy clay loam (21%), sandy loam (16%) and sandy clay (5%). The present investigation suggested that adequate drainage and leaching, crop rotation, blending of saline water with good quality of water, use of manures and mulching and desiltation of Ojhar weir can be adapted as measures to improve soil fertility of the area. Farmerâ&#x20AC;&#x2122;s participation has been looked as the best means of avoiding further degradation of soils in the area. ACKNOWLEDGEMENTS The author is thankful to Dr. N. J. Pawar, Vice-Chancellor, Shivaji University, Kolhapur for his valuable guidance and constant encouragement. The author is also thankful to Head, Department of Environmental Science, University of Pune and Post-Graduate Research Centre in Chemistry, Sangamner College, Sangamner for providing necessary research facilities. The author is also thankful to Head, Department of physics, University of Pune for providing X- ray diffraction analysis.

REFERENCES 1.

2.

3.

4.

5. 6.

Miller R.W. and Donahue R.L., Soils : An introduction to soils and plant growth, Prelatic Hall of India, Pvt Ltd, New Delhi (1992). Thompson L.M. and Troen F.R., Soils and Soil fertility, 3rd edition McGrawhill Book Co. 137161 (1973). Jain V.K., Biofertilizers for Sustainable Agriculture, Oxford Book company, Jaipur, (2009) Colman S.M., Clay mineralogy of rinds and possible implications concerning the sources of clay minerals in soils, Geology, 10: 370 (1982). Tewatia R.K. Singh N, Ghabm S.K. and Singh M., J. Ind. Soc. Soil Sci., 37: 687-691 (1989). Pancharne T.K., Pal D.K. and Deshpande

7.

8.

9.

10.

S.B., J. Ind. Soc. Soil Sci., 44: 300-309 (1996). Durgude A.G., Morphology, characterization and mapping of salt affected soils Agricultural University, Rahuri, Ph.D. Thesis, Rahuri (1999). Marsonia P.J., Polara J.V. and Hadiyal S.T., Characterization and classification of cultivated soils of Gujarat, An Asian J. of soil Science, 3(2): 287-288 (2008) Meena R.B., Balpande S.S., Bahaulkar V.P. and Mandle M.G., Characterization and classification of water logged soils of Upper Wardha area of Maharastra, J. soils and crops, 21(1): 90-94 (2011). Gupta P.K., Soil, Water, Plant and Fertilizer analysis, 2nd Edition, Agrobios Publishers, Jodhpur (2009).

48 11. 12. 13. 14.

15.

16.

17.

18. 19. 20.

DESHMUKH, Curr. World Environ., Vol. 7(1), 41-48 (2012) Briggs D. Soils, Butterwor ths and CoPublishers, London 129-134 (1977). Maji B. and Bandopadhyaya B.K., J. Ind. Soc. Soil Sci., 43(1): 103-107 (1995). Hopkins D.G. and Richardson J.L., Hydrology, 7: 380-392 (1999). Challa O.B.P., Bhaskar S.G., Anatwar and. Gaikwad M.S, Characterization and classification of problematic vertisols in semiarid ecosystem of Maharashtra plateau J. Ind. Soc. Soil Sci. 48 (1): 139-145 (2000). Grace G. and Eta N.E., Research Journal of Chemistry and Environment, 15(2): 1-4 (2011). U.S. Salinity Laboratory Staff, Diagnosis and Improvement of saline and alkali soils, USDA, Handbook No. 60, U.S. Dept of Agriculture, Washington D.C. (1954). Hesse P.R., A textbook of soil chemical analysis, John Murry Publication, London, U.K. (1971). Piper C.S., Soil and plant analysis, Hans. Publication Bombay (1966). Jackson M.L., Soil chemical analysis, Prentice Hall of India, New Delhi (1973). Deshmukh K.K. Impact of irrigation on the Chemistry of the soils and groundwater from

21.

22. 23.

24.

25.

26. 27. 28.

Sangamner area, Ahmednagar district, Maharashtra, Ph.D. Thesis, University of Pune (2001). Deer W.A. Howe R.A. and Zooman J. An introduction to rock minerals, Longman group, London, 250-269 (1980). Singh A, Yadhav R.B. Tripathi S.B. and Arya R.L., Fertilizer News, 43(8): 45-50 (1998). Shinde M.D., Study on soil characteristics and effect on green algae from Pravaranagar area, Ahmednagar district, Ph.D. Thesis, University of Pune (1997). Bharmbe P.R. and Ghonsikar C.P. Physico â&#x20AC;&#x201C; Chemicals Characteristics of Soils in Jayakwadi Command, J. Maharashtra Agri. University, 10: 247-249 (1985). Richards L.A., Diagnosis and Improvement of saline soils U.S. Salinity Laboratory Staff, Agriculture Handbook No. 60, oxford and IBH Publishing Co. New Delhi (1968). Orlov D.S., Soil Chemistry, Oxford and IBH publishers, New Delhi (1992). M. Zamani, Orient. J. Chem., 28(1): 491-497 (2012). R.V. Kumar, A. Arokiaraj and P.M.D. Prasath, Orient. J. Chem. 27(2): 567-571 (2011).

Current World Environment

Vol. 7(1), 49-50 (2012)

The Position of Word “Quality” in Industrial Management FARKHUNDA SAYYED¹ SHOYEB ALI SAYYED² and MUJAHIDA SAYYED³ ¹Lord Krishna College of Technology, Indore (India). ²Royal College of Technology, Indore (India). ³Department of Statistics, College of Agriculture, Ganjbasoda - 464 221 (India). (Received: April 12, 2012; Accepted: May 27, 2012) ABSTRACT In This Paper we deal with the concept of the word quality with reference to industrial management.

Keywords: Physicochemical, Pollutant, Industrial Wastewater in dheradun.

INTRODUCTION The most important word in the progress of any industry is quality. By quality we mean an attribute of the product determines its fitness for use. The range of these attributes is pretty wide – Physical, Chemical, aesthetic etc. A product may have several aspects of quality as well as an over all quality which is something more than the sum of its individual quality aspects. Quality means a level which in turn, depends on four M’s besides many other factors which is materials, man power, machines and management. Literature Review Quality assurance is the products used by our society. Product consist of manufactured goods, such as automobiles, computers, clothing, public transportation and health care. Quality assurance principles apply to both manufactured goods and services. It is essential that products meet the requirement of those who use them. Therefore, the definition of quality is that quality means fitness for use. These are two general aspects of quality: quality of design and quality of conformance. All goods and services are produced in various grades or level of quality are international and consequently, the appropriate technical term is quality of design. The quality of conformance is how will the product conforms to the specifications and

tolerance required by the design. Quality of conformance is influenced a no. of factors, including the choice of manufacturing processes, the training and supervision of the work force, the type of the quality assurance system i.e. process controls tests inspection activities etc, used, the extent to which these quality assurance procedures are followed and the motivation of the work force to achieve quality. To achieve quality of design requires conscious decisions during the product or process design stage to ensure that certain functional requirements will be satisfactory met. Designing quality into the product in this fashion often results in a higher product cost. Quality of conformance are often made by changing certain aspects of the quality-assurance system. Such as the types of inspection in total costs, because it leads to reduced scrap, rework, and a smaller fraction of nonconforming products and services. Quality is becoming the basic consumer decision factor in many products and services. This phenomenon is widespread, regardless of whether the consumer is an individual an industrial corporation, a military defence program, or a retail store. Quality is a key factor leading to business success, growth and enhanced competitive position. There is a substantial return on investment from an effective quality assurance program that provides increased probability to firms that effectively employ quality as a business strategy.

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Quality control determines what, when and how much to inspect and what measures to take so that defective items are not produced. It is preventives rather than a corrective measure. The corrective action rests with the personnel. Quality control is one of the important functions of the management. It is a system set of tools and techniques by which products are made to comply with the specification at minimum cost to the firm. Quality control is concerned with making things right rather than discovering and rejecting those made wrong. Quality is not merely the responsibility of quality control department. Quality control is an integrated function. The quality of a product can be directly traced to the quality of production aids (tools, tigs and fixtures, measuring instruments); quality of manufacturing process and manufacturing facilities employed; quality of workmanship, and the quality of systems set to regulate and control work on the shop floor. Quality control thus aims to produce, better quality products at the least cost to the company and inspection is one of the tools used by it to achieve this objective. Quality control and inspection are, therefore, closely related. The two functions were formerly combined, inspection being a part of quality control or vice versa. One simply way to control the quality is to conduct 100% inspection. However it will be very costly and time consuming. Now a days statistics is used for quality control and this method is known as statistical quality control and this method is known as statistical quality control.

For ex. In the area of ever growing competition has become absolutely necessary for a businessman to keep a continuous watch over the quality of the goods produced moving once bought the product, if the consumers feel satisfied with regard to its quality, price etc., a kind of goodwill for the product is developed which helps to increase the sales. However, if the consumers are not happy with the quality of the product and their complaints are not given proper attention, it shall be impossible for the manufacturer, to continue in the market. Either he would have to improve the quality or else be forced to quit the market to other producers who might start capturing the market by offering better quality. CONCLUSION Quality does not always imply the highest standards of manufacturer for the standard required is often deliberately below the highest standard possible. It is generally the consistency in quality standards which represents the most desirable situation rather than the absolute standards which is maintained.

With the use of quality control we can setup standards of quality acceptable to the customer and economical to achieve and maintain and we can locate and identify the process faults in order to control the defectives, scrap and waste. With the use of quality control we can take necessary corrective measures to maintain the quality of the products and off course we can ensure that substandard products do not reach the customers and achieve better utilization of raw materials and equipments.

REFERENCES

1.

2. 3.

Chiu, W.K. and G.B. Wetherill, “Quality Control Practices”, International Journal of Production Research, 13 (1975). Duncan, A.J. “Quality Control and Industrial Statistics” 4th Ed., Irwin, Homewood III (1974). Jurnan, J.M. and F.M. Gryna, Jr. “Quality Planning and Analysis” 2nd Ed., McGraw Hill,

4.

5.

New York (1980). Montgomerey, D.C. “Introduction to Statistical Quality Control” John Willey and Sons, 2nd Edition (1991). Sanigo, E.M. and L.E. Shirland “Quality Control in Practice – A survey” Quality Progress Vol. 10 (1977).

Current World Environment

Vol. 7(1), 51-54 (2012)

Study on Application Potential of Waste Cake from Secondary Zinc Industry MOHD. AKRAM KHAN¹ and RAJNISH SHRIVASTAVA² ¹Principal Scientist, CSIR-AMPRI, Hoshangabad Road, Bhopal (India). ²Director, National Institute of Technology (NIT), Hamirpur (India). (Received: April 25, 2012; Accepted: June 07, 2012) ABSTRACT Zinc extraction process generates hazardous waste cake during the recovery of electrolytic grade zinc and copper. The characteristics of the waste with reference to basic properties viz. ignitability, corrosivity, reactivity and EP toxicity are important parameters that define the magnitude of hazard of a waste. The waste under study falls under Schedule-I of Hazardous Waste (Management & Handling) Rules, 2003. The Toxicity Characteristics Leachate Procedure (TCLP) test was carried out for extraction of waste cake leachate and subsequently toxic heavy metals present in the waste were estimated. The physic-chemical parameters along with particle size analysis, differential thermal analysis and X-ray diffraction analysis were carried out which provide information on the major constituents present in the hazardous zinc waste cake before and after stabilisation/stabilisation of the waste. The approach would be helpful in safe disposal and exploring application potential of zinc waste through adoption of suitable binder mechanism.

Key words: Hazardous waste, Zinc industry, Waste cake, Leachate, TCLP, Solidification / stabilisation.

INTRODUCTION The rapid industrialisation has lead to severe environmental threats through generation of large quantities of industrial wastes and hazardous sludges. The primar y sources of hazardous wastes in India and other developing countries include waste generated within the country through different industrial units and waste imported into the country as raw materials. A study carried out on solid waste management in nonferrous industries in India mentions alarming levels of hazardous secondary zinc wastes and other industrial wastes that are threatening the environment1. Hazardous waste means a solid waste or a combination of solid waste which by virtue of its quality, concentration or physical or chemical or infectious character may cause to an increase in mortality or serious illness or pose a potential

hazard to human health or the environment when improperly treated, stored, transported or disposed2. India has witnessed nearly fivefold increase in its industrial production in the last few decades and presently more than 500 medium and large chemical and allied industries are in operation3. The present study covers the industrial waste generated by secondary zinc industry located in the western part of India and generates around 5,000 TPA of the waste cake. It is well known that production of pesticides and herbicides used in agricultural application produce wastes of hazardous / toxic nature. Similarly fluoride waste and by-products of phosphate fertilizer industry also generate hazardous toxic wastes. Household sources of hazardous waste include metallurgical scraps, secondary industry process waste cake, toxic paints, solvents, caustic cleaners, batteries, drugs etc. These wastes contaminate the soil and ground

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water and adversely affect the natural eco-system through percolation of heavy metals into the soil and natural water sources3. The release of harmful chemicals / toxic wastes into the environment mainly through industrial, agricultural, household and transport route results in air, soil and water pollution. Major man made sources of pollutants are linked to mining and metal production, metal extraction, fossil fuel burning, coal mining, production of conventional building materials, chemical and pharmaceuticals, use of chemical fertilizers, municipal and industrial waste dumps, incinerators and other specialised dumping sites 4 . The locations par ticularly threatened are areas which are already environmentally overloaded and have no free absorption capacity areas with shallow ground water and porous soil regions. The manufacturing of different computer components involve many industrial processes which lead to generation of liquid wastes. A printed circuit board generates spent electroplating bath that contains metal salts and the production of the computer chips use acids, caustic chemicals and solvents. Hazardous waste is also generated by fiber optics and copper wire used in electronic transmission as well as magnetic disks, paper and photographs for packaging and publicity. The concepts relating to hazardous waste management emerging day by day and undergoing review and upgradation in India. The Government of India has promulgated the Hazardous Waste (Management & Handling) Rules, 1989 through MoEF, New Delhi under the aegis of Environmental Protection Act, 1986. The rules were modified through an amendment as Hazardous Waste (M&H) Amendment Rules, 2002. Based on the further suggestions received and considering the various new methodologies, Govt. of India notified Hazardous Waste (Management & Handling) Rules, 2003 and suggested modifications in Schedule-I with the list of processes generating hazardous wastes. It also mentions the secondary production and / or use of zinc generating sludge and filter press cake, zinc fines / dust / skimming in the list5.

Classification of Hazardous Waste Characterisation and classification of hazardous waste is required for safety reasons to ensure that incompatible wastes are identified and handled separately. Wastes can be classified by using relatively simple and inexpensive test methods during waste collection and laboratory analysis. There are four main characteristics namely ignitability, corrosivity, reactivity and Extraction Potential (EP) toxicity which determine whether a waste is classified as hazardous waste or not [5]. They have been elaborated below: Ignitability Solid waste exhibits the characteristics of ignitability if a representative sample of that waste is a liquid containing less than 50% water and less than 24% alcohol and the flash point is less than 60 oC. Corrosivity Solid waste exhibits the characteristics of corrrosivity if a representative sample of waste is aqueous and has pH less than or equal to 2 or greater than or equal to 12.5 or liquid and corrodes steel at a rate greater than 6.35mm (0.25 inch) per day under a temperature of 55oC. Reactivity Reactive wastes are those that are extremely unstable under normal conditions with tendency to explode or give off dangerous gases. Standard methods to test reactivity currently do not exist and it is possible only to list their physical peculiarities. A solid exhibits the characteristics of reactivity if a representative sample of the waste is typically unstable and readily undergoes violent changes without deteriorating, reacts violently with water and forms potentially explosive mixture with water. EP Toxicity The EP toxicity is the measure of the likelihood that waste will leach out toxic chemicals. A particular waste is considered toxic if concentrations of any of the heavy metals in its extract are greater than standards mentioned as per the permissible limits of Hazardous Waste (M & H) Rules, 2003 [5].

Khan & Shrivastava, Curr. World Environ., Vol. 7(1), 51-54 (2012) MATERIAL AND METHODS TCLP test was adopted in 1968 by the US Environment Protection Agency (USEPA) as a replacement of EP toxicity. The TCLP is also widely used to evaluate the effectiveness of stabilisation of the waste. In this test method, the waste material is crushed to a particle size smaller than 9.5 mm and mixed with a weak acetic acid as extraction liquid (pH 4.93) in a liquid to solid weight ratio of 20:1 and agitated in a rotary extractor for a period of 18 hours at the speed of 30 rpm and 22 oC 6. The sample is filtered through 0.6-0.8 Âľm glass fiber filter paper and the filtrate is defined as the TCLP extract. This extract is analysed for wide variety of hazardous waste constituents including heavy metals of interest in the waste. RESULTS AND DISCUSSION The secondary zinc waste cake is neutral in nature with its pH around 6.3 and particle density to be around 2.4 gm/cc. The moisture content varied in the range of 24 to 35%. The waste cake mainly consists of zinc, copper, manganese, lead and iron as predominant heavy metals present in the sample. Particle Size Analysis The hazardous waste collected from the rotary vacuum filter (waste cake) was dried and particle size analysis was carried using standard sieves and using Laser Particle Size Analyser (Malvern make). The results show that the waste sample consists of clay sized particles upto 20% and silt size particles upto 52% of the total weight.

53

radiation and nickel filter at 40kV and 20mA. The identification of mineral phases was done with the help of mineral powder diffraction file JCPDS and ASTM diffraction data. The major peaks identified in the waste sample are that of Gypsum with Mn2O3 and lime in traces. TCLP Testing Leachability test was carried out by using Millipore make Zero Headspace Extractor (ZHE). The sample is agitated for 18 hours in a rotary agitator for extracting the secondary leachate. The primary and secondary extracts were obtained at 50 psi pressure with glacial acetic acid and NaOH solution as extraction fluid at a pH of 4.93 [6]. The leachate obtained is analysed for different heavy metals using Hitachi make Atomic Absorption Spectrophotometer. The analysis results for the waste sample are as below: Solidification is the process by which the sufficient quantities of solidifying materials are added to the hazardous waste to result in a solidified and encapsulated mass of materials. Stabilisation is a process that uses additives to reduce the hazardous nature of the waste by converting the waste and its hazardous constituents into a form to minimise the rate of contaminant migration in the environment and to reduce the level of toxicity. Many technologies have been proposed for detoxifying the waste by processes that destroy chemical bonds so that the toxic nature is minimised.

X-Ray Diffraction Analysis X-Ray Diffraction Analysis was carried out by Philips Diffractometer model 1710 using CuK

It is reported that approximately 0.5 million tonnes of lead-zinc slag is generated annually and this slag can be used upto the extent of 45% as blending component for the manufacture of Portland Slag Cement7. This indicated that the waste cake has potential for its reuse in different applications.

Table 1.1 Concentration of heavy metals in the Waste Cake

Table 1.2 Concentration of heavy metals in TCLP extract of Waste Cake

Heavy Metals Zinc Copper Lead Manganese Iron

Concentration (%) 3.10-3.40 2.80-3.00 4.10-4.40 3.30-3.80 1.50-1.70

Heavy Metals Zinc Copper Lead Manganese Iron

Leachate Concentration (ppm) 0.51-0.56 1.62-1.85 0.11-0.14 0.135-0.142 0.062-0.071

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The hazardous secondary zinc waste was found suitable for encapsulation with different binders like fly ash, clay and their combinations in defined proportion. The results indicated that leaching properties of heavy metals present in the waste cake got arrested in the solidified-stabilised mass thus converting them into non-hazardous form of waste.

falls in Schedule-I of Hazardous Waste (M&H) Rules, 2003. The hazardous waste can be characterised by TCLP testing to identify the leachable toxic elements and can be solidified & stabilised by using different binder materials. The new material provides good alternative for safe utilisation and disposal of zinc waste cake.

CONCLUSIONS

ACKNOWLEDGEMENTS

The characteristics and categorisation of hazardous waste is one of the important aspects of the hazardous waste management. The secondary zinc extraction process produces waste cake that

The authors are extremely thankful to Director, CSIR-AMPRI Bhopal for the permission to carry out this work and for the facilities provided for the research work.

REFERENCES

1.

2.

3.

4.

Agrawal A., Sahu K.K., Pandey B.D., Solid waste management in non-ferrous industries in India, Resources Conservation & Recycling, 42: 99-120, Elsevier Publication (2004). LaGrega M.D., Buckingham P.L. and Evans J.C., Hazardous Waste Management, McGraw Hill International Edition (1994). Toxic and hazardous waste disposal - An Indian perspective, Nag P.J., Chemical Industry News, 1027-1029 (1996). Stanley E. Manahan, Fundamentals of Environmental Chemistry, Second Edition, Lewis Publishers (2001).

5.

6. 7.

8.

Hazardous Waste (Management & Handling) Rules, Ministry of Environment & Forests, Govt. Of India, notification dated 20th May 2003 (2003). Toxicity Characteristics Leachate Procedure, Millipore Information Booklet (2000). Assessment of Utilisation of Industrial Solid Wastes in Cement Manufacturing, Central Pollution Control Board Report, MoEF, New Delhi, (2006). S. Katanyoon, W. Naksata, P. Sooksamiti, S. Thiansem and Orn-Anong Arquero. Orient J. Chem. 28(1): 373-378 (2012).

Current World Environment

Vol. 7(1), 55-59 (2012)

The Study of Metamorphic Rocks, Zonation and Isogrades in Garnet Rocks in the Hamadan Area ZAHRA HOSSEIN MIRZAEI BENI and ZOHREH HOSSEIN MIRZAEI BENI Young Research Club, Khorasgan (Isfahan) Branch, Islamic Azad University, Isfahan (Iran). (Received: March 03, 2012; Accepted: April 15, 2012) ABSTRACT The study area is a part of the Sanandaj- Sirjan metamorphic belt. We can divide Hamadan metamorphic rocks in three groups: regional metamorphic rocks, contact metamorphic rocks and migmatites. In this area we can’t completely divide zonation of contact and regional metamorphic. In some places that contact metamorphic has influenced to low degree regional metamorphic rocks, contact metamorphic zonations are clearly appear, but when contact and regional metamorphic have a same degree or regional metamorphic has high degree than contact metamorphic, we can’t distinguish them easily. In Hamadan area regional metamorphic zones are Chlorite± Biotite zone (we haven’t garnet rocks in this zone), Biotite± Garnet zone (divided in two sub zone, Biotite and Garnet zone), Andalusite zone, Staurolite zone, Staurolite± Andalusite zone, Sillimanite- Muscovite zone and Sillimanite- Potassium feldspar± Cordierite zone, also contact metamorphic zones are Cordierite zone and Cordierite- Potassium feldspar zone. Key words: Contact metamorphic; Garnet; Isogrades; Metamorphic zonation; Migmatites; Regional metamorphic.

INTRODUCTION Garnet crystallizes in cubic system and mostly in dodecahedron (rhomb-dodecahedron) and trapezohedron (tetragon-trioctahedron) crystal forms. General chemical formula of this mineral is: R3R’2(SiO4)3, which bivaliant cations (i.e. Mg2+, Fe2+, Mn2+, Ca2+) lie in R site and trivaliant cations (i.e. Al3+, Cr3+, Fe3+) in R’ site. Commonly, more than one cation lies in R and R’ sites and therefore garnet crystals give rise to isomorphous (solid solution) series of minerals. If Al3+ is located in R’ site, the pyralspite group [( Fe2+,Mg2+,Mn2+ )3 Al2(SiO4)3] with almandine [(Fe2+)3 Al2 (SiO4)3], pyrope [(Mg2+)3Al2 (SiO 4) 3] and spessartine [(Mn 2+) 3Al 2(SiO 4) 3] end members will form. If Ca2+ is located in R site, the ugrandite group [(Ca2+)3(Al3+,Fe3+,Cr3+)2(SiO4)3] with grossularite[Ca3Al2(SiO4)3], andradite [Ca3(Fe3+)2 (SiO 4) 3] and uvarovite [Ca 3(Cr 3+ )2 (SiO 4) 3] end members will form. Some other cations may also be emplaced in R and R’ sites [1, 2]. The garnet

minerals chemistry in the study area are rich in almandine. Geological Setting The study area is a part of the SanandajSirjan metamorphic belt. The Alvand plutonic complex is the most important plutonic body that regional and contact metamorphic rocks with low to high grade are located around it. The metamorphic sequence comprises pelitic, psammitic, basic, calc-pelitic and calc-silicate rocks. Pelitic rocks are the most abundant lithologies. Pelitic sequence is mostly made up of slates, phillites, micaschists, garnet schists, garnet andalusite (± sillimanite, ± kyanite) schists, garnet staurolite schists, mica hornfelses, garnet hornfelses, garnet andalusite (± fibrolite) hornfelses, cordierite (± andalusite) hornfelses, cordierite K-feldspar hornfelses and sillimanite Kfeldspar hornfelses. Major plutonic rocks of this area are granitoids, diorites and gabbroids, which

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Beni & Beni, Curr. World Environ., Vol. 7(1), 55-59 (2012)

intruded by aplo-pegmatitic and silicic veins (Figure 1). Metamorphic zonation and isogrades of Garnet rocks in study area In this area we can’t completely divide zonation of contact and regional metamorphic. In some places that contact metamorphic has influenced to low degree regional metamorphic rocks, contact metamorphic zonations are clearly appear, but when contact and regional metamorphic have a same degree or regional metamorphic has high degree than contact metamorphic, we can’t distinguish them easily. The metamorphic reaction and thermobarometric studies of metamorphic rocks have shown that garnet mica schist forming at 4.3 ±0.5 Kbar and 568-586 ºC and garnet hornfelses at 2.5 ±0.1 Kbar and 539-569 ºC [3]. Regional metamorphic rocks Low grade rocks (Chl zone) The lowest-grade rocks are very fine grained black,green or cream colored slates and phyllites, interlayered with carbonate rocks and quartzites. Slates contain Quart, Sericite, Chlorite, Graphite, Iron oxides. Phyllites contain Quart, Muscovite, Chlorite, Plagioclase, +/-Garnet, +/Biotite, as well as accessory Tourmaline, Calcite and Iron oxides. Samples of metamorphic reaction that have shown in this zone are: Kln + 2Qtz

→ Prl + H2O

...(4)

2Ms + 6Qtz + 2H+ → 3Prl + 2K

...(5)

Biotite and garnet zone These rocks are medium to coarse grained and their common texture is lepidoporphyroblastic with a usual crenulation cleavage. This zone divided in two sub zone, biotite and garnet zone. They are composed of Quartz, Biotite, Garnet (up to 10 mm in size), Muscovite, Chlorite, with accessory Plagioclase, Graphite, Tourmaline, Apatite, Calcite and Iron oxides (Figure 2). Common porphyroblasts are Garnet, Muscovite and Chlorite. Garnet crystals have complex relationship to deformation, i.e. they are pre-, syn- and post-tectonic. The metamorphic reaction and thermobarometric studies of metamorphic rocks have shown that garnet mica schist forming at 4.3 ±0.5 Kbar and 568-586 ºC [3]. Chl + Ms → Grt + Bt + Qtz + H2O 2Chl + 4Qtz → 3Grt + 8H2O

...(6) ...(7)

Chiastolite zone These rocks are medium to coarsed grained with a common lepidoporphroblastic texture. Their common minerals are Quartz, Biotite, Andalusite (up to 20 cm length), Garnet, Muscovite and minor Graphite, Chlorite, Plagioclase, Tourmaline, Apatite, Sillimanite and Iron oxides (Figure 3). Grt + Ms + Qtz And + Bt + H2O

...(8)

Staurolite zone These rocks are composed of Quartz,

Table 1: Minerals assemblage in metamorphic zonation Sillimanite zone

Staurolite zone

Andalusite zone

Garnet zone

Biotite zone

................................................................................................................................................................... ............................................ ........................................................................................................................................... ............................................................................................................................................. .................................................................................................................... ............................................................... ................................. ............................................................... ...........................

Chlorite zone Quartz Chlorite Biotite Muscovite Garnet Andalusite Staurolite Kyanite Sillimanite

Beni & Beni, Curr. World Environ., Vol. 7(1), 55-59 (2012)

57

Fig. 1: Simplified zonation map of the Hamadan area [10]

Figure 2: Mineral assemblage in Garnet zone.

Fig. 3: Mineral assemblage in Chiastolite zone

Fig. 4: Mineral assemblage in Staurolite zone

Fig. 5: Mineral assemblage in Sillimanite muscovite zone

Fig. 6: First mineral assemblage in Sillimanite- potassium feldspar zone

58

Beni & Beni, Curr. World Environ., Vol. 7(1), 55-59 (2012) Staurolite, Garnet, Biotite, Muscovite, Chlorite, Plagioclase, Graphite and Tourmaline (Figure 4). Their common texture is lepidoporphyroblastic with porphyroblasts of garnet, staurolite (up to 15 cm in legnth). Grt + Chl +Ms + Qtz → St + Bt + H2O

...(8)

Sillimanite muscovite zone Sillimanite andalusite schists contain Quartz, Sillimanite (± andalusite), Biotite, Muscovite, Garnet, Plagioclase and Opaque minerals (Figure 5). Grt + Ms + Qtz →Sil + Bt + H2O Fig. 7: Second mineral assemblage in Sillimanite- potassium feldspar zone

Fig. 8: Mineral assemblage in Cordierite zone

...(8).

Sillimanite- potassium feldspar zone High grade schists and Migmatites are in this zone. The high grade schists in the regional metamorphic sequence contain Sillimanite, Quartz, Biotite, Muscovite, Garnet, Plagioclase, Potassium feldspar, ±Andalusite,±Kyanite, ±Staurolite (Figure 6). Migmatites are a sequence of metatexitediatexite rocks with various structures such as stromatic, schollen, schlieric and massive. The melanosome mineralogy of the most of the metatexites is very similar to high grade Garnet sillimanite (± andalusite and kyanite) schists but Cordierite-bearing interlayers occur, too (Figure 7). Leucosome of migmatites have granoblastic texture and contain Quartz, Plagioclase, Muscovite and ±Garnet. Bt + Ab + Sil + Qtz → Grt + Kfs + L Contact metamorphic rocks Protoliths of the contact metamorphic rocks are similar to those in the regional metamorphic sequence and include abundant metapelitic rocks. Two metamorphic zones are widespread around plutonic bodies.

Fig. 9: Mineral assemblage in Cordierite potassium feldspar zone

Cordierite zone The major rock types in this zone are Cordierite hornfelses. This rocks have porphrogranoblastic texture that containing Quartz, Biotite, Muscovite,contact Cordierite (± andalusite), Plagioclase, Garnet, Tourmaline and Opaque

Beni & Beni, Curr. World Environ., Vol. 7(1), 55-59 (2012) CONCLUSION

minerals (Figure 8). garnet hornfelses forming at 2.5 ±0.1 Kbar and 539-569 ºC [3]. Chl + H2O → Grt + H2O

...(7)

Cordierite potassium feldspar zone The typical mineral assemblage of these rock is Quartz, contact Cordierite (Crd2), orthoclase, Biotite, minor Plagioclase, Garnet and Opaque minerals (Figure 9). Bt + Sil (± And) + Qtz → Crd + Kfs + H2O

...(7)

59

We can divide Hamadan metamorphic rocks in three groups: regional metamorphic rocks, contact metamorphic rocks and migmatites. In this area regional metamorphic zones are Chlorite± Biotite zone, Biotite± Garnet zone, Andalusite zone, Staurolite zone, Staurolite± Andalusite zone, Sillimanite- Muscovite zone and SillimanitePotassium feldspar± Cordierite zone, also contact metamorphic zones are Cordierite zone and Cordierite- Potassium feldspar zone.

Minerals assemblage in metamorphic zonation are shown in table 1. REFERENCES

1.

2.

3.

4.

5.

Locock, A., An Excel spreadsheet torecast analyses of garnet end-member componets, and a synopsis of the crystal chemistry of natural silicate garnets. Computers and Geosciences. V, 34: 1769-1780 (2008). Li Li, H., Kuang, X., Mao, A., Li, Y. and Wang, S., Study of local structures and optical spectra for octahedral Fe3+ centers in a series of garnet crystals A3B2C3O12 (A = Cd, Ca; B = Al, Ga, Sc, In; C = Ge, Si). Chemical Physics Letters, 484: 387-391 (2010) Sepahi, A. A., Whitney D. L. and Baharifar A. A., , Petrogenesis of andalusite-kyanitesillimanite veins and their host rocks, Sanandaj-Sirjan metamorphic belt, Hamadan, Iran. J. Met. Geol, 22:119-134 (2004). Thompson, A.B., A note on the kaolinitepyrophyllite equilibrium. Am. J. Sci, 268: 454458 (1970). Frey, M., Progressive Low grade metamorphism of a Black Shale Formation, Central Swiss Alps, with special reference

6.

7. 8.

9.

10.

to pyrophyllite and margarite bearing assemblages. J. Petrol, 19: 95-135 (1978). Whitney, D.L., Mechum, T.A. and Dilek, Y.R., Progressive metamorphism of pelitic rocks from protolith to granulite facies. Dutchess County, New York, USA: Constraints on the timing of fluid infiltration during regional metamorphism. J. Met. Geol, 74: 163-181 (1996). Kretz, R., Metamorphic crystallization. John Wiley and Sons, 507 (1994). Yang, P. and Pattison, D., Genesis of monazite and Y zoning in garnet from the Black Hills, South Dakota. J. Lithos, 88: 233-253 (2006). Norlander, B.H., Whitney, D.L., Teyssier, C. and Vanderhaeghe, O., Partial melting and decompression of the Thor-Odin Dome, Shuswap metamorphic core complex. Canada. Cord. Lithos, 61: 103-125 (2002). Sepahi, A.A., Typology and petrogenesis of granitic rocks in the Sanandaj-Sirjan metamorphic belt, Iran: With emphasis on the Alvand plutonic complex. N. Jb. Geol. Palaton. Abn, 247: 295-312 (2008).

Current World Environment

Vol. 7(1), 61-67 (2012)

Correlation of Crystal Parameter with Vibrational Data of New Three Tetramethylammonium Salts S. GHAMMAMY1*, SADJAD SEDAGHAT1 and H. SAHEBALZAMANI2 1

Faculty of Science, Islamic Azad University, Malard Branch, Malard (Iran). 2 Departments of Chemistry, Faculty of Science, Islamic Azad University, Ardabil Branch, Ardabil (Iran). (Received: February 25, 2012; Accepted: March 25, 2012) ABSTRACT

Examination of the solid state infrared spectra of the tetramethylammoniumcation in salts shows correlation of infrared spectral properties with C–H···X hydrogen bonding and crystal habits in these tetramethylammonium salts. The IR predicted crystal habits are comprised by experimental and theoretical data. A good relation between three data has been found. The C–H stretching region characteristic hydrogen bonding shifts in the above salts. In this research three complexes of tetramethylammoniumcation have been synthesized and the structures of them have been analyzed by correlation of vibrational data with crystal structures. These correlation shows that crystal symmetry (Tetrahedral), cation distortion (undistorted), site symmetry (D2d), unite cell symmetry (D4h7) for (CH3)4NPF6 and crystal symmetry (Tetrahedral), cation distortion (distorted), site symmetry (D2d), unite cell symmetry (D4h7) for (CH3)4NOH and crystal symmetry (Tetrahedral), cation distortion (undistorted), site symmetry (D2d), unite cell symmetry (D4h7) for (CH3)4NF.

Key words: Crystal parameter, Vibrational data, Tetramethylammonium salts.

INTRODUCTION Tetramethylammonium compounds have many applications in science and biology. It is extremely difficult, if not impossible, to prepare single crystals of tetramethylammonium salts suitable for diffraction studies; the available methods of preparation give microcrystalline powders that are not suitable for X-ray single crystal diffraction. Scientists’ effort to find and use simple substituted methods for studying crystal habits of tetramethylammonium salts. One of the suggested methods is the use of infrared spectra and assigning of it by symmetry. The vibrational spectrum of the tetramethylammonium (Me4N+) ion has been the subject of several publications during the last four decade1-3. Many studies had been done on the vibrational spectra of tetramethylammonium salts and ahowed that it possible to correlate of infrared spectral properties with C-H…X hydrogen bonding and crystal habit in tetramethylammonium salts

such as Harmon et al., 4-6. On the base of these studies founds that the C-H stretching region gives characteristic hydrogen bonding shifts in the tetramethylammonium salts; this effect is particularly intense in the halideand hydroxidecompounds. The C-H deformation modes in the 1400-1500 cm-1 region and N-C breathing band near 950 cm-1 show perturbations which can be qualitatively used to identify crystal type, and which can be reasonably explained by site symmetry and factor group analysis considerations. Intensity changes in some absorption can be empirically related to steric, size and packing effects. Infrared spectra are correlated with known crystal structures and bond distances for ten of the salts in this paper. MATERIAL AND METHODS All chemicals were of reagent grade quality such as(CH3) 4NOHwas purchased from Merck company. Tetramethyl ammonium

62

Ghammamy et al., Curr. World Environ., Vol. 7(1), 61-67 (2012)

fluoride,(CH 3) 4NFwas synthesized by reported method7. The substrates and the solvents were used after drying and purifying by distillation by usual procedures. The middle fractions were collected after rejecting the head and the tail portions. The IR spectra were recorded on a Shimadzu model 420 spectrophotometer. The UV/ Visible measurements were made on a Shimadzu model 2100 spectrometer. Proton, 13C, 19F NMR were carried out on a Bruker AVANCE DRX 500 spectrometer at 500, 125, 470.66 MHz. All the chemical shifts are quoted in ppm using the highfrequency positive convention; 1H and 13C NMR spectra were referenced to external SiMe4 and 19F NMR spectra to external CFCl 3. This salt was estimated iodometrically after oxidizing the compound with acidic persulphate solution. Fluoride content was determined gravimetrically as PbClF8-9. The percentage compositions of carbon, hydrogen and nitrogen were obtained from the microanalytical Laboratories, Department of Chemistry, OIRC, Tehran. Synthesis of tetramethylammonium compounds (CH3)4NPF6was prepared inside a glove box purged with argon. PF5 was dissolved in dry acetonitrile (25 ml) in a polyethylene beaker and a stoichiometric amount of tetramethylammoniumfluoride was added with stirring at room temperature. Within 5 minutes a solution formed which upon refrigerating, gave solid (CH3)4NPF6, which was isolated by filtration. The solid was washed with dry isopropanol and diethyl ether, and dried under vacuum for 1 hour. UV/Visible, 19F-NMR, 13 C-NMR and 1 H-NMR were used for characterization of these compoundsformula. For (CH 3) 4 NPF 6green microcrystalline was obtained. The compound was finally dried in vacuum over phosphorous penfluoride. The yield of (CH 3) 4N[MoCl 5 F] was ca 98%. Satisfactory elemental analysis was obtained.For (CH3)4NPF6, IR data and spectrum for cation and anions have been assigned to different modes, respectively. (Fig.1, Table 1) For (CH3)4NOH,IRdata and spectrum for cation and anion have been assigned to different modes, respectively.(Fig. 2, Table 2)

For (CH3)4NF,IR data and spectrum for cation and anion have been assigned to different modes, respectively.(Fig. 3, Table 3) Structure solution and refinement The structure of crystallized compounds have been solved by direct methods and refined by full-matrix-least squares techniques on F2. All non-hydrogen atoms were refined anisotropically. The position of hydrogen atom was assigned an isotropic thermal parameter. Corrections for the LP as well as the empirical correction for absorption using the SADABS programs were applied. All structural calculations were carried out by using the SHELXTL V. 5.10 structure determination software. The intensity data were collected on a SIMENS SMART CCD diffractometer with graphitemonochromated Mo KĂĄ radiation. The crystal structure was solved by directed methods9. RESULTS AND DISCUSSION The crystal and molecular structure of tetramethylammoniumcompounds, have been determined at 130(2) K by X-ray diffraction. X-ray data clearly demonstrate inequality between different bonds that is responsible for the higher reactivity of these compounds over similar agents in terms of the amount of solvent required, short reaction times and high yields. The reason for this inequality is due to the CHâ&#x20AC;ŚN hydrogen bond that forms between the methyl hydrogen of the cation and hydroxide or halide atoms of the anion10. This type of hydrogen bonding in tetramethylammonium salts has been studied by Harmon et al.The IR spectrum and hydrogen bonding of these compounds is similar to the other tetramethylammoniumsalts that show the existence of hydrogen bonding. Halo complexes of transition metals are also as general purpose, stoichiometric oxidant in synthetic organic chemistry,and a variety of reaction pathways including both atom-transfer and electron-transfer are involved12. The results of chemical analyses of the(CH 3 ) 4 NPF 6 green product revealed the occurrence of C:H:N in the atomic ratio, while that of chemical determination of the different state of

Ghammamy et al., Curr. World Environ., Vol. 7(1), 61-67 (2012) phosphorous by iodometry conspicuously showed the presence of phosphorous. It may be emphasized that the chemical estimation of oxidation state of a metal, capable of displaying variable oxidation numbers, is particularly important and crucial in assessing its actual oxidation state in a specific compound11. Also magnetic susceptibility measurements show that (CH3)4NPF6has two odd

63

electrons. Magnetic moment is 2.91BM that to confirm to amount mentioned in sources for phosphorous compound and d 2 electronic configuration of central metal. The IR spectra of the (CH3)4NPF6recorded both in KBr and in nujol media showed the characteristics of tetramethylammonium (CH3)4N+ ion, and this part of the spectrum is similar to that observed for (CH 3 ) 4 N + in the case of

Table 1: The frequencies (cm-1) and assignment of cation and anion of (CH3)4NPF6 υ, cm-1

3430 3370 3102 3015 2990 2772 2640 2470 1838

Assignment

Intensity

υ, cm-1

Assignment

Intensity

(CH3)4N+

(w)

1470 1400 1279 470 446

ν15 ν15 νrock ν19 ν19

(s) (m) (w) (m) (m)

νCH3 + ½19 νCH3 + ½8 νCH3, asym. Str. ν13, νCH3, asym. Str ν14, νCH3, asym. Str. ν14, νCH3, asym. Str ν7 + ν16 ν3 + ν8+ ν16 ν8 + ν15

(w) (m) (s) (w) (s) (w) (w) (w)

PF6νasP-F νsP-F ν P-F

935 904 636

(s) (s) (s)

Table 2: The frequencies (cm-1) and assignment of cation and anion of (CH3)4NOH υ, cm-1

Assignment

Intensity

(CH3)4N+

3430 3370 3102 3015 2990 2772 2640 2470 1838

νCH3 + ν19 νCH3 + ν8 νCH3, asym. Str. ν13, νCH3, asym. Str ν14, νCH3, asym. Str. ν14, νCH3, asym. Str ν7 + ν16 ν3 + ν8+ ν16 ν8 + ν15

(w) (m) (s) (w) (s) (w) (w) (w) (w)

υ, cm-1

Assignment

1470 1400 1279 470 446

ν15 ν15 νrock ν19 ν19

Intensity (s) (m) (w) (m) (m)

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Ghammamy et al., Curr. World Environ., Vol. 7(1), 61-67 (2012)

tetramethylammoniumsalt. The additional bands have been appeared and have been assigned respectively [11].Which owe their origins to the presence of coordintatedphosphorous and fluoride group at PF6-ion. Table 1 shows the assignment of (CH 3) 4NPF 6IR spectrum. Thus considering the results of elemental analyses, chemically estimated oxidation state phosphorous, electrochemical analyses and IR spectral studies it may be safely inferred that the brown reduced product is (CH 3 ) 4 NPF 6 with the metal occurring as phosphorous. This again lends support to our notion that the phosphorous of(CH3)4NPF6 is reduced to a Molibden species in the oxidations of organic substrates studied herein. Calculation of structure of PF6- by DFT method shows the declined trigonal structure. Similar results have been found for (CH3)4NOHand (CH3)4NFcompound. Infrared and Raman spectra of tetrahedral M(CH 3 ) 4 molecules have been discussed in considerable details.It is commonly assumed that tetramethylammonium ion on the average has Td symmetry, and an approximate tetrahedral C 4N skeleton has been established for many (CH 3 ) 4 N + salts by means of X-ray

crystallography. In this approximation, the 45 degrees of vibrational freedom of the ion are distributed on the symmetry species of point in this way by: Ãvib=3A1+1A2+4E+4T1+7 T2. The Me4N+ ion has 19 normal vibrations which belong to the following irreducible representations of its symmetry group Td: 3A1+A2+4E+4T1.From group theoretical it follows that of all these vibrations only those with T2 symmetry are infrared active, whereas in isotropic Raman scattering only the A1 modes and in anisotropic scattering only the E and T2 modes are allowed. Species of this type have seven infrared active T2 bonds under Td symmetry, but formation of hydrogen bonding between tetramethylammonium and suitable anions can distort Td symmetry of this cation. At this state the infrared spectrum may be modified through the appearance of previously forbidden bands or the splitting of bands can arise from the coupling of the vibrations of molecules in the same unit cell. By examination of the solid state infrared spectrum of tetramethylammonium ion salt it is possible to predict the lattice, the approximate size of the anion, the closeness of approach of the cation to each other, the presence or absence of cation to anion hydrogen bonding and whether or not the cation is distorted from tetrahedral. The detail assignment of IR spectrum of tetramethyl ammonium compounds, show (Fig. 1, 2, 3). The IR

Table 3: The frequencies (cm-1) and assignment of cation and anion of (CH3)4NF υ, cm-1

Assignment

Intensity

(CH3)4N+

3430 3370 3102 3015 2990 2772 2640 2470 1838

νCH3 + ν19 νCH3 + ν8 νCH3, asym. Str. ν13, νCH3, asym. Str ν14, νCH3, asym. Str. ν14, νCH3, asym. Str ν7 + ν16 ν3 + ν8+ ν16 ν8 + ν15

(w) (m) (s) (w) (s) (w) (w) (w) (w)

υ, cm-1

Assignment

Intensity

1470 1400 1279 470 446

ν15 ν15 νrock ν19 ν19

(s) (m) (w) (m) (m)

Ghammamy et al., Curr. World Environ., Vol. 7(1), 61-67 (2012)

Fig. 1: The IR spectrum regions of the (CH3)4NPF6

Fig. 2:The IR spectrum regions of the (CH3)4NOH

Fig. 3: The IR spectrum regions of the (CH3)4NF

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Ghammamy et al., Curr. World Environ., Vol. 7(1), 61-67 (2012)

D4h7 D4h7 D4h7 D 2d D 2d D 2d Undis Dis Undis Tet Tet Tet 2.93 2.75 2.93 3.20 3.61 3.20

Unit6 site Cation5 Crystal4 0.5rmin3C-X 2 cal C-X

r B B B

S D S

-

-

D T D

3.04 3.78 3.04

C-X

r obsd1 C-N

νB ν rock CH3 ν rot δsym C-H

(CH3)4NPF6 (CH3)4NOH (CH3)4NF

νs

C-H

Parameters Crystalline Structure Classification of IR Spectrum Compound

Table 4: IR specification of tetramethylammonium salts

Parameters Symmetry

cell

66

specification of (CH 3 ) 4 NPF 6 , and symmetry correlations shows that this compound is crystallized such as (CH3)4NClO4 and must have the same crystal habits and parameters. The IR spectrum of the (CH3)4NOHand symmetry correlations shows that this compound is crystallized such as (CH3)4NCl and must have the same crystal habits and parameters.The IR spectrum of the (CH3)4NFand symmetry correlations shows that this compound is crystallized such as (CH3)4NClO4 and must have the same crystal habits and parameters. The assignments of the IR spectra in tables 1, 2, 3 refer to the cation and anion spectra. The specification of the tetramethylammonium compounds, on the base of IR spectra splitting and Harmon regions shows Table 3.As told, if the infrared spectra of the tetramethylammonium ions in crystalline salts correlated with known crystal structures, it might be possible to predict the crystal habit of salts where diffraction data are not available. CONCLUSSIONS We published these three complexes separately, but now we compare their spectroscopic data especially electronic transitions. As seen the number and shapes of transitions completely different with three similar ions. The salts of [(CH3)4N] were synthesized in one step and characterized by elemental analysis, IR, UV/Visible, and 81F-NMR techniques. Production of these compounds show the ability of salts in bromide addition to transition metal and main group elements compounds. The optimized structures are in good agreement with the available experimental results.These correlation shows that crystal symmetry (Tetrahedral), cation distortion (undistorted), site symmetry (D2d), unite cell symmetry (D4h 7) for (CH3)4NPF6 and crystal symmetry (Tetrahedral), cation distortion (distorted), site symmetry (D2d), unite cell symmetry (D4h7) for (CH3)4NOH and crystal symmetry (Tetrahedral), cation distortion (undistorted), site symmetry (D2d), unite cell symmetry (D4h7) for (CH3)4NF. ACKNOWLEDGMENTS The authors wish to express their sincere thanks to Dr.Gh. RezaeiBehbahani and Islamic Azad University, for their assistance.

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REFERENCES

1.

2. 3. 4. 5. 6. 7.

Crosthwaite J. M., Muldoon M. J., Dixon J. K.,Anderson J. L. andBrennecke J. F., J. Chem. Thermodyn., 37: 559 (2005) Ghammamy S. and Dastpeyman S. Transition Metal Chemistry, 31: 482 (2006). A. Wahab, Orient. J. Chem., 27(3): 1199-1202 (2011). Harmon K. M., Gennick I. and Madeira S. L.J. Phys. Chem.,78: 1845 (1974). Mahjoub A. R., Ghammami S. and Kassaee M. Z.Tetrahedron Lett.,44: 4557 (2003). Granier W., Vilminot S., Vidal J. D. and Cot L.J. Fluor. Chem., 19: 123 (1981). Antharjanam P. K. S., Jaseer M., Ragi K. N. and Prasad E.,J. Photochem. Photobiol. A: Chem., 203: 50 (2009).

8.

9. 10. 11. 12.

13.

Christe K. O., Wilson W. W., Wilson R. D., Bau R. and Feng J.,J. Am. Chem. Soc., 112: 7619 (1990). Zhao D. Z., Fei R. and Scopelliti P., J. Inorg.Chem., 43: 2197 (2004). Mahjoub A. R., Ghammami S., Abbasi A. R., Hossainian A J. Chem. Res., 200: 48 (2000). Ghammamy S. and RahnamaBaghy M.Russ. J. Inorg. Chem., 32:456 (2007). Anouti M., Caillon-Caravanier M., Dridi Y., Jacquemin J., Hardacre C. and Lemordant D., J. Chem.Thermodyn., 41: 799 (2009). Ghammamy S., Wing-Tak W., Rahnamabaghy M., Mehrani K., Afrand H. and DastpeymanS.J. Coord. Chem., 61: 3225 (2008).

Current World Environment

Vol. 7(1), 69-77 (2012)

Synthesis and Investigation of a Novel pH- and Salt-Responsive Superabsorbent Hydrogel Based on Pectin MOHAMMAD SADEGHI*, ESMAT MOHAMMADINASAB and FATEMEH SHAFIEI Department of Chemistry, Science Faculty, Islamic Azad University, Arak Branch, Arak (Iran). (Received: March 25, 2012; Accepted: April 13, 2012) ABSTRACT In the present paper, attention is paid to synthesis and investigates swelling behavior of a superabsorbent hydrogel based on Pectin (Pec) and polyacrylic acid (PAcA). acrylic acid (AcA) was graft copolymerized onto Pectin backbones by a free radical polymerization technique using ammonium persulfate (APS) as initiator and methylene bisacrylamide (MBA) as a crosslinker. A proposed mechanism for hydrogel formation was suggested and the structure of the product was established using FTIR and SEM spectroscopies. Under the optimized conditions concluded, maximum capacity of swelling in distilled water was found to be 348 g/g. Absorbency of the synthesized hydrogels was also measured in NaCl and CaCl2 salt solutions. Results indicated that the swelling ratios in compare to water decreased with an increase in the ionic strength of solution. In addition, swelling capacity was conducted in solutions with pH ranged from 1 to 13. The H-Pecpoly(sodium acrylate) hydrogel exhibited a pH-responsiveness character so that a swellingdeswelling pulsatile behavior was recorded at pHs 3 and 9.

Key words: Pectin, Hydrogel, pH- and salt-responsive, Acrylic acid monomer.

INTRODUCTION Highly swelling polymers, i.e. super absorbent hydrogels, are hydrophilic, three dimensional networks that can absorb water in the amount from 10% up to thousands of times their dry weight. They are widely used in various applications such as hygienic, foods, cosmetics, and agriculture1. This accounts for increase in the worldwide production of superabsorbent polymers (SAPs) from 6000 tons in 1983 to 450000 tons in 1996 2-4. Nowadays, the worldwide production of SAPs is more than one million tons in year. Hence, synthesis and characterization of superabsorbent hydrogels is the main goal of the several research groups in the world3-6. Pectin is a naturally occurring biopolymer that is finding increasing applications in the pharmaceutical and biotechnology industry. It has been used successfully for many years in the food and beverage industry as a thickening agent, a

gelling agent and a colloidal stabiliser. Pectin also has several unique properties that have enabled it to be used as a matrix for the entrapment and/or delivery of a variety of drugs, proteins and cells. The modification of natural polymers is a promising method for the preparation of superabsorbt hydrogels. Graft copolymerization of vinyl monomers onto natural polymers is an efficient approach to achieve these materials. Superabsorbing resins were first developed with a view to utilizing agricultural materials, and are typed by the hydrolyzed starch-g-poly(acrylonitrile), HSPAN 6 . Since then, starches from different resources as well as other polysaccharides, for example, cellulose 8, hydroxyethyl cellulose, agar , sodium alginate and guar gum were graft copolymerized to achieve water absorbing polymers. Polyacrylonitrile (PAN), polyacryamide, and poly(acrylic acid) 10-11 have been frequently grafted, mostly onto starch, using different initiators especially the ceric-saccharide redox system12.

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Radical polymerization, however, has several disadvantages. The reproducibility of this method is poor, and there is little control over the grafting process, so the molecular weight distribution is polydisperse. In addition, the necessity for inert gases (e.g., argon) to prepare an oxygen-free atmosphere and the need for initiators, toxic and/ or expensive monomers, and crosslinkers are other disadvantages of free-radical polymerization reactions. These problems have been reviewed in detail 12-13. For the first time, Fanta et al. 14, with a new method, tried to synthesize of HSPAN superabsorbent hydrogel. They indicated by a solubility test that crosslinks were formed during graft copolymerization, by coupling of the two growing PAN radicals, and during saponification, by the attack of Pectin alkoxide ions on the nitrile groups as the initioation reaction of nitrile polymerization in the early stages of saponification. The nitrile groups of PAN were converted to a mixture of hydrophilic carboxamide and carboxylate groups during alkaline hydrolysis followed by in situ crosslinking of the grafted PAN chains. The initially formed oxygen–carbon bonds between the Pectin hydroxyls and nitrile groups of the PAN chains remained crosslinking sites. Then, Fanta and Doane 14 attempted to extend this idea to the preparation of superabsorbent hydrogels by the saponification of PAN in the presence of polyhydroxy polymers. Finally, Yamaguchi et al.115 reported the preparation of superabsorbing polymers from mixtures of PAN and various saccharides or alcohols. In this investigation, we paid attention to the synthesis and investigation of a superabsorbent based on Pectin and PAcA. The effects of the variables reaction on the swelling properties as well as the salt and pH sensitivity of the hydrogels were investigated. EXPERIMENTAL Materials Pectin (chemical grade, MW 50000) was purchased from Merck Chemical Co. (Germany). Acrylic acid (AcA, Merck) was used after vacuum distillation. Ammonium persulfate (APS, Merck) and Methylene bisacrylamide (MBA, Fluka) were used as received. All other chemicals were of analytical grade. Preparation of hydrogel

Preparation of hydrogel A facial one step preparative method was used for synthesis of Pec-poly(sodium acrylate) hydrogel, Pec-poly(NaAcA), hydrogel. Pectin(0.501.5 g) was added to a three-neck reactor equipped with a mechanical stirrer (Heidolph RZR 2021, three blade propeller type, 50-500 rpm), including 35 mL doubly distilled water. The reactor was immersed in a thermostated water bath. After complete dissolution of Pectin to form a homogeneous solution , a definite amount of APS solution (0.15 g in 5 mL H2O) was added to pectin solution and was allowed to stir for 10 min. After adding APS, certain amounts of monomer (AcA 1.50 g in 5 mL H2O ) was added to the pectin solution. MBA solution (0.08 g in 5 ml H2O) was added to the reaction mixture after the addition of monomer and the mixture was continuously stirred. After 60 min, the reaction product was allowed to cool to ambient temperature and neutralized to pH 9 by addition of 1N sodium hydroxide solution. The hydrogel was poured to excess non solvent ethanol (200 mL) and kept for 3 h to dewater. Then ethanol was decanted and the product scissored to small pieces. Again, 100 mL fresh ethanol was added and the hydrogel was kept for 24 h. Finally, the filtered hydrogel is dried in oven at 60oC for 10 h. After grinding using mortar, the powdered superabsorbent was stored away from moisture, heat and light16. Swelling measurements using tea bag method The tea bag (i.e. a 100 mesh nylon screen) containing an accurately weighed powdered sample (0.5 ± 0.001 g) with average particle sizes between 40–60 mesh (250-350 m ) was immersed entirely in distilled water (200 mL) or desired salt solution (100 mL) and allowed to soak for 3 h at room temperature. The tea bag was hung up for 15 min in order to remove the excess fluid. The equilibrated swelling (ES) was measured twice using the following equation17:

...(1) The accuracy of the measurements was ±3%.

Sadeghi et al., Curr. World Environ., Vol. 7(1), 69-77 (2012) Absorbency at various pHs Individual solutions with acidic and basic pHs were prepared by dilution of NaOH (pH 13.0) and HCl (pH 1.0) solutions to achieve pH≥6.0 and pH<6.0, respectively. The pH values were precisely checked by a pH-meter (Metrohm/620, accuracy ±0.1). Then, 0.5 ± 0.001 g of the dried hydrogel was used for the swelling measurements according to Eq. 1. pH-sensitivity pH-sensitivity of the hydrogel was investigated in terms of swelling and deswelling of the final product at two basic (pH 9.0) and acidic (pH 3.0) solutions, respectively. Swelling capacity

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of the hydrogels at each pH was measured according to Eq. 1 at consecutive time intervals (50 min). Instrumental analysis Fourier transform infrared (FTIR) spectra of samples were taken in KBr pellets, using an ABB Bomem MB-100 FTIR spectrophotometer (Quebec, Canada), at room temperature. The surface morphology of the gel was examined using scanning electron microscopy (SEM). After Soxhlet extraction with methanol for 24 h and drying in an oven, superabsorbent powder was coated with a thin layer of gold and imaged in a SEM instrument (Leo, 1455 VP).

Fig. 1: FTIR spectra of pure pectin (a) and H-Pec-poly(sodium acrylate) hydrogel (b).

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Sadeghi et al., Curr. World Environ., Vol. 7(1), 69-77 (2012) RESULTS AND DISCUSSION

Synthesis of hydrogels A general reaction mechanism for Pecpolyacrylic acid hydrogel formation is shown in Scheme 1. At the first step, the thermally dissociating initiator, i.e. APS, is decomposed under heating to produce sulfate anion-radical. Then, the anion-radical abstracts hydrogen from one of the functional group in side chains (i.e. OH) of the substrate to form corresponding radical (alkoxide radicals). Then, these macroalkoxides initiate crosslinking reaction between some adjacent polyacrylic acid pendant chains. In addition,

crosslinking reaction was carried out in the presence of a crosslinker, i.e., MBA, so that a three dimensional network was obtained. Scheme 1. FTIR spectroscopy The monomer grafting was confirmed by comparing the FTIR spectra of the pectin substrate with that of the grafted products in Fig. 1. The bands observed at 1643 cm-1 and 1705 cm-1 can be attributed to C=O stretching in carboxamide and carboxylate functional groups of crosslinker and grafted acrylic acid monomers on to pectin backbone respectively. The band observed at 1553

Fig. 2: SEM photograph of the pure Pectin(a), and H-Pec-poly(sodium acrylate) hydrogel. Surfaces of hydrogel was taken at a magnification of 2000, and the scale bar is 10 ĂŹm.

Sadeghi et al., Curr. World Environ., Vol. 7(1), 69-77 (2012) cm-1 due to asymmetric stretching in carboxylate anion that is reconfirmed by another peak at 1411 cm-1 which is related to the symmetric stretching mode of the carboxylate anion20.

morphologies. The surface morphology of the samples was investigated by scanning electron microscopy. Fig. 2 shows an SEM micrograph of the polymeric hydrogels obtained from the fracture surface. The hydrogel has a porous structure. It is supposed that these pores are the regions of water permeation and interaction sites of external stimuli with the hydrophilic groups of the graft copolymers.

Swelling, g/g

Scanning electron microscopy One of the most important properties that must be considered is hydrogel microstructure

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Swelling, g/g

Fig. 3: Effect of pH of buffered solution on swelling of H-Pec-poly(sodium acrylate) hydrogel.

Time (min) Fig. 4: On-off switching behavior as reversible pulsatile swelling (pH 9.0) and deswelling (pH 3.0) of the hydrogel.

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Sadeghi et al., Curr. World Environ., Vol. 7(1), 69-77 (2012) anions are protonated, so the main anion-anion repulsive forces are eliminated and consequently swelling values are decreased19. At higher pHs 5-9, some of carboxylate groups are ionized and the electrostatic repulsion between COO - groups causes an enhancement of the swelling capacity. Again, a charge screening effect of the counter ions (cations) limit the swelling at higher basic pHs (pHs>9).

Swelling, g/g

Effect of pH on Equilibrium Swelling Since the H-Pec-poly(sodium acrylate) hydrogel comprise anionic carboxylate groups, they exhibit sharp swelling changes at a wide range of pHs. Therefore, the equilibrium swelling of H-Pecpoly(sodium acrylate) hydrogel was measured at various buffer solutions with pH ranged from 1 to 13 (Fig. 3). Under acidic pHs, most of the carboxylate

Time (min)

Swelling, g/g

Fig. 5: swelling窶電eswelling cycle of the H-Pec-poly(sodium acrylate) hydrogel in distilated water and 0.9 wt% sodium choloride salt.

Time (min) Fig. 6: swelling窶電eswelling cycle of the H-Pec-poly(sodium acrylate) hydrogel in sodium choloride and calcium choloride solution(0.9 wt%) .

Sadeghi et al., Curr. World Environ., Vol. 7(1), 69-77 (2012) pH-responsiveness Behavior of the Hydrogel In this series of experiments, the pHdependent swelling reversibility of the H-Pecpoly(sodium acrylate) hydrogel was examined in two acidic and basic buffered solutions. Fig. 4 shows the reversible swelling-deswelling behavior of the hydrogel at pHs 3.0 and 9.0. At pH 9.0, the hydrogel swells due to anion-anion repulsive electrostatic forces, while at pH 3.0, it shrinks within a few minutes due to ½screening effect½ of excess cations. This sudden and sharp swelling-deswelling behavior at different pH values makes the system to be highly pH-responsive and consequently it may be a suitable candidate for designing controlled drug delivery systems. This behavior has also been observed in the case of commercial acrylic acidbased SAPs 15 as a standard crosslinked polyelectrolyte. Similar swelling-pH dependencies have been reported in the case of other hydrogel systems 21-22. Salt-sensitivity of H-Pec-poly(sodium acrylate) hydrogel The swelling capacity of superabsorbent hydrogels could be significantly affected by various factors of the external solutions such as its valencies and salt concentration. The presence of ions in the

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swelling medium has a profound effect on the absorbency behavior of the superabsorbent hydrogels. Many theories were reported in the case of swelling behavior of ionic hydrogels in saline solutions. The simplest one of the theories is Donnan equilibrium theory. This theory attributes the electrostatic interactions (ion swelling pressure) to the difference between the osmotic pressure of freely mobile ions in the gel and in the outer solutions. The osmotic pressure is the driving force for swelling of superabsorbents. Increasing the ionic mobile ion concentration difference between the polymer gel and external medium which, in turn, reduces the gel volume, i.e. the gel shrinks and swelling capacity decreases (charge screening effect). In addition, in the case of salt solutions with multivalent cations, “ionic crosslinking” at surface of particles causing an appreciably decrease in swelling capacity. For example, Castel et al. reported that calcium ion can drastically decrease the swelling capacity for a hydrolyzed starch-graftpolyacrylonitrile, due to the complexing ability of the carboxylate group to include the formation of intra- and inter-molecular complexes23. In fact,Since the pectin-based hydrogels are comprised poly(NaAA) chains with carboxylate

Scheme. 1: Proposed mechanistic pathway for synthesis of the pectin-based hydrogels.

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groups that can interact with cations, they exhibit various swelling capacity in different salt solutions with same concentrations. The effect of cation on swelling can be concluded from Figure 5. In salt solution, degree of crosslinking is increased and swelling is consequently decreased. Therefore, the absorbency of the synthesized hydrogel is in the order of H2O > NaCl. In the presence of the bivalent calcium ions, the crosslinking density intensity increases because of a double interaction of Ca2+þ with carboxylate groups leading to “ionic crosslinking”. The swelling–deswelling cycle of the hydrogel in sodium and calcium salts are shown in Fig. 6. In sodium solution, swelling of the hydrogel is increased with time. When this hydrogel is immersed in calcium chloride solution, it deswells to a collapsed form. When the shrinked hydrogel is immersed in sodium chloride solution again, the calcium ions are replaced by sodium ions. This ion exchange disrupts the ionic crosslinks leading to swelling enhancement. As a result, when hydrogel is treated alternatively with NaCl and CaCl 2

solutions with equal molarity, the swelling reversibility of hydrogel is observed21-24. CONCLUSION A novel superabsorbent hydrogel, H-Pecpoly(sodium acrylate), was synthesized in an aqueous solution by graft copolymerization of acrylic acid onto pectin. The maximum water absorbency in distillated water (348 g/g) was achieved. Swelling measurement in NaCl salt solutions shows a swelling-loss, in comparison with distilled water. This behavior can be attributed to charge screening effect and ionic crosslinking for mono- and multi-valent cations, respectively. In addition, the swelling of hydrogels in solutions with various pHs, exhibited high sensitivity to pH, so that the pH reversibility and on-off switching behavior makes the intelligent hydrogel as a good candidate for considering as potential carriers for bioactive agents, e.g. drugs.

REFERENCES

1.

2.

3. 4. 5.

6. 7. 8. 9. 10.

Buchholz, F.L., Graham, A.T. Modern Superabsorbent Polymer Technology, New York: Wiley, (1997). Cheng, H., Zhu, J.L., Sun, Y.X., Cheng, S.X., Zhang, X.Z., Zhuo, R.X. Bioconjug. Chem.19: 1368-1374 (2008). Chu, L.Y., Kim, J.W., Shah, R.K., Weitz, D.A. Adv. Funct. Mater.17: 3499-3504 (2007). Chu, L.Y., Yamaguchi, T., Nakao, S.Adv. Mater. 14: 386-389 (2002). Crescenzi,V., Cornelio, L.,DiMeo, C.Nardecchia, S.,Lamanna, R. Biomacromolecules. 8: 1844-1850 (2007). J. Wu, J. Lin, M. Zhou, C. Wei, Macromol. Rapid Commun. 21: 1032-1034 (2000). Eddington, D.T., Beebe, D.J.Adv. Drug Deliv. Rev. 56: 199-210 (2004). J. Lin, J. Wu, Z. Yang, M. Pu, Polymers & Polymer Composites., 9: 469-471 (2001). J. Wu, Y. Wei, J. Lin, S. Lin, Polymer. 44: 6513-6520 (2003). Hoffman, A. S. Polymeric Materials Encyclopedia;, Salamone, J. C.; Ed.; CRC

11.

12. 13.

14.

15. 16. 17.

18.

Press, Boca Raton, FL. 5: 3282 (1996). Kirk RE, Othmer DF. Encyclopedia of Chemical Technology, Kroschwitz JI, HoweGrant M. (eds). John Wiley & Sons: New York, 4: 942 (1992). Barvic, M.; Kliment, K.; Zavadil, M. J. Biomed Mater Res.1: 313-323 (1967). Chirila, T. V.; Constable, I. J.; Crawford, G. J.; Vijayasekaran, S.; Thompson, D. E.; Chen, Y. C.; Fletcher, W. A.; Griffin, B. J. Biomaterials., 14: 26-38 (1993). G.F. Fanta, W.M. Doane, Grafted Starches, in: Modified Starches: Properties and Uses, Q.B. Wurzburg, (Ed.), CRC Press, Boca Raton (Florida), 149: (1986). Yamaguchi, M.; Watamoto, H.; Sakamoto, M. Carbohydr Polym., 9: 15 (1988). Pourjavadi A, Harzandi AM, Hosseinzadeh H.Eur. Polym. J. 40: 1363 (2004). Flory PJ. Principles of Polymer Chemistry, Ithaca, Cornell University Press, New York, (1953). Lim, D.W.; Whang, H.S.; Yoon, K.J. J Appl

Sadeghi et al., Curr. World Environ., Vol. 7(1), 69-77 (2012)

19.

20.

21.

Polym Sci, 79: 1423-1430 (2001). Hosseinzadeh, H.; Pourjavadi, A.; Zohouriaan-Mehr, M. J.; Mahdavinia, G. R. J Bioact Compat Polym, 20: 475-491(2005). Silverstein RM, Webster FX. Spectrometric Identification of Organic Compounds, 6 th Edn., Wiley, New York, (1998). G. R. Mahdavinia, A. Pourjavadi, H.

22. 23. 24.

77

Hosseinzadeh, M.J. Zohuriaan-Mehr, Eur. Polym. J. 40: 1399-1407 (2004). Chen J, Zhao Y.J Appl Polym Sci. 75: 808 (2000). Lim DW, Whang HS, Yoon KJ. J. Appl. Polym. Sci. 79: 1423 (2001). Barbucci R, Maganani A, Consumi M.Macromolecules; 33: 7475 (2000).

Current World Environment

Vol. 7(1), 79-85 (2012)

Investigation of Exhaust Emission Factors Based on Vehicle Models FARNAZ TAKIZAD Department of Environment, Tonekabon Branch, Islamic Azad University, Tonekabon (Iran). (Received: May 09, 2012; Accepted: June 10, 2012) ABSTRACT Hydrocarbon and Carbon monoxide emissions in passenger cars of Iranâ&#x20AC;&#x2122;s production is very high. This research is trying to technical examination of three vehicle models (Pride, Peugeot 206 and Samand) production of 2004, 2006 and 2008 check out amount of HC and CO emissions. MGT5 device was used to measure exhaust emission factors from this vehicle. The result of this study indicate that Pride and 206 Peugeot production of 2006 and Samand production of 2004 have most pollution in the production of HC. Most CO emissions was in vehicle production of 2004. Samand and Pride have lowest and most emissions, respectively. vehicles manufactured in 2008 is close to Euro IV Standard. However, vehicles manufactured since 2004 are Euro II standard. by increasing vehicle age was obsorved emissions increase.

Key words: HC and CO emissions, Vehicle, Pride, Samand, Peugeot 206.

INTRODUCTION Emissions of many air pollutants have been shown to have variety of negative effects on public health and the natural environment . Emissions that are principal pollutants of concern include: Hydrocarbons, Carbon monoxide(CO), Nitrogen oxides (NOx), Particulate matter, Sulfur oxide (SOx), Volatile organic compounds (VOCs). hydrocarbons are toxins. Hydrocarbons are a major contributor to smog, which can be a major problem in urban areas. Carbon Monoxide poisoning is also a major killer. By 1964, most new cars sold in the U.S. were so equipped, and PCV quickly became standard equipment on all vehicles worldwide (Rosen and Erwin, 1975). Air pollution and cars were first linked in the early 1950â&#x20AC;&#x2122;s by a California researcher who determined that traffic was to blame for the smoggy skies over Los Angeles. At the time, typical new cars were emitting nearly 13 grams per mile hydrocarbons (HC), 3.6 grams per mile nitrogen oxides (NOx), and 87 grams per mile carbon monoxide (CO) (Milestones in Automobile Emissions, 1994). Emission levels are dependent

upon many parameter including vehivle-related factors such as model. Size, fuel type, technology level and milage, and opration factors such as speed, acceleration, gear selection, road gradient and ambient temperature (Boulter et al, 2007). The power to move a car comes from burning fuel in an engine. Pollution from cars comes from by-products of this combustion process (exhaust) and from evaporation of the fuel itself (Automobile Emissions, 1994). Similarly, Ford Motor Company Chemistry Department Research Staff has instrumented a 1992 Aerostar van with Fourier transform infra-red instrumentation to measure approximately 20 species of emissions (e.g., CO, CO2, methane, total hydrocarbons, NO, and so forth) at high time resolution while on the road (Jession, 1994). Diesel engines while they have many advantages, they also have the disadvantage of emitting significant amounts of particulate matter (PM) and the oxides of nitrogen (NOx) and lesser amounts of hydrocarbon (HC), carbon monoxide (CO) and toxic air pollutants (Manufacturers of Emission Controls Association. 2009).

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Air pollution is the most serious environmental problem in Tehran with exhaust emissions from spark-ignition engines accounting for a major part of problem. The formation and accumulation of deposits on the internal surfaces of engines could adversely affect the exhaust emission from vehicles. It is the perception that some of fuel additives can remove these deposits due to their detergency. It is found that the decarbonization process could reduce the exhaust CO and HC emissions, significantly. Emissions from Peykan and Pride vehicles decreased considerably after decarbonization (Daryabeigi Zand et al, 2007). Quoting from Office of Vehicle If you consider the useful life of passenger cars in 20 years, This means that the vehicles to get out before the 1982, Number 1541200 old car are the traffic in Iran that make up The 40.21 percent of all passenger vehicles. According to statistical surveys, The share of cars in polluted air are approximately 60% and other emissions are about 40% (Khanfekr et al, 2009). about 1.5 million tons of pollutants are produced in Tehran every year. Carbon monoxide makes up a large percentage of this material (Roshan Zamir and Eikani, 2004). Given that the share of hydrocarbon and Carbon monoxide emissions in passenger cars of Iranâ&#x20AC;&#x2122;s production is very high, This research is trying to technical examination of three vehicle models (Pride, Peugeot 206 and Samand) production of 2004, 2006 and 2008 check out amount of HC and CO emissions produced from this vehicle. MATERIAL AND METHODS Technical examination as an accepted method was done around the world by government agencies or quasi-governmental for evaluation of vehicles that consistent with defined standards of safety and pollution. This study was done 2011 and was attempted using the data collected in previous years by the center of vehicl technical examination. Three types of domestically produced cars (Pride, Peugeot 206 and Samand modeles years 2004, 2006 and 2008) based on years of production and operation were compared the amount of emissions. MGT5 device was used to measure exhaust emission factors from gasoline-powered

vehicles such as CO2 - CO - HC - O2 - NO. If the vehicle is out of state or there is a defect in performance ignition systems, exhaust pollutants will go beyond the standard. This device consists of a Propp that placed inside the vehicle exhaust and Pumps. MGT5 device analysis the exhaust gases by using a computer system and displays on the monitor or LED. Then the result of vehicle test is printed. CO and HC emissions of exhaust gases of vehicles, operating years and car model are the input data of this study. It is worth noting that the amount of suffering to pass a technical examination of the test are as follows: in Auto injector for the CO gas approval number is up 2.5 and HC gas to number 250. RESULTS AND DISCUSSION Pay attention to Table1, between HC emission of Samand vehicle and 206 Peugeot production of 2004 is no significant difference. It means, The amount of their pollution is close together but the difference emissions of Samand, Pride and 206 Peugeot, Pride in this yearâ&#x20AC;&#x2122;s production is significant at level of 0.05 percent. between HC emission in vehicles produced 2006 and 2008 is no significant difference exept of Pride and Samand cars production in 2008, this difference is significant because of Samand car is be more modern. Result of correlation measure the amount of CO emission of vehicle manufactured of 2004, 2006 and 2008 showed that only between emissions of Peugeot 206 and Pride production of 2008 are no significant difference. Between the amount of CO emission in other vehiceles production of different years in this study are significant different at level of 0.05 percent (table 2). Kelly and Groblicki, 1993 found that during moderate to heavy loads on the engine, the vehicle ran under fuel enrichment conditions, resulting in CO emissions 2,500 times greater than those at normal stoichiometric operation (HC was 40 times as great). LeBlanc et al 1995 in their study appear capable of adequately distinguishing the CO emission effects associated with variations in engine and vehicle operations for individual vehicle

Takizad, Curr. World Environ., Vol. 7(1), 79-85 (2012) makes and models. However, it should be noted that the large variability in vehicle-to-vehicle CO emission response to changes in operating modes that has been noted in ongoing studies indicates that a model based on vehicle speed and acceleration profiles alone may not provide sufficient CO emission rate predictive capabilities for the fleet.

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97 percent of CO and 92.8 percent of HC in Tehran air caused by pollution from the transportation sector in 1995 year (Department of Energy, 1996). in 2008 year, The share of HC and CO emissions from passenger cars was 59 percent and 88 percent, respectively in Iran (Department of Energy, 1999). Yli-Tuomi et al (2005) by research on emissions of fine particles, NOx and CO from

Table1: Correlation measures the amount of HC between Pride, Peugeot 206 and Samand, production of 2004, 2006 and 2008 years by using the Pearson correlation test. Production 2004 Pride*206 Pearson Correlation Sig. (2-tailed) N Pearson Correlation Sig. (2-tailed) N Pearson Correlation Sig. (2-tailed) N

Samand* Pride

-0.065 0.098 0. 01 0.05 411 395 2006 production -0.024 -0.043 0.063 0. 053 395 391 2008 production 0.001 0.003 0.093 0.04 393 393

Samand* 206 -0.04 0.417 407 -0.07 0. 161 398 0.001 0.098 388

Table 2: Correlation measures the amount of CO between Pride, Peugeot 206 and Samand, production of 2004, 2006 and 2008 years by using the Pearson correlation test Production 2004 Pride*206 Pearson Correlation Sig. (2-tailed) N Pearson Correlation Sig. (2-tailed) N Pearson Correlation Sig. (2-tailed) N

Samand* Pride

0.05 0.055 0.01 0.031 344 363 2006 production -0.051 -0.028 0.01 0.05 397 392 2008 production 0.014 0.015 0.056 0.042 393 393

Samand* 206 0.001 0.05 365 -0.035 0.02 402 0.061 0.022 388

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Takizad, Curr. World Environ., Vol. 7(1), 79-85 (2012) Table 3:European emission standards for CO emission in passenger cars (g/km). Euro I July 1992 2.72 (3.16)

Euro II Euro III Euro IV Euro V Euro VI (future) January 1996 January 2000 January 2005 September 2009 September 2014 1.0

0.64

0.5

0.5

0.5

Table 4: The average HC and CO emissions during 2004, 2006 and 2008 years between three Production: Pride, Peugeot 206 and Samand

HC Pride 2004 2006 2008 HC 206 Peugeot 2004 2006 2008 HC Samand 2004 2006 2008

Mean

Std. Error Mean

129.37 142.12 111.22

3.98 3.68 3.70

75.66 89.89 79.15

2.87 4.63 2.77

95.38 88.63 47.11

4.74 5.58 3.24

on-road vehicles in Finland resulted: Relative to fixed site urban PM2.5, street air PM2.5 concentrations of Cu, BC, Fe, and Zn were elevated. Weather and road conditions influenced PM concentrations more than the differences between the city and highway traffic environments. Iranâ&#x20AC;&#x2122;s government in line with environmental protection and prevent air pollution, Timeline standards limit emissions of gasoline, diesel and dual burner vehicles, Domestic and imported and motorcycles be determined. Accordingly, the standards limit emissions of light vehicles, semi-heavy and heavy vehicles in 2010 and 2011 is Euro II, But the years 2012, 2013 and 2014 the vehicles must earn Euro IV standard. Table 3 shows european emission standards for CO emission in passenger cars. The results of Table 4 indicate that Pride and 206 Peugeot production of 2006 and Samand production of 2004 have most pollution in the production of HC. Most CO emissions was observed in vehicle production of 2004. Samand and Pride have lowest and most emissions, respectively.

CO Pride 2004 2006 2008 CO 206 Peugeot 2004 2006 2008 CO Samand 2004 2006 2008

Mean

Std. Error Mean

0.91 0.43 0.27

0.088 0.029 0.020

0.71 0.64 0.41

0.04 0.03 0.024

0.69 0.68 0.24

0.042 0.045 0.023

According to the results in table 4 can be said newer car models closer to international standards and we see a reduction of gas emissions. Comparison of CO emissions with Europe emissions standards can be stated vehicles manufactured in 2008 is close to Euro IV standard. However, vehicles manufactured since 2004 are Euro II standard. by increasing vehicle age we have emissions increase. Kuhns et al in 2004 resulted that Emission factors were related to vehicle age, weight class and fuel type by matching license IDs to the state registration data. No relationship was observed between PM (particulate matter) emissions and VSP (vehicle specific power). PM emission factors from LDGV (light-duty gasoline vehicles) increased with vehicle age. Good agreement was observed for HC emission factors for vehicles less than 20 years old. CO emission factors were 2 times greater than measured CO emission factors for vehicles less than 13 years old. Measured NO emission factors were 50% greater than factors for vehicles 7â&#x20AC;&#x201C;15 years old but in good agreement for vehicles less than 7 years old. Measured PM emission factors showed a clear increase with vehicle age.

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control.Therefore, effective multi-pollutant control strategies and in-use compliance programs are imperative to reduce the overall emissions from the transportation sector.

Wang et al (2012) shows that trucks with high BC EFs do not usually have high NOx EFs, and vice versa, indicating that the current emission standards implemented in Beijing and nationwide have only limited impact on NOx emissions

Table 5: Correlation measures the amount of HC between production years (2004, 2006 and 2008) by using t test in three modeles: Pride, Samand and 206 Peugeot HC Pride 2004*2008

2004*2006 Pearson Correlation DF t Sig. (2-tailed)

0.08 393 -2.42 0.016

Pearson Correlation DF t Sig. (2-tailed)

-0.009 413 -2.161 0.031

Pearson Correlation DF t Sig. (2-tailed)

-0.076 390 0.89 0.037

2006*2008

0.057 398 3.801 0 HC 206 Peugeot 0.11 409 -0.85 0.039 HC Samand -0.019 389 8.22 0

0.018 392 5.783 0 0.63 396 1.573 0.001 0.032 390 6.268 0

Table 6: Correlation measures the amount of CO between production years (2004, 2006 and 2008) by using t test in three modeles: Pride, Samand and 206 Peugeot

2004*2006 Pearson Correlation DF t Sig. (2-tailed) Pearson Correlation DF t Sig. (2-tailed) Pearson Correlation DF t Sig. (2-tailed)

CO Pride 2004*2008

0.008 366 5.6 0 CO 206 Peugeot 0.039 372 6.3 0 CO Samand 0.004 390 9.2 0

2006*2008

-0.025 366 6.697 0

-0.033 395 4.33 0

-0.029 368 6.233 0

-0.098 397 5.334 0

0.023 389 9.44 0

0.054 390 8.625 0

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Another test that was used to measure the HC and CO emissions in three models of vehicle in different years was t test. This test was performed on a product in 2004, 2006 and 2008 years. The results showed that between HC emission in vehicles manufactured in 2004, 2006 and 206 Peugeot manufactured of 2004 and 2008 are significant difference at the level of 0.05 percent. This difference between models of vehicles manufactured of 2004 and 2008 , 2006 and 2008 years was quite significant at level of 0.01 percent (table 5).pay attention to table 6, amount of CO emission between 2004 and 2006, 2004 and 2008, 2006 and 2008 years in Samand, Pride and 206 Peugeot have significant different at level of 0.01 percent. It is reason to reduce emissions of HC and CO in the newer cars. Experimental results of (Horng Tsai et al,2000), indicate that the emissions of CO and THC from in-use motorcycles are significantly higher than new ones, but not for NOx, and the emissions of THC from 2-stroke motorcycles are much higher than 4-stroke ones. The emissions of VOCs (volatile organic compounds) from in-use motorcycles are higher than new motorcycles for all five driving patterns, and those from 2-stroke engines are higher than 4-stroke motorcycles. Emission of VOCs in the modes of deceleration and idle accounts for the most mass emitted during the test driving cycle.

There is reasonable agreement between the different types of studies for emissions of NOx, but agreement for emissions of other pollutants is qualitative. Remote sensing studies indicate that emissions of NO are normally distributed, while emissions of CO and HC are skewed to a few high emitting vehicles. (Yanowitz. et al, 2000) indicate that average emissions of PM, CO, and HC have been reduced during the past two decades, but average emissions of NOx have not changed. Thus, emissions regulations for PM have been somewhat effective, although the degree of PM reduction is less than expected based on changes in the standards. Emission regulations have apparently not been effective at reducing in-use NOx. In comparison, there are estimates that transit buses generate less than 5% of the vehicle miles traveled for heavy-duty vehicles. CONCLUSION Today one of the impor tant factors affecting the issue of vehicle emissions is receiving tax of the vehicles. in Europe and other developed countries around the world receiving tax depends on their pollution. High consumption and high polluting vehicles pay more taxes . for approaching emissions standards to international standards should be made legal with non-standard products and with full compliance standardization of vehicles and construction technical examination centers trying to improve pollution problem in Iran.

REFERENCES 1.

2.

3.

Automobile Emissions: An overview. U.S. Enviromental protection agency office of mobile sources. EPA. 400-F-92-014 (1994). Boulter, P.G., MeCare, I. S., Barlow,T. J., A review of instantaneous emission models for road vehicles. Transpor t Research Laboratory, Published project report per 267. Version: final (2007). Daryabeigi Zand, A., Nabi bidhendi, G., Mikaeili, A., Pezeshk, H., The influence of deposit control additives on exhaust CO and HCemissions from gasoline engines (case study: Tehran). Transportation Research Part D: Transport and Environment. 12(3): 189-

4.

5.

6.

7.

194 (2007). Department of Energy,. Understanding Iranâ&#x20AC;&#x2122;s energy sector and provide basic data. Department of Environment. Iran. (1999). Department of Energy,. 1999. Feasibility of developing an electric car in Iran. Office of Planning. Technical Faculty of Tehran University. Iran. (1999). Horng Tsai, J., Chyun Hsu, Y., Cheng Weng, H., Yinn Lin, W., Tien Jeng, F., Air pollutant emission factors from new and in-use motorcycles, Atmospheric Environment. 34(28): 4747â&#x20AC;&#x201C;4754 (2000). Jession, G., Studies Relating On-Board

Takizad, Curr. World Environ., Vol. 7(1), 79-85 (2012)

8.

9.

10.

11.

Emissions Measurements with Engine Parameters and Driving Modes. Proceedings of the Fourth CRC-APRAC OnRoad Vehicle Emission Workshop, San Diego, Calif., 3(41): 3-58 (1994). Kelly, N.A. and Groblicki, P.J., Real-World Emissions from a Modern Production Vehicle Driven in Los Angeles. Journal of the Air & Waste Management Association, 43: 1351–1357 (1993). Khanfekr, A., Amroni Hoseini, M., Nemati, Z., Arzani, K., Azadmand, M., Production of catalytic converters for hybrid vehicle Roa and comparison with catalytic converters import Iran Khodro. Environmental Science and Technology. 11(2): 87-95 (2009). Kuhns, H. D., Mazzoleni, C., Moosmüller, H., Nikolic, D., Keislar, R. E., Barber, P. W., Li, Z., Etyemezian, V., Watson, J. G., Remote sensing of PM, NO, CO and HCemission factors for on-road gasoline and diesel engine vehicles in Las Vegas, NV. Science of The Total Environment. 322(1-3): 123–137 (2004). LeBlanc, D C., Saunders, F M., Meyer, M D., Guensler, R., Driving pattern variability and impacts on vehicle carbon monoxide emission. Transportation Research Board.

12.

13.

14.

15.

16.

17.

85

1472, ISSN: 0361-1981. 45-52 (1995). Manufacturers of Emission Controls Association., Retrofitting Emission Controls for Diesel-Powered Vehicles. 1730 M Street, NW, Suite 206 , Washington, D.C. 20036 (2009). Rosen, E.D., Erwin, M., The Peterson automotive troubleshooting & repair manual. Grosset & Dunlap, Inc.. ISBN 978-0-44811946-5 (1975). Roshan Zamir, S., Eikani, M. H., Research of Tehran air pollution. Third National Conference on Iran’s energy. Iran (2004). Yanowitz. J., McCormick. R L., and Graboski. M.S., In-Use Emissions from Heavy-Duty Diesel Vehicles. Environmental Science and Technology ., 34(5): 729-740 (2000). Yli-Tuomi, T., Aarnio, P., Pirjola, L., Makela, T., Hillamo, R. and Jantunen, M., Emissions of fine particles, NOx and CO from on-road vehicles in Finland. Atmospheric Environment 39(35): 6696-6706 (2005). Wang, X., Westerdahl, D., Hu, J., Wu, Y., Yin, H., Pan, X., Zhang, M., 11-On-road diesel vehicle emission factors for nitrogen oxides and black carbon in two Chinese cities. Atmospheric Environment. 46: 45-55 (2012).

Current World Environment

Vol. 7(1), 87-91 (2012)

Detecting the Level of Contaminations Caused by Heavy Metals in the Zayandeh Roud River and Clean up by Leaves of Beech Tree MOHAMMAD KARIMI Department of Chemistry, Budelkhand University Jhansi - 284 128 (India). (Received: April 25, 2012; Accepted: May 28, 2012) ABSTRACT Zayandeh Roud is one of the most important rivers flowing in the central part of Iran. It originates from the Kouhrang Mountains. This river passes through Chahar Mahal & Bakhtiari and Esfahan Provinces and finally flows into the Gavakhouni pond. The water of this river is used for agriculture, industry and potable water. Determination of contamination level of heavy metals throughout the river is important and has a major role in controlling the ecological conditions of its environment. Clean up of the contaminations caused by heavy metals based on the natural methods including use of plants such as beech leaves will result in a healthy surrounding life while leaving no negative effects. The reason for selecting the leaves of beech tree is the abundance of this plant in different parts of Iran as well as its easy preparaation for use. In the spring of 2011, contamination level of the river to Cu, Zn, and Pb metals was measured in 6 stations and three stages and the effect of using the leaves of beech tree on the absorption of heavy metals was investigated.

Key words: Zayandeh Roud, Water Pollution, Heavy Metals, Heavy Metals Clean-up.

INTRODUCTION Contamination of heavy metals causes a serious problem for health and generally for manâ&#x20AC;&#x2122;s life. Discharge of these metals is caused as the result of several activities such as production of chemicals, dyeing, plastering, mining activities, extractive metallurgy, nuclear activities and other industries. These metals have a destructive effect on the animals, lakes and rivers (Sayeri, Hamoudi, & Yang, 2005). Human activities such as urban and industrial sewages as well as atmospheric sediments and runoffs with unknown sources are the main source of the existing metals in the rivers. They are also one of the major environmental pollutants that are accumulated in the living organisms and cause serious hematological diseases, brain damage, anemia and bad performance of kidneys. Recently, the existing heavy metals in different rivers have been investigated (Wakida, Lara-Ruiz, Rodriguez-

Ventura, Diaz, & Garcia-Flores, 2008). The toxicity caused by heavy metals is an issue for which there is much concern since it is very important for peopleâ&#x20AC;&#x2122;s health as well as for ecology. Furthermore, heavy metals may be accumulated in the soil in toxic levels due to long term use of untreated sewages. In the soils irrigated by using sewage, heavy metals are accumulated in the surface. When the soil capacity for keeping heavy metals is reduced due to frequent use of sewage, these metals flow into the underground water or into the existing soil solution for absorption by plants. Here is the beginning of the main risk and the transfer of contamination to the critical points should be avoided in a way (Sridhara, Kamalaa, & Samuel, 2008). Several methods have been used to clean up the contaminations caused by heavy metals and some troubles have also been observed after the application of the said methods (Qureshi & Memon, 2012). Efforts have been made in this study to investigate the acceptable reduction of heavy

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metals based on using the leaves of beech tree. One of the common techniques for measuring the concentration of heavy metals is Flame Atomic Absorption Spectrometry (FAAS). FAAS method is classified as a single-element method which requires a longer time to analyze several elements in a sample. Multi-element methods such as X-Ray Florescence (XRF) (Talebi, 1998), Neutron Activation Analysis (NAA) (Guéguen, Gilbin, Pardos, & Dominik, 2004), and Atomic Emission Spectrometry using Inductively Coupled Plasma (ICP-AES) (Bruder, Lgrade, Lerosy, Coughanower, & Enguehard, 2002), are used for synchronous and critical determination of heavy metals and provide reliable results. In this study, ICP-AES method was used as a multi-element technique to identify rare heavy metals in water. In this study, the analysis of the selected metals (Zn, Pb, and Cu) in the Zayandeh Roud River at Esfahan Province (Central Part of Iran) and also clean up of the contamination of the aforesaid heavy metals by the leaves of beech tree were investigated. It should be noted that Esfahan province is one of the most important industrial centers of Iran. There are different industries in this province including steel (the largest industry of the country), power plants, aluminum, wood production factories, electronic, computer, petrochemical complexes and refineries. As a result, copper, zinc and lead may leak into the water ecosystem of Zayandeh Roud River. MATERIALS AND METHODS Water samples were collected from 6 stations along Zayandeh Roud River at Esfahan, Iran. The list and specifications of sampling points are shown in table 1. Sampling was made in the spring of 2011 in three stages within one month. The tools for sampling and analyzing the rare metals were completely cleansed by acid before being used. Digestion of metals was performed based on USEPA method, 3010 (acidic digestion of extracts for analyzing dissolved or completely recoverable metals by FLAA or ICP spectroscopy) (US-EPA, 1991). All references were of analytic type. Hydrochloric, hydrofluoric and nitric of the acids were used for digestion of samples and preparation of standards. Standards solutions were used to determine the ICP

of the analyzed elements. Glass and Teflon containers were treated in a 10% volumetric solution of nitric acid for 24 hours and were then washed by distilled and deionized water. The digested samples were kept in 15 ml polyethylene tubes in a cold room with a temperature of 4°C. The samples were measured by using AA 220 Spectrophotometer Varian Spectra and Atomic Emission Spectrometer with Inductive Coupled Plasma (ICP-AES) and were analyzed for three times for the existence of Cu, Pb and Zn metals. The analytic qualitative control involved daily standard analysis as well as repeating the analysis of samples and blanks (Martin & Meybeck, 1979). After preparing the samples and measuring the concentration of Cu, Pb and Zn metals, it was the turn for preparing the leaves of beech tree to be injected into the water samples. The reason for selecting the leaves of beech tree is the abundance of this tree in different parts of Iran and its positive effect in similar studies for absorption of other pollutant elements. A sample leaf of beech tree is shown in figure 1. In order to prepare the leaf of beech tree for injection into the water sample, 5 grams of the beech leaf were dried in a container in a temperature of 70°C. Then, one gram of the dried material was changed into ash by keeping in a furnace with a temperature of 450°C for 6 hours (Natarajan, et al., 2010). The ashes of the samples were poured into 100 ml polyethylene containers and 3 ml of nitric acid were added to them. They were then heated on a water bath with a temperature of 100°C to be completely digested. After digestion, the sample was removed from the water bath and was completely cooled. The obtained combination was measured by using AA 220 Spectrophotometer Varian Spectra and Atomic Emission Spectrometer with Inductive Coupled Plasma (ICP-AES). In the next stage, 5 grams of beech leaf were injected into each of the water samples prepared from the river. Samples were then taken from the solutions within 30, 60, 90, 120, and 150minute time intervals and were measured.

Karimi, Curr. World Environ., Vol. 7(1), 87-91 (2012) RESULTS AND DISCUSSION

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concentration of the three ions of Cu, Pb and Zn based on the time are shown in figures 2 through 4.

The results of measuring the samples of river water before injecting the leaf of beech tree are shown in tables 2 through 4. It should be noted that the concentrations of heavy metals including Cu, Pb and Zn are determined on ppm basis. Basic concentrations of the three ions Cu, Pb and Zn in the beech leaf are shown in table 5. Average final reduction percentages for concentration of each of the three ions of Cu, Pb and Zn as absorbers after the use of beech leaf are shown in table 6. Average reduction percentages for the

As it can be seen, the concentrations of the three ions of Cu, Pb and Zn in the river water have different values based on the station; however, as we get close to the downstream of the river, their concentrations increase. As a vital lifeline in the center of Iran, Zayandeh Roud River has several consumptions including supply of potable water and also necessary water for industries and agricultural activities (Nemati Varnosfaderany, Ebrahimi, Mirghaffary, & Safyanian, 2009). Rapid growth of population and agricultural and industrial activities has resulted in the entry of a considerable volume of toxic materials including heavy metals into the river. Absorption of heavy metals seems to have been reduced in the recent years due to

Table 1: List and specifications of sampling points Table 2. Concentrations of heavy metals related to sample of first stage based on ppm

No.

Station

Position

1 2

Mourgan Keleh

3 4 5 6

Falavarjan Khajou Choum Varzaneh

Southwest of Esfahan Between Esfahan and Chadegan Dam Near Esfahan City Esfahan City 7 km from Sedeh Waterfall Varzaneh City, 125 km from South of Esfahan

Table 3. Concentrations of heavy metals related to sample of first stage based on ppm Station Mourgan Keleh Falavarjan Khajou Choum Varzaneh

Cu

Pb

Zn

0.063 0.068 0.054 0.082 0.064 0.092

0.47 0.37 0.82 0.53 0.47 1.39

0.06 0.04 0.05 0.04 0.05 0.07

Table 5: Concentrations of heavy metals in the beech leaf based on ppm Station Beech Tree Leaf

Cu

Pb

Zn

0/10

0/18

0/08

Station Mourgan Keleh Falavarjan Khajou Choum Varzaneh

Cu

Pb

Zn

0.062 0.068 0.053 0.081 0.064 0.091

0.43 0.38 0.71 0.44 0.36 1.42

0.06 0.04 0.05 0.04 0.05 0.08

Table 4. Concentrations of heavy metals related to sample of first stage based on ppm Station Mourgan Keleh Falavarjan Khajou Choum Varzaneh

Cu

Pb

Zn

0.065 0.073 0.058 0.081 0.064 0.092

0.46 0.39 0.72 0.44 0.34 1.31

0.05 0.04 0.04 0.04 0.05 0.06

Table 6. Reduction percentage of each of the metals after the use of beech leaf Station Reduction Percentage

Cu

Pb

Zn

39/69

51/89

29/91

90

Karimi, Curr. World Environ., Vol. 7(1), 87-91 (2012)

Fig. 1: A leaf of beech tree

Fig. 2: Reduction Percentage of Cu

Fig. 3: Reduction Percentage Pb

Fig. 4: Reduction Percentage Zn

saturation of pollution. This issue can be observed in the downstream points of the river (Zhao, Qiana, Huang, Li, Xuea, & Hua, 2012); (Laia, Yang, Hsieh, Wu, & Kao, 2011); (Chahinian, et al., 2011).

and agricultural waters. Population increase has been followed by increased consumption of river water and the contaminations caused by such consumptions have had negative effects on its quality. Considering the use of river water for irrigation of farming lands, high concentrations of heavy ions will cause irreparable damages in the near future. Therefore, one of the major concerns is to use a method for cleaning up the contaminations caused by heavy metals which is cost effective from economical and facilities viewpoints and above all, it lacks any secondary trouble. In this study, the effect of beech leaf on the absorption and reduction of concentrations of Cu, Pb and Zn ions was investigated. Considering the suitable reduction of concentrations of Cu, Pb and Zn ions after the use of beech leaf, it is recommended to use the leaf of beech tree as an almost free and quite natural solution in case of any need to the cleaning up of contaminations caused by heavy metals including Cu, Pb and Zn.

After sampling and injection of beech leaf into the samples, it can be seen that considerable percentages of the concentrations of heavy metals are absorbed. These percentages were almost 40% for copper, 52% for lead and 30% for zinc. Such reduction level seems acceptable considering the initial concentrations of the ions in the water samples (Liu, Jiang, Zhang, & Xu, 2011); (KertĂŠsz, Bakonyi, & Farkas, 2006); (Shikazono, Zakir, & Sudo, 2008). CONCLUSION Zayandeh Roud River, as the main source of water supply in the central plateau of Iran, has several consumptions including potable, industrial

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REFERENCES

1.

2.

3.

4.

5.

6.

7.

8.

9.

Bruder, V., Lgrade, F., Lerosy, M., Coughanower, C., & Enguehard, F. (2002). Application of a sequential extraction procedure to study the release of elements from municipal solid waste incineration bottom ash. Anal, Chim, Acta , 258-295. Chahinian, N., Bancon-Montigny, C., Caro, A., Got, P., Perrin, J., Rosain, D., et al. (2011). The role of river sediments in contamination storage downstream of a waste water treatment plant in low flow conditions: Organotins, faecal indicator bacteria and nutrients. Estuarine, Coastal and Shelf Science , 4. Guéguen, C., Gilbin, R., Pardos, M., & Dominik, J. (2004). Water toxicity and metal contamination assessment of a polluted river: the Upper Vistula River (Poland). Applied Geochemistry . Kertész, V., Bakonyi, G., & Farkas, B. (2006). Water pollution by Cu and Pb can adversely affect mallard embryonic development. Ecotoxicology and Environmental Safety , 4. Kubiak, J. J., Khankhane, P. J., Kleingeld, P. J., & Lima, A. T. (2012). An attempt to electrically enhance phytoremediation of arsenic contaminated water. Chemosphere , 3. Laia, Y., Yang, C., Hsieh, C., Wu, C., & Kao, C. (2011). Evaluation of non-point source pollution and river water quality using a multimedia two-model system. Journal of Hydrology , 2-3. Liu, X., Jiang, S., Zhang, P., & Xu, L. (2011). Effect of recent climate change on Arctic Pb pollution: A comparative study of historical records in lake and peat sediments. Environmental Pollution , 2-4. Martin, J., & Meybeck, M. (1979). Elemental mass balance of material carried by major world rivers. Mar Chem . Natarajan, S., Stamps, R. H., Ma, L. Q., Saha, U. K., Hernandez, D., Cai, Y., et al. (2010). Phytoremediation of arsenic-contaminated groundwater using arsenic

10.

11.

12.

13.

14.

15.

16.

17.

18.

hyperaccumulator Pteris vittata L.: Effects of frond harvesting regimes and arsenic levels in refill water. Journal of Hazardous Materials , 2-6. Nemati Varnosfaderany, M., Ebrahimi, E., Mirghaffary, N., & Safyanian, A. (2009). Biological assessment of the Zayandeh Rud River, Iran, using benthic macroinvertebrates. Biological assessment of the Zayandeh Rud River, Iran, using benthic macroinvertebrates , 3-4. Qureshi, I., & Memon, S. (2012). Synthesis and application of calixarene-based functional material for arsenic removal from water. Appl Water Sci , 1-2. Sayeri, A., Hamoudi, S., & Yang, Y. (2005). Applications of pore-expanded malodorous silica, removal of heavy metal captions and organic pollutants from waste water. Shikazono, N., Zakir, H., & Sudo, Y. (2008). Zinc contamination in river water and sediments at Taisyu Zn–Pb mine area, Tsushima Island, Japan. Journal of Geochemical Exploration , 3-6. Sridhara, C., Kamalaa, C., & Samuel, D. (2008). Assessing risk of heavy metals from consuming food grown on sewage irrigated soils and food chain transfer Ecotoxicology and Environmental Safety. Environmental Contamination and Toxicology . Talebi, S. (1998). Determination of lead associated with air- borne particulate matter by flame atomic absorption and wave-length dispersive X-ray fluorescence spectrometry. Environ. Anal. Chem. US-EPA. (1991). Test Method for Evaluating of Solid Waste. Cincinnati. OH: US Environmental Protection Agency. Wakida, F., Lara-Ruiz, J., Rodriguez-Ventura, J., Diaz, C., & Garcia-Flores, E. (2008). Heavy metals in sediments of the Tecate River, Mexico. Environ Geol (54), 637-642. Zhao, L., Qiana, Y., Huang, R., Li, C., Xuea, J., & Hua, Y. (2012). Model of transfer tax on transboundary water pollution in China’s river basin. Operations Research Letters , 2.

Current World Environment

Vol. 7(1), 93-100 (2012)

Synthesis, Characterization and Thermal Studies of a N, N’- bis(2- hydroxy –alpha- methyl benzylidene) Isobutyl Diamine Uranyl (VI) Nitrate [UO2 (HMBUD)]2+ SHAHRIAR GHAMMAMY* and SAJJAD SEDAGHAT Department of Chemistry, Faculty of Science, Imam Khomeini International University, Qazvin (Iran). (Received: December 20, 2011; Accepted: March 25, 2012) ABSTRACT N, N’- bis(2- hydroxy –alpha- methyl benzylidene) isobutyl diamineabbreviated as HMBUD was synthesized and characterized. N, N’- bis(2- hydroxy –alpha- methyl benzylidene) isobutyl diamineUranyl (VI) nitrateprepared by reaction of nitrate salt of UO2(NO3)2.6H2O with HMBUD. In this research, some of the inorganic complexes of uranyl with N- donor ligands were synthesized. Complexes were characterized by FT-IR and UV, ¹HNMR, ¹³CNMR spectra, TG/DTG measurements and some physical properties. The results of simultaneous TG-DTG-DTA analyses of the complexes show the final degradation product for these complexes are UO3. Also the results show chelation causes drastic change in the biological properties of the ligands and also the metal moiety. So the toxic effects of uranyl can be prevented by using chelating agent and complexation of the potentially multidentate ligands.

Key words: N, N’- bis(2- hydroxy –alpha- methyl benzylidene) isobutyl diamineUranyl (VI) nitrate,Synthesis, Thermal analysis, FT-IRand UV–Visible spectroscopy, Schiff bases.

INTRODUCTION The coordination chemistry of transition metals with ligands from the uranyl family hasbeen of interest due to different bonding modes shown by these ligands with both electron rich and electron poor metal. In principle, the central transition metal atoms of different soft and hard Lewis acidity usually need to be satisfied in the most suitable fashion.Schiff base metal complexes have been widely studied because they have industrial, antifungal, antibacterial, anticancer and herbicidal applications. Nitrogen-containing ligands such as Schiff bases and their metal complexes played an important role in the development of coordination chemistry resulting in an enormous number of publications, ranging from pure synthetic work to physicochemical 1 and biochemically relevant studies of metal complexes 2–6 and found wide range of applications. Other kinds of nitrogen-containing

ligands are well-known pyrimidine systems such as purine analogues that exhibit a wide range of biological activities. Fused pyrimidine compounds are valued not only for their rich and varied chemistry, but also for many important biological properties. Among them, the furopyrimidine ring system, because of a formal isoelectronic relationship with purine, is of special biological interest. It has numerous pharmacological and agrochemical applications, namely, antimalarials, antifolates, and antivirus, as well as potential radiation protection agents. Recently, some furopyrimidines were shown to be potent ascular endothelial growth factor receptor 2 (VEGFR2) and epidermal growth factor receptor (EGFR) inhibitors. Because of the importance of furo (2,3-d) pyrimidine derivatives, several methodologies for synthesizing them have already been developed. However, many of the synthetic protocols reported so far prolonged reaction times, harsh reaction suffer from disadvantages, such as relying on multistep

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reactinos, needing anhydrous conditions, low yields, use of metal- containing reagents, and special instruments or starting materials. Therefore, the development of new and efficient methods for the preparation of furo (2,3-d) pyrimidine derivatives is still strongly desirable7. Pyrimidines represent a very interesting class of compounds because of their wide applications in pharmaceutical, phytosanitary, analytical, and industrial aspects, for example, as antibacterial, fungicide8, antihelmintics, antitubercular, anti-HIV, antidegenerative and hypothermic activities 8, and herbicides , and have biological activities 9–13. It has long been known that metal ions involve in biological processes of life and have been subject of interest. The modes of action of these metal ions are often complex but are believed to involve bonding to the heteroatom of the heterocyclic residues of biological molecules, that is, proteins, enzymes, nucleic acids and so forth 14. From these points of view, it is interesting to study different types of transition metal complexes of these biologically active ligands. In this paper, the synthesis characterization, and antitumor properties of a number of the ligands and uranyl complexes have been studied. In this work, we report the synthesis and structural studies of the ligand and N, N’- bis(2hydroxy –alpha- methyl benzylidene) isobutyl diamineUranyl (VI) nitrate.

MATERIAL AND METHODS Solvents were purified bystandard methods. All reagents were supplied by Merck and were used without further purification. Melting point was determined in an Electro thermal 9200. The FT-IR spectra were recorded in the range 400–4000 cm-1byKBr disk using a Bruker Tensor 27 M 420 FTIR spectrophotometer. The UV–Vis spectra in CH3CN were recorded with a WPA bio Wave S2 100 spectrophotometer. Thermo gravimetric analyses were done on a Perkin Elmer TGA/DTA lab system l (Technology by SII) in nitrogen atmosphere with a heating rate of 20°C/min from 35- 700°C.¹ H and ¹³ C-NMR spectra were measured on a BRUKER DRX-500 AVANCE spectrometer at 500 MHz. Synthesis of the [UO2 (HMBUD)]2+ For synthesis of the [UO2 (HMBUD)]2+to a magnetically stirred of ligand (0.45g, 1.4mmol) in acetonitrile(10ml) was added uranyl (VI) nitrate (0.69g, 1.4mmol) at room temperature. The reaction mixture was further stirred for 3 hours to ensure the completion and precipitation of the formed complex. The precipitated solid complex was filtered and washed several times with diethyl ether to remove any traces of the unreacted starting materials.Yield, 85%.Anal.Mp: 225 °C. ¹HNMR (DMSO): 6.8-8 (CH

Fig. 1: FTIR spectrum of HMBUD (KBr Disk)

GHAMMAMY & SEDAGHAT, Curr. World Environ., Vol. 7(1), 93-100 (2012) phenol), 2.7 (CH3), 3.1 (CH2), FT-IR (KBr, cm-1): 1287s (ν C-N), 1622 s (ν C=N), 2929 br(ν OH), 572 m (ν U-O), 464m (ν U-N), 921 s (ν O=U=O), UV-vis (DMSO): λmax 260nm(ε 22000), 320nm(å 10000), 410nm(å 3600)(Figure 1-9). [UO2 (HMBUD)] 2+is soluble in acetone, DMF and DMSO and insoluble

95

in water, methanol, Acetonitrile, dichloro methane, diethyl ether and hexane and little soluble in chloroform and ethanol.Figure 10, 11 shows Chemical structures of HMBUD and [UO 2 (HMBUD)]2+.

Fig. 2: FTIR spectrum of [UO2 (HMBUD)]2+(KBr Disk)

Fig. 3: 1H- NMR spectrum of HMBUD

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Analysis of HMBUD Ligand Anal:%69. Calcd of C20H24N2O2; C;74.09, H; 7.4, N; 8.63; found: C; 80.11, H. 8.20, N; 9.12. Mp192-194 °C, ¹HNMR (DMSO): 6.7-7.6 (CH phenol), 1.5 (CH3), 3.6 (CH2), 12.8 (OH), FT-IR (KBr, cm-1): 1309s (ν C-N), 1612 s (ν C=N), 2931br(ν

OH), UV-vis (DMSO): λmax 268nm(ε 28000), 355nm(ε 10000). HMBUDis soluble in acetonitrile, DMSO, chloroform, dichloro methane and diethyl ether and insoluble in acetone, water, methanol, ethanol and hexane and little soluble DMF.

Fig. 4: 1H- NMR spectrum of [UO2 (HMBUD)]2+

Fig. 5: 13C- NMR spectrum of HMBUD

GHAMMAMY & SEDAGHAT, Curr. World Environ., Vol. 7(1), 93-100 (2012) RESULTS Preparation of Ligand and complex In this paper, we report a new method of the synthesis of N, N’- bis(2- hydroxy –alpha- methyl benzylidene) isobutyl diamineUranyl (VI) nitrate. The compound was obtained by reaction of UO2(NO3)2.6H2O and HMBUDand was synthesized

97

through a one-step reaction. Our procedure for producing compound has some advantages. For example, there is no side product in preparing [UO2 (HMBUD)]2+ in our method, the reaction is quite fast and does not require any severe conditions such as high pressure or high temperature, and it is not sensitive to air.Compounds were characterized by several techniques using FT-IR, UV-Visible and

Fig. 6: UV/ Vis spectrum of HMBUD(DMSO, 5×10-4 M)

Fig. 7: UV/ Vis spectrum of [UO2 (HMBUD)]2+(DMSO, 5×10-4 M)

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NMR spectra Thermal analysis were studied for these compounds. The [UO2 (HMBUD)]2+has225 °C melting points respectively. It is soluble in acetone, DMF and DMSO and insoluble in water, methanol, Acetonitrile, dichloro methane, diethyl ether and hexane and little soluble in chloroform and ethanol. The spectral data of the complexes have good relationship with the literature data.The IR spectra of the Schiff base show characteristic bands due to ν(OH), ν(C=N) and ν(C-N) in the region 2931cm-1,

(1612, 1309) cm-1respectively. The strong band in the region 1612, 1309cm-1 in the IR spectra of the Schiff base are assigned to ν( C=N), ν( C-N) respectively. In the case of U(VI) complex we observed the following changes. The bands appeared around 572, 464, 921, 1287, 1622, 2929cm-1 due to ν(U-O), ν(U-N), ν (O=U=O), ν (CN), ν(C=N), ν (OH) IR spectra of ligand (HMBUD) show a broad medium intensity band in the region 2931cm-1due to OH.

Fig. 8: Thermal analysis data of [UO2 (HMBUD)]2+

Fig. 9: Chemical structure of HMBUD

GHAMMAMY & SEDAGHAT, Curr. World Environ., Vol. 7(1), 93-100 (2012)

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Fig. 10: Chemical structure of [UO2 (HMBUD)]2+ Thermo gravimetric analyses The thermal properties of these compounds were investigated by thermo grams (TG, DTG andDTA). Figure 9shows TGA and DTA curves for[UO2 (HMBUD)]2+. In the temperature range from 300-410°C, 60% weight losing was observed which was related to the loss ofmostparts of compound.

synthesized. Complexes were characterized by FTIR and UV, ¹HNMR, ¹³CNMR spectra, TG/DTG measurements and some physical properties. The results of simultaneous TG-DTG-DTA analyses of the complexes show the final degradation product for these complexes are UO3.

DISCUSSION

We gratefully acknowledge the financial support from the Research Council of Imam KhomeiniIslamic Azad University and many technical supports that provided by TarbiatModarres University.

In this research, some of the inorganic complexes of uranyl with N- donor ligands were

ACKNOWLEDGMENTS

REFERENCESES

1. 2. 3. 4. 5.

6.

VidmarR.J.IEEE Trans.Plasma Sci., 21: 876 (1992). Murthy A.S.N. andReddy A.R.Journal of Chemical Sciences, 90: 519 (1981). RazakantoaninaV.N.K. and Phung P. Parasitology Research,86: 665 (2000). Royer R.E. and Deck L.M. Journal of Medicinal Chemistry,38: 2427 (1995). Flack M.R. and Pyle R.G. The Journal of Clinical Endocrinology & Metabolism, 76:1019 (1995). BaumgrassR. andWeiwadM. Journal of

7.

8. 9. 10. 11.

Biological Chemistry, 276: 47914 (2001). TeimouriM.B. and Bazhrang R. Bioorganic & Medicinal Chemistry Letters, 16: 3697(2006). TeimouriM.B. Tetrahedron, 62: 10849 (2006). GrevyJ.M.,TellezF. Inorganica ChimicaActa, 339: 532 (2002). BernalteA. andBarrosF. J. Polyhedron, 18: 2907 (1999). Lemma K. andBerglund J. Journal of Biological Inorganic Chemistry, 5: 300 (2000).

100 12. 13. 14.

GHAMMAMY & SEDAGHAT, Curr. World Environ., Vol. 7(1), 93-100 (2012) Campbell M.J.M. Coordination Chemistry Reviews,15: 279 (1975). Padhy´eS. andKauffman G.B. Coordination Chemistry Reviews, 63: 127 (1985). Erwin B. and OmoshileC. Journal of the

15.

Chemical Society Perkin Transactions, 2: 1333 (1995). Zhao G. andLin H. Journal of Inorganic Biochemistry, 70: 219 (1998).

Current World Environment

Vol. 7(1), 101-108 (2012)

Study and Analysis of Geometric Effect of Ball Burnishing Process of Different Materials and Evaluation of Forces and Strain for Ballizing Process PAWAN K. UPADHYAY1, A. R. ANSARI2 and PANKAJ AGARWAL3 1

Department of Mechanichal Enggineering. NIIST., (India). Department of Mechanichal Enggineering S.S.C.T (India). 3 Department of Mechanichal Enggineering (India).

2

(Received: May 12, 2012; Accepted: June 20, 2012) ABSTRACT The process consists of forcing an oversized ball of a hard material through a premachines hole in softer material .The interference between the ball and the hole causes the hole to expand such that its deformation is partly plastic and partly elastic. The elastic deformation of the hole is recovered due to elastic spring back whereas the plastic deformation results in a slight permanent increase in the hole diameter after ballizing. Ball burnishing or Ballizing is a production process for improve the accuracy and surface finish of holes. This process is a mass production process for sizing and finishing holes. The sizing and finishing of holes depends upon the interference adopted for ballizing process. This paper is an attempt toward comparing surfaces effects ,Estimation of deflection, deformation, radial strain, stress and finished dimensions of Mild steel and Aluminium.

Key words: Ballizing, Alluminum Alloy, Alloy steel, C.L.A., Elastic Pressure, Plastic Deformation, BHN, Machining, Surface roughness, Technology devices and equipment.

INTRODUCTION Geometrical Effects When the ball passes through undersized hole, plastic deformation (ip) takes place, this plastic deformation of the hole may be due to many variables. It has been confirmed experimentally that interference (if) and plastic deformation (ip) have got a linear relationship i.e. they are proportional to each other. If deviation is defined as the difference of ball diameter and hole diameter after ballizing the experiment also establishes that this deviation is also proportional to the amount of interference, velocity of movement of ball, and hardness of the base material. In the graphs all the dates are depicted which are gathered during experiments. In the experiments hardened steel balls were used for Aluminium and Mild steel bushes.

We get a finished desired diameter of hole, after the ball of definite diameter is passed from the initial diameter. These data of initial and final diameters of hole and diameters of ball are based on the data accumulated by trial and error experimentation as discussed earlier. By dividing with D (the diameter of ball) we have made the values of interference and plastic deformation.Non-Dimensional these nondimensional quantities are plotted which give a linear relationship as shown. Construction of mathematical Models & equations When the linear relationship is combined with the Hertzâ&#x20AC;&#x2122;s theory of contact stress of elastic bodies the equation is obtained in the form Y = m. x + c Let d1 = initial diameter of hole

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db and df after ballizing.

= =

initial diameter of ball final diameter of hole

Then i f = interference = d b -d i and permanent plastic deformation = ip = df-di. During the process, the ball and hole both will under go elastic deformation, although ball is hardened and bush is made of a softer material. There fore interference = if = ip + eh + eb ...(1) If we plot if against X axis and ip against y asix we get. ip=m.if + C ...(2) Where m C

= =

slope of the line and a constant, which is an intercept on y axis.

For perfect elastic deformation ip = 0 and for this Also

if if ip

= = =

eb + eh 0 eb = 0 eh

From above we get m = eh/eb +eh and C = -eh

ip ď&#x20AC;˝

eh eh ď&#x20AC;Ť eb

i f ď&#x20AC;­ eh

...(3)

EXPERIMENTAL From experimental observations value of m and C can be obtained. Referring to figs it is seen that the slope m of the linear relationship line is of the order of unity. However from the authors model it was proposed that.

This suggests that the value of e B is negligible. Thus it can be inferred that if the value of

eB = 0

Hence

m =1

The author has observed in his study of ballizing experiments that during the travel of the ball, the bush indicates a marked bulge and the ball bas less likelihood of strain. It may be pointed out that for excessively thick walled bushes the value of eB cannot be adopted as zero. A detailed theoretical model can be developed for estimating the values of strain eH. This model is based on the Classical contact stress analysis founded by H. Hertz and presented in next section. In Ballizing there is almost rectangular strip contact between ball and the hole. A comparison of experimental results with Authors model is indicated in fig. . Evaluation technique and methodology (For Strains) Mathematical Model for strains in Ballizing Referring the fig. is the length of contact and 2b is the breadth or width of contact. The interference between the ball and the hole wall gives rise to say pressure P per unit length. The max. deflection is obviously occurring along xx. We have to find an expression for this max. deflection. It is true that the uniform pressure P along the line contact will give rise to semi elliptical pressure distribution as shown in the side view over the width of contact. Adopting a simplified assumption that the pressure distribution is uniform of intensity q instead of semi elliptical (Based on Timoshenko and Goodier. Theory of Elasticity) a model is developed in this article. Load Distributed over a part of the Boundary of a semi- infinite solid referring to

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103

FIg. 1:

Fig. 2: diagram Deflection at o due to load q.s. dĎ&#x2C6;. ds on the element is, processing on the lines.

and the total deflection due to distributed pressure is.

Estimation of deflection due to pressure (4 is used because there are 4 quadrants and the integral is only for the Ist quadrant) since Ć&#x2019;

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Fig. 3:

Fig. 4:

Fig. 5:

Fig. 6: ƒ ds

ds is the length of the chord for area b/a OAB, O ≤ ψ1 ≤ tan-1 ƒ ds = 2d. Sec ψ1 Similarly for area OBC, ≤ ψ2 ≤ tan-1 a/b

Where

=

b. Sec. ψ2

UPADHYAY et al., Curr. World Environ., Vol. 7(1), 101-108 (2012)

105

Fig. 7:

Fig. 8:

(Formula for calculation of deflection) Substituting in the expression for w,

...(5)

Where q = Pave For calculating the radial strain in the wall of the hole

adopting δ = i f /2

Thus the radial strain in the wall of the hole Ballizing. RESULT AND DISCUSSION

b = width of strip of contact and is calculated by the equations

a.Evaluation and analysis of different interference

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and with help of Fig. Calculation for Radial Strain Aluminium Bushes It is observed that with 150 and 50 microns interference respectively the final diameters obtained are 15.08 mm and 15.16 mm respectively. In the two bushes of 180 microns interference, from very rough surface as shown in fig. the final surface finish obtained was of 0.29 CLA, which indicates that a very good surface finish is obtained In the two bushes, in which interference was kept only 50 microns, the surface finish was not so good as it gave the C.L.A. value as 0.65 . Calculation for Radial Strain For Mild steel Bush with 80 Microns interference

The intercept on the Y axis is 1.35 microns according to authors model and aimed at adopting equal to 1. A value of 50 microns has been adopted for strain calculations in the case of steel, whereas an interference of 150 microns is adopted for Aluminum because of sinking in tendency of Aluminum, under the load of an indenting ball. Fig. indicate comparison between authors model and Experimental results. .

E = 1.96 x 106 kg/sq mc p = 9903 kg/sq cm 2 a = π R1 = 5.677 cm. µ = 0.3 R1 = 0.9 cm R2 = 1.8 cm and b = 0.0042 cm

Linear Relationship (a) For M.S. ip/D = 0.989 (if/D) - 0.49275 x 10-3 (b) For Aluminum : ip/D=0.9644 (if/D) - 2.2 x 10-3 more, with high interference. Test result show that in the harder points

The value of e H calculated from the equation 3 which is

in other DISCUSSIONS

eH = 0.5 x 10-3 cm Taking D = 1.8 cm Making it non dimensional

eH  D =

0.5  103 1.8 0.3 x 10-3

For Aluminum Bush of 180 microns interference E = 0.675 x 106 kg/cm2 µ = 0.34 R1 = 0.9 cm R2 = 1.8 cm 2a = 2 p R1 = 5.677 cm. b= 0.0114 c, p = 3342.70 kg/ sqcm The value of e H calculated from the equation eH = 2.41 x 10-3 cm

On the result of investigation following Concluding remarks can be made 1. From C.L.A. equation as well as C.L.A. plots it is clearly seen that improvement in surface finish is obtained material and more interference, axial load has increased. However, load is found to be independent of velocity. 2. Temperature does not rise so much during ballizing that it may affect the surface finish. 3. After, ballizing internal diameters of bushes were measured; which established the fact that ballizing is a microsizing process. 4. There is very slight increase in diameter when interference is less. Keeping the same oversized ball. 5. Theoretically as well as experimentally it is confirmed that if ballizing is done with more interference high velocity and on moderate BHN value, improved surface finish is obtained. 6. Small circular contacts will be observed on

UPADHYAY et al., Curr. World Environ., Vol. 7(1), 101-108 (2012)

7.

8.

9.

10.

the entire circumference as shown in Fig. 6.1. Co-relation factor for C.L.A. equation is 0.9583 whereas for load equation correlation factor is calculated to be 0.8677. Both the results show values are quite high and curve fitting is satisfactory in both the cases. Variation of load on the length of bush shown that, nearly at the center of the bush length the load is maximum. Vibration in he load curve may be due to variation in the geometry accuracy while boring.

Objectives of the Proposed work Sizing of bushes and final results will be of utility to industries. This will help in achieving high precision by selecting appropriate “Ball-Tube” combination. (a) determination of optimum interference for best surface finish. (b) Proposing Mathematical models based on the theory of elasticity (Hertz contact stress equations) and theory of plasticity involving slip line field solutions. (c) Strain models – Graph between ip and if. (d) Axial force models (calculation of F for ballizing) (e) A comparison of the Mathematical Models of the Ballizing process with experimental Investigations. (f) Surface finish evaluations using qualitative and quantitative measures. Some of the application are listed below 1. Honned and Lapped surfaces can be further smoothened. 2. Sizing and finishing of cross hole recesses. 3. Hallize can pre-stress the bores. 4. Slight tapers can be removed. 5. Holes of gears, arms, valves, plates, levers, and chain links can be ballized. 6. Good results can be obtained by ballizing for the following materials. 7. Stainless steels, even Nickle chromium Alloys 8. Lead, Chromium, Copper and even some non-metals. 9. Sintered iron, sintered brass i.e. powdered

10.

107

metals. Case hardened surfaces can also be ballized, but these should be free from hard chromium layer.

Calculations applies equally for the β line starting at any points in AB wide range of application and being used as a noble process (ballizing), it has some Observations, Concluding remarks can be made are listed below : 1. Interference (if) should never exceed 2x of the hole diameter. 2. It has given very good results for bores ranging from 0.5 mm to 125 mm diameter. 3. The length to diameter ratio has also been recommended length should not be more than 10 times or less than 1/10 of the bore diameter. 4. Wall thickness should also be greater than 1/10th of bore diameter. 5. Ballizing gave good results for hole diameters of 1.5 mm to 25 mm. 6. Part to be ballized should not be harder than 45 Rc. The balls must be more hard than 65 Rc. (65 Rockwell C scale). 7. Materials should be homogeneous. 8. Wherever ballizing length is more, arrangement, for pressing or pulling the ball though the bore has to be devised. 9. Porous, spongy or parts that wave hard spots due to casting, ballzing does not give uniform surface finish, 10. Although some cast parts are successfully ballized. 11. Every curved tubing cannot be ballized. 12. Parts that have case hardened layer upto 0.4 mm, can be ballized, but beyond 0.4 mm case hardened depth, ballizing connot be carried out successfully. 13. When heat treatment is done after ballizing, sizing and finishing of the ballized hole get disrupted. 14. It has given a relationship of Ball over size and bore undersize to obtain the final diameter desired. 15. It has established that in a particular soft material (Medium Carbon Steel) 16. When ballizng is done with a hard material ball the required bore diameters can be obtained as mentioned in the diagram (Fig. )

108

UPADHYAY et al., Curr. World Environ., Vol. 7(1), 101-108 (2012) REFERENCES

1. 2.

3.

4.

5.

6.

7.

8.

Gazen, G.A. : Sizing and Finishing Holes by Ballizing Tooling and production, (2003). Agrwal, A.S. : ‘Ballzing process for burnishing holes’ Dissertation for P.G. Diploma in Production Engineering (Royal College of Science and Technology Glasgow, U.K.). (1992) Fedrov, V.B. : Residual stresses and fatigue strength with centrifugal ball strain hardening. Trans. Of Ural polytechnical Institute, 112: (1991) Enlimash and orgstankinprom : Improving gear efficiency by Burning Machine and Tooling, 3: 54 (1999). Kononenko, V.T. and shamlin, V.Yu. : ‘Carbide burnishing unit for broaches’, Machine and Tooling, 8: 35 (2005). Ryzhov, E.V. ‘Increasing contact stiffness by vibratory burnishing’ machine and tooling., 1: 59 (2002) Vestnik Mashinostroeniya : ‘Self Centering Three Roller Attachment with Instrument to check Burnishing Forces’. Russian Engineering Journal, 57(7): 59-69 (2007). Vestnik Mashinostroeniya : ‘Calculating the

9.

10.

11.

12.

13.

14.

Depth of plastic Deformation when Stengthening parts by Plastic surface Deformation’. Russian Engineering Journal, Vol.59(1): 19-23 (2009). Vestnik Mashinostroenita and M.M. zhasimov : The principal feature of Machining Methods Involving plastic surface Deformation , Russian Engineering Journal , 60(3): 33-34 (2000). Papcheff , D.D. : The formation of the microproflle on burnished workpiece’ , Microtechnic , XXI(2) (2002). Kudryavtsev , I. V. : Surface Plastic Deformation and its practical application’, Russian Engineering Journal 1: 25 (2002). Investigation of some effects of Ballizing on Aluminium and Mild Steel. First Indian Engg. 9-13 (1987). Investigation of Elastic and plastic forces in Ballizing process [Ball Burnishing] for Aluminium and Mild steel. First Indian Engg. 9-13 (1987). Investigation of surface Effects in Ballizing on Aluminum and Mild Steel. First Indian Engg. (1988).

Current World Environment

Vol. 7(1), 109-115 (2012)

Status of Air Pollutants after Implementation of CNG in Delhi PALLAVI SAXENA*, RICHA BHARDWAJ¹ AND CHIRASHREE GHOSH¹ *Department of Environmental Biology, University of Delhi, Delhi - 110 007 (India). ¹Environmental Pollution Laboratory, Department of Environmental Biology, University of Delhi, Delhi-110007 (India). (Received: March 03, 2012; Accepted: April 09, 2012) ABSTRACT Air pollution kills more than 5.9 million people annually, with more than 90 per cent of these deaths in capital city of India, Delhi. For improving the status of air pollution in Delhi, various policies and laws have been implemented. But even after the implementation of CNG, there was no significant change of pollutants (NOx, O3, SPM, RSPM & CO) except SO2. The objective of our study is whether CNG conversion has impinged on the primary pollutant and tropospheric ozone pollution profile and for the improvement in the quality of air in post CNG period. To carry out the analysis, daily ambient air quality secondary data (Jan 2002-Dec 2009; Source-CPCB) of all the above discussed pollutants were used. For generating own data, NOX and O3 monitoring were carried out at four different sites viz. Site I (Yamuna Biodiversity Park, away from traffic intersection), Site II (Traffic intersection at outside YBP, outer ring road, Gandhi vihar), Site III (Aravalli Biodiversity Park, away from traffic intersection) and Site IV (traffic intersection at outside ABP, ring road, Vasant vihar) during monsoon season (Aug-Sept, 2009). The concentration of ozone was higher at sites which are at traffic intersection (Site II & IV) than those which are away from traffic intersection (Site I & III). The results however, do not indicate an all round improvement in ambient air quality of Delhi. Hence, our short term study suggests that after the implementation of CNG in Delhi there is no remarkable improvement in the status of the pollutants and moreover, the sites which are near to traffic intersection possess high concentration of pollutants than the sites which are away from traffic intersection.

Key words: tropospheric ozone, air pollution, NOx, CNG, traffic intersection, Delhi.

INTRODUCTION Clean air is considered to be a basic requirement of human health and for the well-being. However, air pollution continues to pose a significant threat to health worldwide (WHO 2005). The state of air pollution is often expressed as Air Quality (AQ). Air pollution has implications in a number of contemporary issues including: human health, (e.g. respirator y, cancer, allergies.), ecosystems (e.g. crop yields, loss of biodiversity), national heritage (e.g. buildings), and regional climate (aerosol and smog formation) (Monks et al, 2009). The World Health Organization estimated that 2.4 million people die each year from causes

directly attributable to air pollution with 1.5 million of these deaths are only due to indoor air pollution (WHO 2002). In Eastern Canada vehicular emission are the major contributor to Canada’s air where NOx emissions contributes to 8% and 5% contributes to total PM and SOx emissions specially during bad smog days (Environment Canada’s Performance Report 2003). Biomass burning constitutes an important anthropogenic NOx source in the tropics and subtropics of America, Africa and in South Asia. Due to high population density and higher economical growth rates, emission of these gases are increasing in Asia and more so in central and South Asia (Lelieveld and Crutzen 1994). China is the largest contributor of pollutant among Asian countries where increase in NOx growth rate is found to be about 7% per year (1990 to 1994)

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(WMO 1998). In India, most of the cities are experiencing rapid urbanization and the majority of the country’s population is expected to be living in cities within a span of next two decades (CPCB 2010). Under National Air Quality Monitoring Programme (NAMP) 2008, annual average for SO2 has not been exceeded in both the industrial (80%) & residential areas (93%) which is less than 20 ìg/ m3. Decreasing trend of SO2 may be due to various interventions that have taken place in recent years such as reduction of sulphur in diesel, use of cleaner fuel such as CNG in Delhi etc. Also there has been a change in domestic fuel used from coal to LPG which may have contributed to reduction in ambient levels of SO2. The total emission of NOx in India is in the range of 3.4 to 4.6 Tg/year. The average annual concentration of NO2 is reported to be 71µg/m3 in residential areas whereas 91µg/m3 in industrial areas during 2008. Various interventions have been taken place to mitigate ambient NO2 levels but at the same time number of vehicles has been increased exponentially which is one of the major sources of NO2 emission. During the same year i.e. 2008, the annual average concentration of RSPM is reported to be more in industrial areas (351 µg/ m3) as compared to residential areas (278 µg/m3). The reason for high particulate matter levels may be vehicles, gensets, small scale industries, biomass incineration, re-suspension of traffic dust, commercial and domestic use of fuels, etc. (CPCB 2008-09). In Delhi, the contribution of vehicular pollution has increased only in past 2-3 decades, earlier it was partly 23% in 1971 rose to 43% in 1981 and became 63% in 1991 (WWF 1995). There were 2.5 million vehicles registered in Delhi during 1996, while this number has reached 4.17 million in 2004 (MORTH 2004). Vehicular pollution accounts significantly to the total pollution generated in Delhi (Gurjar et al, 2004). After the implementation of CNG, only SO2 concentrations develop a decreasing trend, whereas the NOx concentration seems to be increasing. The explanation for increasing NOx concentration seems to be related with the significant increase in total number of vehicles each year in Delhi and with the higher flash-point of CNG (540 °C) compared to that of diesel (232–282 °C). At such a high temperature, more nitrogen from the air compresses and reacts with oxygen in the combustion chamber of CNG driven vehicles and

thus produces more NOX. A study conducted by CPCB (2009) shows that 97% of hydrocarbon (HC), 76% of CO and 50% of NOx emission comes in air from vehicular activity and hence a fall/increase in the levels of these pollutants can be related to the CNG implementation. As per the studies done by various agencies, it has been observed that even after the implementation of CNG there is no improvement in the status of the pollutants except SO2. Therefore, the objective of our present study is based on whether CNG conversion has impinged on the primary pollutant and tropospheric ozone pollution profile and for the improvement in the quality of air in post CNG period (2002-2009) at secondary data collection site (ITO-X) and generated data collection sites i.e. Site I (Yamuna Biodiversity Park, away from traffic intersection), Site II (Traffic intersection at outside YBP, outer ring road, Gandhi vihar), Site III (Aravalli Biodiversity Park, away from traffic intersection) and Site IV (traffic intersection at outside ABP, ring road, Vasant vihar). The data collected on generated sites was only performed in monsoon season (Aug-Sept, 2009). Methodology The secondary data of the air pollutants (NO2, SO2, SPM, RSPM, CO & O3) were collected from ITO-X site in the last 7 years (2002-2009) from CPCB website (www.cpcb.nic.in). For generated data, four sites were selected which are distinct on the basis of two zones: Riverine zone [Site I Yamuna Biodiversity Park (YBP), near Gandhi vihar, Delhi and Site II - Traffic intersection outside YBP, near Gandhi vihar, outer ring road, Delhi] and Hilly zone [Site III - Aravalli Biodiversity Park (ABP), inside Vasant Vihar, Delhi and Site IV – Traffic Intersection outside ABP Vasant Vihar, Ring Road, Delhi]. The sampling was done during monsoon season (AugSept, 2009) for regularly 7 days with time interval of 8 hrs of both the pollutants one primary (NO2) and secondary (O3). High Volume Sampler (Model No: ENVIRO APM 430), was used to measure NO2 at Site I & III. The instrument has been kept at the height 10 m above the ground. Simultaneously the hourly metrological data were also recorded at these sites at all the four selected sites with the help of pocket weather monitor (Kestrel, K3000-342127,USA). For the measurement of ground level ozone (O3), ozone sensor (Model No: Aeroqual,Series 500), was used

SAXENA et al., Curr. World Environ., Vol. 7(1), 109-115 (2012) for regularly 7 days for 8 hrs at all the sites (Site I – IV). RESULTS AND DISCUSSION For secondary data collection, primary pollutants which CPCB has been taken into account are NO2 ,SO2 ,SPM ,RSPM & CO and one of the secondary pollutants viz.O3. The trend of fluctuation of primary and secondary pollutants in last 7 years (2002-2009) at ITO-X site has been compiled and taken in Fig.1(a-f). The highest concentration of NO2 (126.66µg/m3) was reported in the year 2008 and in other reported years, either it crosses permissible limit (80µg/m3) or hovered around it (taken in Fig. 1a). So, it is quite interesting to note that even after the implementation of CNG programme in Delhi, NOx level is still showing increasing trend. It may be due to diesel vehicles whose sale in Delhi has registered an increase of 106% since 1999. These vehicles emits 3 times more NOx than petrol vehicles. Surprisingly, emission from a poorly maintained CNG fleet can also increase NOx because advanced testing facilities are not available for accurate NOx measurements (CSE 2004). Taken in Fig.1b), the concentration of ozone was highest (48.44µg/m 3) in the year 2009. However, it did not cross the threshold level (80µg/ m3) for plant species as prescribed by NCLAN (National Crop Loss Area Network). Increase in ozone level may be due to the increase in precursor gases (NOx, CO, VOCs) (Leone and Seinfeld 1984). The profile of SO2 (Taken in Fig.1c) shows highest concentration (22.57 µg/m3) in the year 2007. Interestingly, SO2 is the only pollutant which shows significant decrease in the level after

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implementation of CNG programme. Here only, Government’s mitigation policy measures that appears to have had a positive impact on air quality. The reduction of sulphur dioxide in the ambient air is due to the lowering of suphur content of diesel and petrol which converts SO2 to sulphates ( a fine particle) (Narain and Krupnick 2007) . We can notice taken in Fig. 1d, the highest concentration of CO ( 3028.228µg/m3 ) which was observed in the year 2002 and in other years (2002- 2009) either it crosses or have approached the threshold value ( 2000µg/m3). Taken in Fig.8e highest concentration of SPM ( 597.34 µg/m3) was recorded in the year 2009 and also in case of RSPM highest concentration ( 301.87µg/m3 ) was also recorded in the year 2009 (Taken in Fig.8f). In other years their concentration crossed their respective permissible limits (200µg/m3) for SPM and (100µg/ m3) for RSPM. After the implementation of CNG programme, these pollutants are not showing decreasing trend, rather their concentration is increasing due to poor three-wheeler technology which includes poor quality of piston rings as well as the improper maintenance of air filters (Narain and Krupnick 2007). For generated data collection, as discussed in methodology section, four sites were taken into account. Yamuna Biodiversity Park (YBP) is designated as ‘away from traffic intersection’ (Site I) with dense vegetation monitoring site. The nitrogen dioxide (NO2) and ground level ozone (O3) monitoring was done during daytime (10:00a.m6:00p.m) in monsoon month (20th -27th Aug’ 2009). Take in Fig.2, it is clearly depicted that the average concentration (for 7 days) of NO2 was found to be

Table 1 : Meteorogical parameters observed at four Sites Parameters

Site I

Site II

Site III

Site IV

Ambient Temperature (0C)

32.45-30.4

32.4 - 30.3

34.2 - 27.8

35.8 - 32.4

Relative Humidity (%)

41.2 - 29.28

35.42 - 23.14

80 - 51.57

31.0 - 23.8

Wind speed (Km/hr)

1.48 - 0.22

0.23 - 0.9

0 - 0.5

1.8 - 1.2

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2.92 µg/m3 and for O3 was 23.25 µg/m3. The highest concentration of NO2 (4.16 mg/m3) was recorded on 23rd Aug’09 (4th day) and for O3 (27.1µg/m3) on 26th Aug (6th day). Moreover, from their diurnal profile, it has also been noticed that the high peaks of ozone were found at 12:00 hrs (26.87µg/m3) and at 14:00 hrs (30.98µg/m3). During the monsoon month, recorded concentrations of NO2 and O3 depicted that the peak levels were under the permissible limit for both the pollutants i.e. NO2 (80µg/m3) and O3 (80µg/m3). This observation can be supported in the earlier study at the same site (Saxena and Ghosh 2009) where they have already reported lower values of pollutant (ozone) during monsoon month as compared to summer and winter months. It is obviously due to the scavenging

action of rain. Besides this, Table 1 also shows that recorded onsite meteorological data at Site I, where wind speed was little higher than other sites this can be a reason for the dispersion of pollutants which ultimately resulted in decrease in the concentration of NO 2 & O 3. At Site II (Traffic intersection outside YBP, Gandhi Vihar, outer ring road) has high density of vehicles (particularly heavy load trucks and buses) with less vegetation. During monsoon month, the ground level ozone (O3) was monitored during daytime (10:00a.m.6:00p.m) (10th Aug -17th Aug’2009). Taken in Fig.3, it was clearly depicted that the average concentration (for 7 days) of O3 was 27.07 mg/m3. The highest concentration of O3 (31.26mg/m3) (6th day) and the lowest was 22.25 mg/m3. Moreover,

Fig. 2: Comparison of average concentration of NO2 & O3 in August 2009 at YBP (Site I)

Fig. 4: Comparison of average concentration of NO2 & O3 in September 2009 at ABP (Site III)

Fig. 3: Comparison of average concentration of O3 in August 2009 at YBP & traffic intersection outside YBP (Site I & Site II)

Fig. 5: Comparison of average concentration of O3 in September 2009 at ABP & traffic intersection outside ABP (Site III & Site IV)

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from their diurnal profile, it has also been noticed that the high peaks were found at 13:00 pm (38.99mg/m3) and 15:00 hrs (41.75mg/m3). The recorded concentrations of O3 depicted that the peak levels were also crossing the permissible limit. This is due to the fact that as compared to Site I, Site II had shown comparatively higher concentrations of ozone due to high emission of precursor gases from the heavy traffic flow as this site is located near outer ring road and comprised of heavy vehicles like trucks and buses, which accelerates the photochemical reactions. In general, as per previous studies (Saxena and Ghosh 2010), there were high concentrations of ozone in summer as well as in winter months but this study analyzes the concentration of ozone in monsoon season, that’s why the reported values were generally less due to the scavenging action by rain (Chan and Kwok 2001). Moreover, in case of tropospheric ozone there is non-availability of sufficient solar radiation and the diurnal amplitude of ozone which is found to be very small during monsoon months (Lal et al, 2000; Saraf et al, 2003 and Jain et al, 2004). Recorded onsite meteorological data at Site II (Table 1), was also clearly reported that due to increase in the rate of wind speed there is dispersion of pollutants which ultimately resulted in decreasing in the concentration of O3 in monsoon period. Aravalli Biodiversity Park (ABP) is designated as ‘away from traffic intersection’ (Site III) with dense vegetation monitoring site. This site is closest to residential area of Vasant Vihar. The nitrogen dioxide (NO2) and ground level ozone (O3) monitoring was done during daytime (10:00a.m-6:00p.m) in monsoon month (22nd -28th Sept’ 2009). Take in Fig.4, it was clearly depicted that the average concentration (for 7 days) of NO2 was found to be 5.72 mg/m3 and for O3 was 19.70 mg/m3. The highest concentration of NO2 (9.54 mg/m3) was recorded on 25th Sept’09 (4th day) and for O3 (24.47 µg/m3) on 28th Sept (7th day). Moreover, from their diurnal profile, it has also been

noticed that the high peaks of ozone were found at 14:00 hrs (21.54µg/m3) and 16:00 hrs (22.98µg/ m3). The recorded concentrations of NO2 and O3 depicted that the peak levels were under the permissible limit of both NO2 (80µg/m3) and O3 (80µg/m3) during the monsoon month. The values of O3 are generally higher in summer and winter months at this site (Saxena et al, 2009) as per previous studies but our present study was conducted during monsoon month that’s why it has somewhat lower values of ozone due to the scavenging action of rain, besides this site was also away from traffic intersection area, therefore on site emission was less which ultimately gave rise to low concentration of pollutants (Lal et al, 2000). At Site IV (Traffic intersection outside ABP, Vasant Vihar, ring road) is a densely vegetative area about 3 km away from Site III (ABP) located near Vasant vihar at ring road with heavy traffic flow (particularly two- wheelers and buses). The ground level ozone (O3) was monitored during daytime (10:00a.m.6:00p.m) in monsoon month (15 th Sept – 21 st Sept’2009). Taken in Fig.5, it was clearly depicted that the average concentration (for 7 days) of O3 was 21.74 µg/m3. The concentration of O3 range from 24.55µg/m3- 19.54 µg/m3 (on 5th and 3rd day). Moreover, from their diurnal profile, it has also been noticed that the high peaks of ozone were found at 13:00 hrs (28.99µg/m3) and 15:00 hrs (35.15µg/ m3). The recorded concentrations of O3 depicted that the peak levels were at below the threshold or permissible limit. Thus, the present study concludes that even after the implementation of CNG there is no remarkable progress in the variation of air pollutants except SO2 in the last 7 years (20022009). Our generated data also suggests that variation in ozone concentration was very site specific. Concentration of secondary pollutant ozone was higher at site II & IV which are kerbside area, facing heavy traffic flow in comparison to vegetative site (site I & III).

REFERENCES

1.

WHO Air Quality Guidelines for Particulate Matter, Ozone, Nitrogen dioxide and Sulfur Dioxide. World Health Organization, Geneva, Switzerland 2: 1-212 (2005).

2.

Monks PS, Granier C, Fuzzi S, Stohl A, Williams ML, Akimoto H, Amanni M, Baklanov A, Baltensperger U, Bey I, Blake N, Blake RS, Carslaw K, Cooper OR,

SAXENA et al., Curr. World Environ., Vol. 7(1), 109-115 (2012)

3.

4.

5.

6.

7.

8.

9.

10.

11.

Dentener F, Fowler D, Fragkou E, Frost GJ, Generoso S, GinouxP, Grewe V, Guenther V, Hansson HC, Henne S, Hjorth J, Hofzumahaus A, Huntrieser H, Isaksen ISA, Jenkin ME, Kaiser J, Kanakidou M, Klimont Z, Kulmala M, Laj P, Lawrence MG, Lee JD, Liousse C, Maione M, McFiggans G, Metzger A, Mieville A, Moussiopoulos N, Orlando JJ, O’Dowd CD, Palmer PI, Parrish DD, Petzold A, Platt U, Po¨ schl . Pre´voˆt ASH, Reeves CE, Reimann S, Rudich Y, Sellegri K, Steinbrecher R, Simpson D, Brink H, Theloke J, Van der Werf GR, Vautard R, Vestreng,V, Vlachokostas Ch, Glasow R Atmospheric Composition Change Global and Regional Air Quality. Atmos Environ .43: 5268–5350 (2009) . WHO World Health Report: Reducing Risks, Promoting Healthy Life. World Health Organization,Geneva, Switzerland l.1: 191(2002). Environment Canada’s Performance Report Ground Level Ozone: Occurrence and Transport in Eastern North America. USCanada Air Committee 2: 1-50 (2003). Lelieveld J, Crutzen PJ Role of Deep Cloud Convection in the Ozone Budget of the Troposphere. Science 264: 1759-1761 (1994). WMO Scientific Assessment of Ozone Depletion. Meteorological Organization, Global Ozone Research and Monitoring Project- WMO, Geneva, Switzerland 2: 1-45 (1998). Central Pollution Control Board (CPCB) India Status of the Vehicular Pollution Control Programme in India. 1: 1-65 (2010). Central Pollution Control Board (CPCB) India National Ambient Air Quality Status.1: 1-85 (2008-2009). WWF Delhi Environmental Status Report, An Information Handbook for Citizen Action. World Wide Life Fund for Nature, India l.1: 1100 (1995). Ministry of Road Transport and Highways, Motor transport statistics, MORTH. Government of India, New Delhi, Retrieved on 26th March 2006 from http: morth. nic.in/ mts.htm (2004). Gurjar BR, Van Aardenne JA, Lelieveld J,

12.

13.

13.

14.

15

16.

16.

17.

18.

19.

115

Mohan M Emission Estimates and Trends (1990–2000) for Megacity Delhi and Implications. Atmos Environ 4: 5663 5681 (2004). CSE Report Right to Clean Air Campaign: Advocating Ways to Reduce Air Pollution. 2: 1-219 (2004). Leone JA, Seinfeld, JH Analysis of the Characteristics of Complex Chemical Reaction Mechanisms: Application to Photochemical Smog Chemistry. Environ. Sci. Technol 184: 280-287(1984) . Narain U, Krupnick A The Impact of Delhi’s CNG Program on Air Quality Resources of the Future, DP 07-06 (2007) . Saxena P, Ghosh C Comparative Variation of Tropospheric Ozone and its Precursor Gases at Traffic Intersection sites in Delhi. Evn Poll Cont J 12(6): 73-76 (2009). Saxena P, Ghosh C Comparative Variation of Ground level Ozone Pollution before and after the Implementation of CNG in Delhi. As J Chem 10: 7498-7506 (2009). Chan LY, Kwok WS Roadside Suspended Particulates at Heavily Trafficked Urban Sites of Hong Kong- Seasonal Variation and Dependence on Meteorological Conditions. Atmos Environ 35: 3177-3182(2001). Lal S., Naja M, Subbaraya BH Seasonal Variations in Surface Ozone and its Precursor Over an Urban Site in India. Atmos Environ 34: 2713-2724 (2000). Saraf N, Beig G, Schultz M Tropospheric Distribution of Ozone and its Precursor Over the Tropical Indian Ocean. J Geo Phy Res 108: 4-9. Jain SL, Arya BC, Kumar A, Ghude SD, Kulkarni PS Observational Study of Surface Ozone at New Delhi, India. Int. J. Rem. Sens. 24: 25-33 (2004). Saxena P, Kumar S, Ghosh C Pattern Change in the Concentration of Greenhouse Gas, Tropospheric Ozone at two Distinct Sites in Delhi during Post CNG Era. In Proceedings of CETAS International Conference on Changing Environmental Trends and Sustainable Development, Guru Jambheshwar University, Hisar, India. 67-71 (2009).

Current World Environment

Vol. 7(1), 117-124 (2012)

Need of Biomedical Waste Management System in Hospitals - An Emerging issue - A Review PRAVEEN MATHUR, SANGEETA PATAN* and ANAND S. SHOBHAWAT Department of Environmental Science, MDS University Ajmer - 305 009 (India). (Received: April 24, 2012; Accepted: May 27, 2012) ABSTRACT Medical care is vital for our life and health, but the waste generated from medical activities represents a real problem of living nature and human world. Improper management of waste generated in health care facilities causes a direct health impact on the community, the health care workers and on the environment Every day, relatively large amount of potentially infectious and hazardous waste are generated in the health care hospitals and facilities around the world. Indiscriminate disposal of BMW or hospital waste and exposure to such waste possess serious threat to environment and to human health that requires specific treatment and management prior to its final disposal. The present review article deals with the basic issues as definition, categories, problems relating to biomedical waste and procedure of handling and disposal method of Biomedical Waste Management. It also intends to create awareness amongst the personnel involved in health care unit.

Key words: Hazardous waste, Biomedical Waste Management, Health care unit.

INTRODUCTION Biomedical waste management has recently emerged as an issue of major concern not only to hospitals, nursing home authorities but also to the environment. the bio-medical wastes generated from health care units depend upon a number of factors such as waste management methods, type of health care units, occupancy of healthcare units, specialization of healthcare units, ratio of reusable items in use, availability of infrastructure and resources etc.1 The proper management of biomedical waste has become a worldwide humanitarian topic today. Although hazards of poor management of biomedical waste have aroused the concern world over, especially in the light of its far-reaching effects on human, health and the environment.2 Now it is a well established fact that there are many adverse and harmful effects to the environment including human beings which are caused by the “Hospital waste” generated during

the patient care. Hospital waste is a potential health hazard to the health care workers, public and flora and fauna of the area. The problems of the waste disposal in the hospitals and other health-care institutions have become issues of increasing concern. 3 Definition According to Biomedical Waste (Management and Handling) Rules, 1998 of India “Any waste which is generated during the diagnosis, treatment or immunization of human beings or animals or in research activities pertaining thereto or in the production or testing of biologicals. 4 The Government of India (notification, 1998) specifies that Hospital Waste Management is a part of hospital hygiene and maintenance activities. This involves management of range of activities, which are mainly engineering functions, such as collection, transportation, operation or treatment of processing systems, and disposal of wastes. 4

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One of India’s major achievements has been to change the attitudes of the operators of health care facilities to incorporate good HCW management practices in their daily operations and to purchase on-site waste management services from the private sector. (Bekir Onursal, 2003)

• • •

World Health Organization states that 85% of hospital wastes are actually non-hazardous, whereas 10% are infectious and 5% are noninfectious but they are included in hazardous wastes. About 15% to 35% of Hospital waste is regulated as infectious waste. This range is dependent on the total amount of waste generated (Glenn and Garwal, 1999).5

Problems relating to biomedical waste A major issue related to current BioMedical waste management in many hospitals is that the implementation of Bio-Waste regulation is unsatisfactory as some hospitals are disposing of waste in a haphazard, improper and indiscriminate manner. Lack of segregation practices, results in mixing of hospital wastes with general waste making the whole waste stream hazardous. Inappropriate segregation ultimately results in an incorrect method of waste disposal.

Classification of Bio-Medical Waste The World Health Organization (WHO) has classified medical waste into eight categories: ´ General Waste ´ Pathological ´ Radioactive ´ Chemical ´ Infectious to potentially infectious waste ´ Sharps ´ Pharmaceuticals ´ Pressurized containers Sources of Biomedical Waste Hospitals produce waste, which is increasing over the years in its amount and type. The hospital waste, in addition to the risk for patients and personnel who handle them also poses a threat to public health and environment. Major Sources • Govt. hospitals/private hospitals/nursing homes/ dispensaries. • Primary health centers. • Medical colleges and research centers/ paramedic services. • Veterinary colleges and animal research centers. • Blood banks/mortuaries/autopsy centers. • Biotechnology institutions. • Production units. Minor Sources • Physicians/ dentists’ clinics • Animal houses/slaughter houses.

• •

Blood donation camps. Vaccination centers. Acupuncturists/psychiatric clinics/cosmetic piercing. Funeral services. Institutions for disabled persons

Inadequate Bio-Medical waste management thus will cause environmental pollution, unpleasant smell, growth and multiplication of vectors like insects, rodents and worms and may lead to the transmission of diseases like typhoid, cholera, hepatitis and AIDS through injuries from syringes and needles contaminated with human.6 Various communicable diseases, which spread through water, sweat, blood, body fluids and contaminated organs, are important to be prevented. The Bio Medical Waste scattered in and around the hospitals invites flies, insects, rodents, cats and dogs that are responsible for the spread of communication disease like plague and rabies. Rag pickers in the hospital, sorting out the garbage are at a risk of getting tetanus and HIV infections. The recycling of disposable syringes, needles, IV sets and other article like glass bottles without proper sterilization are responsible for Hepatitis, HIV, and other viral diseases. It becomes primary responsibility of Health administrators to manage hospital waste in most safe and eco-friendly manner6. The problem of bio-medical waste disposal in the hospitals and other healthcare establishments has become an issue of increasing concern, prompting hospital administration to seek new ways of scientific, safe and cost effective

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Fig. 1 management of the waste, and keeping their personnel informed about the advances in this area. The need of proper hospital waste management system is of prime importance and is an essential component of quality assurance in hospitals.

Need of biomedical waste management in hospitals The reasons due to which there is great need of management of hospitals waste such as: 1. Injuries from sharps leading to infection to all categories of hospital personnel and waste handler. 2. nosocomial infections in patients from poor infection control practices and poor waste management. 3. Risk of infection outside hospital for waste handlers and scavengers and at time general public living in the vicinity of hospitals. 4. Risk associated with hazardous chemicals, drugs to persons handling wastes at all levels. 5. â&#x20AC;&#x153;Disposableâ&#x20AC;? being repacked and sold by unscrupulous elements without even being washed. 6. Drugs which have been disposed of, being repacked and sold off to unsuspecting

7.

buyers. Risk of air, water and soil pollution directly due to waste, or due to defective incineration emissions and ash3.

Biomedical Waste Management Process There is a big network of Health Care Institutions in India. The hospital waste like body parts, organs, tissues, blood and body fluids along with soiled linen, cotton, bandage and plaster casts from infected and contaminated areas are very essential to be properly collected, segregated, stored, transported, treated and disposed of in safe manner to prevent nosocomial or hospital acquired infection. 1. Waste collection 2. Segregation 3. Transportation and storage 4. Treatment & Disposal 5. Transport to final disposal site 6. Final disposal Biomedical Waste Treatment and Disposal Health care waste is a heterogeneous mixture, which is very difficult to manage as such. But the problem can be simplified and its dimension reduced considerably if a proper management system is planned.

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Incineration Technology This is a high temperature thermal process employing combustion of the waste under controlled condition for converting them into inert material and gases. Incinerators can be oil fired or electrically powered or a combination thereof. Broadly, three types of incinerators are used for hospital waste: multiple hearth type, rotary kiln and controlled air types. All the types can have primary and secondary combustion chambers to ensure optimal combustion. These are refractory lined.7 Non-Incineration Technology Non-incineration treatment includes four basic processes: thermal, chemical, irradiative, and biological. The majority of non-incineration technologies employ the thermal and chemical processes. The main purpose of the treatment technology is to decontaminate waste by destroying pathogens. Facilities should make certain that the technology could meet state criteria for disinfection. 9 Autoclaving ´ The autoclave operates on the principle of the standard pressure cooker. ´ The process involves using steam at high temperatures. ´ The steam generated at high temperature penetrates waste material and kills all the micro organism ´ These are also of three types: Gravity type, Pre-vacuum type and Retort type. In the first type (Gravity type), air is evacuated with the help of gravity alone. The system operates with temperature of 121 deg. C. and steam pressure of15 psi. for 60-90 minutes. Vacuum pumps are used to evacuate air from the Pre vacuum autoclave system so that the time cycle is reduced to 30-60 minutes. It operates at about 132 deg. C. Retort type autoclaves are designed much higher steam temperature and pressure. Autoclave treatment has been recommended for microbiology and biotechnology waste, waste sharps, soiled and solid wastes. This technology renders certain categories (mentioned in the rules) of bio-medical waste innocuous and unrecognizable so that the treated residue can be land filled. 8

Microwave Irradiation ´ The microwave is based on the principle of generation of high frequency waves. ´ These waves cause the particles within the waste material to vibrate, generating heat. ´ This heat generated from within kills all pathogens. Chemical Methods ´ 1 % hypochlorite solution can be used for chemical disinfection Plasma Pyrolysis Plasma pyrolysis is a state-of-the-art technology for safe disposal of medical waste. It is an environment-friendly technology, which converts organic waste into commercially useful byproducts. The intense heat generated by the plasma enables it to dispose all types of waste including municipal solid waste, biomedical waste and hazardous waste in a safe and reliable manner. Medical waste is pyrolysed into CO, H2, and hydrocarbons when it comes in contact with the plasma-arc. These gases are burned and produce a high temperature (around 1200oC).9 Biomedical Waste Management Rules Safe disposal of biomedical waste is now a legal requirement in India. The Biomedical Waste Management & Handling) Rules, 1998 came into force on 1998. In accordance with these rules, it is the duty of every “occupier” i.e. a person who has the control over the institution or its premises, to take all steps to ensure that waste generated is handled without any adverse effect to human health and environment. It consists of six schedules. Schedule I Schedule II Schedule III Schedule IV Schedule V Schedule VI Schedule IV Label for Transport of Bio-Medical Waste Containers/Bags Day ………… Month ………….......Year ………...... Date of generation ………………............................. Waste category No …….. Waste class

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Schedule 1. Categories of Bio-Medical Waste Option

Treatment & Disposal

Waste Category

Cat. No. 1

Incineration /deepburial

Cat. No. 2

Incineration /deep burial

Cat. No. 3

Local autoclaving/ micro waving/ incineration

Cat. No. 4

Disinfections (chemical treatment /autoclaving/micro waving and mutilation shredding

Cat. No. 5

Incineration / destruction & drugs disposal in secured landfills

Cat. No. 6

Incineration , autoclaving/micro waving

Cat. No. 7

Disinfections by chemical treatment autoclaving/micro waving& mutilation shredding.

Cat. No. 8

Disinfections by chemical treatment and discharge into drain

Cat. No. 9

Disposal in municipal landfill

Cat. No. 10

Chemical treatment & discharge into drain for liquid & secured landfill for solids

Human Anatomical Waste (human tissues, organs, body parts) Animal Waste Animal tissues, organs, Body parts carcasses, bleeding parts, fluid, blood and experimental animals used in research, waste generated by veterinary hospitals / colleges, discharge from hospitals, animal houses) Microbiology & Biotechnology waste (wastes from laboratory cultures, stocks or specimens of micro-organisms live or attenuated vaccines, human and animal cell culture used in research and infectious agents from research and industrial laboratories, wastes from production of biological, toxins, dishes and devices used for transfer of cultures) Waste Sharps (needles, syringes, scalpels blades, glass etc. that may cause puncture and cuts. This includes both used & unused sharps) Discarded Medicines and Cytotoxic drugs (wastes comprising of outdated, contaminated and discarded medicines) Solid Waste (Items contaminated with blood and body fluids including cotton, dressings, soiled plaster casts, line beddings, other material contaminated with blood) Solid Waste (waste generated from disposable items other than the waste sharps such as tubing, catheters, intravenous sets etc.) Liquid Waste (waste generated from laboratory & washing, cleaning , housekeeping and disinfecting activities) Incineration Ash (ash from incineration of any bio-medical waste) Chemical Waste (chemicals used in production of biological, chemicals, used in disinfect ion, as insecticides, etc)

(Source- The Bio Medical Waste (Management and Handling) Rules, 1998)

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Schedule II: Colour Coding and Type Of Container for Disposal of Bio-Medical Wastes Colour Coading

Type of Containers

Waste Category

Treatment Options as per Schedule 1

Yellow Red

Plastic bag Disinfected Disinfected Container/Plastic bag Plastic bag/puncture proof container Plastic bag

1,2,3,6 3,6,7

Incineration/deep burial Autoclaving/Micro waving/ Chemical Treatment Autoclaving/Micro waving/chemical treatment and destruction/shredding Disposal in second landfill

Blue/White Translucent Black

4,7 5,9,10 (solid)

Schedule III: Label for Bio-Medical Waste Containers/Bags

Waste description Sender’s Name & Address Receiver’s Name & Address Phone No …..........…... Phone No .......…………… Telex No …...................Telex No ……..........……… Fax No ……………....... Fax No ………...........…….. Contact Person ……................................................... Contact Person ……… In case of emergency please contact Name & Address: Phone No. Note: Label shall be non-washable and prominently visible. Schegule-V Standards for Treatment and Disposal Of Bio-Medical Wastes Standards For Incinerators Schegule-VI Schedule for Waste Treatment Facilities

like Incinerator/ Autoclave/ Microwave System.10 (Source- The Bio Medical Waste (Management and Handling) Rules, 1998). Benefits of Biomedical Waste Management ´ Cleaner and healthier surroundings. ´ Reduction in the incidence of hospital acquired and general infections. ´ Reduction in the cost of infection control within the hospital. ´ Reduction in the possibility of disease and death due to reuse and repackaging of infectious disposables. ´ Low incidence of community and occupational health hazards. ´ Reduction in the cost of waste management and generation of revenue through appropriate treatment and disposal of waste. ´ Improved image of the healthcare establishment and increase the quality of life.

MATHUR et al., Curr. World Environ., Vol. 7(1), 117-124 (2012) Recommendations 1. For the use of incinerator Training should be given to some number of persons from staff. 2. Specific fund should be allocated for the use of incinerator. 3. Every hospital should have special boxes to use as dustbin for bio-medical waste. 4. Bio-medical waste should not be mixed with other waste of Municipal Corporation. 5. Private hospitals should also be allowed to use incinerator, which is installed, in govt. hospital. For this purpose a specific fee can be charged from private hospitals. 6. Special vehicle i.e. bio-medical waste vehicle should be started to collect waste from private hospitals and private medical clinics and carry it up to the main incinerator. 7. As provided by bio-medical waste rules, the whole of the waste should be fragmented into colours due to their hazardous nature. 8. Bio-medical waste Management Board can be established in each District. 9. Either judicial powers should be given to the management board or special court should be established in the matters of environment pollution for imposing fines and awarding damages etc. 10. Housekeeping staff wear protective devices such as gloves, face masks, gowned, while handling the waste.

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There is biomedical waste label on waste carry bags and waste carry trolley and also poster has put on the wall adjacent to the bins (waste) giving details about the type of waste that has to dispose in the baggage as per biomedical waste management rule. Carry bags also have the biohazard symbol on them. CONCLUSION

Medical wastes should be classified according to their source, typology and risk factors associated with their handling, storage and ultimate disposal. The segregation of waste at source is the key step and reduction, reuse and recycling should be considered in proper perspectives. We need to consider innovative and radical measures to clean up the distressing picture of lack of civic concern on the part of hospitals and slackness in government implementation of bare minimum of rules, as waste generation particularly biomedical waste imposes increasing direct and indirect costs on society. The challenge before us, therefore, is to scientifically manage growing quantities of biomedical waste that go beyond past practices. If we want to protect our environment and health of community we must sensitize our selves to this important issue not only in the interest of health managers but also in the interest of community.

REFERENCES

1.

2.

3.

4.

Mandal S. K. and Dutta J. , Integrated BioMedical Waste Management Plan for Patna City, Institute of Town Planners, India Journal 6-2: 01-25 (2009). Singh V. P., Biswas G., and Sharma, J. J., Biomedical Waste Management - An Emerging Concern in Indian Hospitals Indian, Journal of Forensic Medicine & Toxicology, Vol. 1, No. 1. (2007-12). Hem Chandra, Hospital Waste an Environmental Hazard and Its Management, (1999). Govt. of India, Ministry of Environment and Forests Gazette notification No 460 dated

5.

6. 7.

8.

July 27, New Delhi: 1998: 10-20 Glenn, Mc.R & Garwal, R. Clinical waste in Developing Countries. An analysis with a Case Study of India, and a Critique of the BasleTWG Guidelines (1999) CEET: Biomedical Waste ManagementBurgeoning issue (2008) Gravers PD. Management of Hospital Wastes- An overview. Proceedings of National workshop on Management of Hospital Waste, (1998) Thornton J., Tally MC, Orris P., Wentreg J. Hospitals and plastics Dioxin prevention and

124

9.

10. 11.

MATHUR et al., Curr. World Environ., Vol. 7(1), 117-124 (2012) Medical Waste Incineration; Public Health Reports. 1996; 1:299- 313. Surjit S. Katoch Biomedical Waste Classification and Prevailing Management Strategies, Proceedings of the International Conference on Sustainable Solid Waste Management, p. p.169-175 (2007). The Bio Medical Waste (Management and Handling) Rules, (1998). Dr. Saurabh Sikka, Biomedical Waste in

12.

13.

Indian Context. Shalini Sharma* and S.V.S.Chauhan, Assessment of bio-medical waste management in three apex Government hospitals of Agra, Journal of Environmental Biology, 29(2), p. p 159-162 (2008) Bekir Onursal, Health Care Waste Management in India. The world Bank (2003).

Current World Environment

Vol. 7(1), 125-131 (2012)

Physico-chemical Characterization of Water Body with Special Reference to Battery, Power Sources and Metal Plating Effluents DHANANJAY DWIVEDI1 and VIJAY R. CHOUREY2 1

Department of Chemistry, PMB Gujarati Science College, Indore - 452 001 (India). 2 Government Holkar Autonomous Science College, Indore - 452 001 (India). (Received: April 03, 2012; Accepted: May 20, 2012) ABSTRACT

The World is facing a tremendous set of environmental problems which are due to the contaminated ground water and hazardous waste effluents coming out of process industries due to advanced industrialization in different field. Thus, it is essential to rectify this problem.

Key words: Water bodies, Battery, power sources, Metal plating effluents.

INTRODUCTION

EXPERIMENTAL

The life on the earth depends on the water. Everything originated in the water and sustain by water. It is most common abundant, indispensable, inorganic component of the earthâ&#x20AC;&#x2122;s environment, constitutes living matter predominantly. It is a prime resource and physiological necessity to mankind.

The samples collected from the effluents at the time of mixing into the river khan were analyzed to determine various physico-chemical parameter and to study the preserve of cations and anione. As there are no. of different resourced which are discharging continuously their effluents in the river. Due to this a separate study was carried out on the effluents of each source at the function point and tabulized accordingly work is performed on the effluents discharge by, i. Battery and power sourced effluents. ii. Metal plating effluents.

This work include the sample collection technique, collection, preservation and handling of collected sample. The collected samples were analyzed for the determination of Physico-chemical parameter i.e. colour, temperature, Eh, pH, specific conductivity, total solid, dissolved solids, acidity total hardness, alkalinity, TDIC, TOC, DO, BOD, COD & Phenols1-2. Analysis of cadmium, chromium, nickel, copper, iron, lead, zinc, manganese, magnesium, arsenic, calcium & vanadium ions performed with the help of Flame Atomic Absorption spectroscopy13-14. Carbonates, bicarbonates, sulphide, sulphate, phosphate, total-N, nitrate-N, nitrite-N, organic nitrogen and chlorides are analyzed using standard method.

For the determinants of undertaken parameters, a set of four sample from each source on each data as given in the table were analyzed for the year 2005-06 and results are summarized in the subsequent tables. RESULTS AND DISCUSSION Battery & power sources The effluent contains toxic cations viz. Vi, Cd, Zn, Pb & traces of v. The major fractions constituted from this industry is lead itâ&#x20AC;&#x2122;s highest concentration was found in March and April. The

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Table 1:Battery and Power Sources : Analysis of physico chemical characteristics of effluents Date

9-Jan-05

SS→ →P↓ I 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41

Bf 23 5.2 49 13.5 300 82 382 nd 610 13 nd 19 581 341 390 321 nd 38 nd 132 6.2 12 262 nd nd 2.8 1 nd 11 0.4 7.5 7.3 6.2 nd nd 6.6 1.3 0.6 nd

15/4/2005

28-Jul-05

8-Nov-05

II

III

IV

I

II

III

IV

I

II

III

IV

I

II

III

22 5.4 49 13.8 281 73 342 559 9.6 2.2 532 320 362 301 26 nd 109 4.2 8 242 1.8 0.7 6.9 0.8 3.9 5.6 5.2 4.8 4.1 0.03

20.8 7.1 37 14.3 123 42 161 200 1.6 2.6 301 158 162 162 19 61 0.9 200 1.2 0.46 0.4 0.8 0.4 2.8 0.9 -

Bf 21.2 7.1 37 14.3 164 45 211 241 2.1 2.3 322 173 181 178 15 85 0.7 1.1 180 1.4 nd 1.5 0.6 1.2 2.9 1 1.5 2.9 nd -

31 4.9 48 13.2 12.2 72 192 nd nd 702 3.9 3.3 642 411 260 342 41 52 4.2 2 300 4.2 1.7 nd 4.1 nd 11 6.1 18 nd nd 1.4 13 0.02 nd

29 4.9 48 13.6 109 69 178 nd nd 663 3.5 3.3 611 386 253 318 34 46.9 3.2 1.8 280 3.,9 1.5 3.1 8.3 4.2 10 0.4 11 nd -

29.2 6.9 57 12.3 90 52 142 212 1.3 2.9 361 141 140 181 30 42 nd 0.4 254 2.6 0.9 0.6 0.3 0.8 0.9 8.1 -

Bf 27 6.7 57 13.2 98 66 163 242 1.5 2.9 415 159 149 192 25 47 0.6 0.6 216 1.9 1 0.8 1.4 1.1 2.3 11 -

31 4.4 61 14.1 211 52 262 nd nd 601 18 nd 2.6 512 353 470 311 26 161 10 8.1 220 2.9 0.9 nd 8.2 nd 1.8 4.8 5.3 nd nd nd 11 nd nd

31 4.6 59 13.4 184 45 232 579 12.4 2.8 470 340 449 302 12 149 7.7 6 176 1.9 0.6 5.3 0.7 3.3 3.8 6.6 -

30.3 7.3 30 12.6 121 66 184 163 1.6 3.3 282 166 138 136 9 53 0.6 110 1.4 nd 0.8 0.2 0.5 0.3 3 -

Bf 30.3 7.3 30 12.8 136 73 211 221 3 4 293 160 162 152 12 66 0.6 0.9 122 1.2 0.11 1.2 0.3 2.9 0.8 3.6 -

28.7 4.4 61 14 142 61 201 nd nd 542 2.1 3.1 483 301 456 262 36 36 111 8.2 6.2 298 4 1.3 4.2 1.4 2.6 2.8 3.3 nd nd 4.3 4.2 nd nd

28.4 4.5 58 12.9 113 58 169 511 1.69 3 478 304 429 242 30 30 91 6.7 5.4 235 3.6 1.2 3.2 1 1.3 2.2 2.8 3.3 2.8 -

23 7 32 12.9 111 53 163 142 1.4 3.2 288 152 134 146 14 14 56 0.5 0.6 186 2.8 0.8 0.6 0.3 0.5 0.2 1.9 -

IV Bf 23.9 6.9 35 13.5 113 59 172 181 2.8 3.2 306 148 161 158 19 19 65 0.6 1 211 1.2 0.9 1.8 0.6 0.4 1.1 0.8 2.1 -

DWIVEDI & CHOUREY, Curr. World Environ., Vol. 7(1), 125-131 (2012)

127

Table 2: Battery and Power Sources : Analysis of physico chemical characteristics of effluents Date

28-Nov-05

SS→ →P↓ I 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41

bn 26 4.7 54 14.1 241 71 311 nd 562 17 nd 2.4 nd 312 573 342 312 nd nd nd 156 6 12 nd nd nd nd 6.6 nd 9 2.2 14 5.8 7.2 nd nd 3.9 17 0.04 nd

10-Mar-06

20-Jun-06

20-Sep-06

II

III

IV

I

II

III

IV

I

II

III

IV

I

II

III

24 4.9 50 14.5 216 63 283 540 13 2.8 297 563 328 310 134 3.8 7 3 6.8 1.6 9.3 4.4 5.9 2.9 9 nd -

22.6 7.1 58 13.2 131 39 162 242 2.3 3.6 177 373 173 182 53 0.8 1.4 0.8 0.8 0.6 0.8 0.2 0.8 3.4 -

22.2 6.9 55 13.6 145 58 201 284 3.2 3.4 189 391 192 189 72 0.4 0.6 1.6 1.3 1 2.2 2.2 1.2 1.6 4.2 -

bf 27.1 5.1 50 13.6 145 58 201 nd 641 12 nd 3.2 nd 419 711 282 362 nd nd nd 61 4 3.4 nd nd nd nd 5.3 nd 5.6 nd 8.2 8.1 13 nd nd 2 13 -

26 5.2 49 13.5 133 49 180 610 9.3 3.6 407 681 261 341 nd nd nd 60 2.8 2.2 3 4.4 6.6 6.3 9.2 1.4 11 -

26.2 6.8 52 13.8 96 38 133 262 2 2.8 166 390 163 214 -

25.9 6.7 56 13.9 102 72 172 232 2.5 2.8 161 456 172 131 46 0.5 0.9 3 1.2 1 3.6 1.8 1.2 6.4 -

bf 38.5 4.8 54 14.2 156 66 221 nd 654 16 nd 3.4 nd 393 581 372 372 nd nd nd 81 5.3 1.9 nd nd nd nd 8 nd 6.3 nd 6.2 8.3 9.2 nd nd 2.4 9 0.1 nd

36.9 4.9 62 12.1 143 62 239 642 12.8 3.4 381 577 356 346 73 2.7 1.4 7.3 5.2 5.2 6.7 6.2 6.6 -

33 6.9 58 13.2 98 33 129 282 2.4 3.2 161 381 155 212 47 0.2 0.5 4.8 0.6 0.8 1.3 0.3 0.6 5 -

33.3 6.9 55 13.9 108 43 43 292 3.2 3.2 169 412 172 229 47 0.4 0.6 5 1.6 1.2 4 1.2 0.8 6.5 -

bf 38 4.8 62 12.1 192 79 268 nd 512 21 nd 2.8 nd 328 543 400 402 nd nd nd 140 6.2 9.6 nd nd nd nd 6 nd 6.2 2.1 6.2 5.3 4.2 nd nd 1.6 14 nd nd

37 4.8 61 12.1 168 66 256 484 16 2.9 314 521 376 373 126 4.6 8.3 4.4 4.9 1.6 4.8 4.6 3.6 1.2 15 -

30.8 7.1 58 13.2 128 39 158 211 2.7 3.1 179 332 163 186 41 0.5 0.6 3.2 0.8 0.5 0.6 0.6 0.6 1 9 -

42 0.4 0.6 2.7 0.2 0.2 1.1 0.6 0.6 9 -

IV 30.9 6.9 55 13.9 129 42 176 239 3.4 3.1 192 356 188 201 51 0.4 0.9 3.8 1.2 1 1.6 1.8 0.8 1.2 11 -

128

DWIVEDI & CHOUREY, Curr. World Environ., Vol. 7(1), 125-131 (2012) Table 3 :Battery and Power Sources : Analysis of physico chemical characteristics of effluents

Date

09-Jan-05

SS→ →P↓ I 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41

G 21 3.9 67 15.2 999 236 1236 101 69 nd nd 0.8 2.6 471 171 171 150 44 34 nd 0.1 26 nd 7.1 13 15 1 5.3 nd 21 20.1 1.5 18 nd 0.48 101 nd nd

15-Apr-05

28-Jul-05

08-Nov-05

II

III

IV

I

II

III

IV

I

II

III

IV

I

II

III

20 4.8 49 13.2 901 201 101 93 63 0.66 2.7 463 153 162 126 38 30 0.1 25.3 6.3 10.8 1.4 0.7 3.3 16.4 16.3 0.6 13 0.3 81 -

20 6.8 56 13.2 316 126 441 241 451 0.5 3.3 163 153 142 115 0.2 92 110 15 4.5 4.2s 1.4 nd 0.4 0.7 7 0.1 0.7 nd 75 -

21.1 6.8 57 13.4 482 222 711 246 451 0.2 3.1 236 113 160 110 104 112 16 5 6.3 3.8 0.3 1.2 3.2 9.9 0.2 5.1 79 -

G 25 5 47 13.6 2901 701 3601 716 531 nd nd 1.1 1.5 496 181 202 625 nd 282 252 nd 0.3 28 9.2 4.2 7 1.3 16 2.1 20 15 0.5 30 nd nd 101 nd nd

26 5.8 38 15.6 2631 472 3101 669 476 0.9 1.7 471 171 148 606 nd 1.5 241 215 19 6.2 3.2 5.1 1.2 9.3 2.2 9 11.3 0.2 17

28 6.8 58 13.2 1211 392 160 601 366 0.3 2.1 171 101 161 131 4 201 165 12 5 3.8 0.9 0.3 1.6 4.1 7.2 41 -

28.1 6.8 55 12.9 2051 242 2291 616 401 0.2 1.8 241 121 168 196 1.3 221 81 18 5.4 4 2 1 4.1 1 1.9 10 0.1 12 63 -

T 29 4.8 43 13.8 661 331 990 211 96 nd nd 0.66 2.6 411 156 150 121 59 36 nd 0.6 30 nd 8 7.4 14 0.6 5.8 4.1 10 25 1 20 nd nd 181 nd nd

27.9 5.8 37 14.7 606 304 910 193 85 0.5 2.8 393 148 139 99 50 32 18.4 7.2 6.2 11 0.5 5 1.3 6 20 0.5 15.2 121 -

27.4 8 57 12.8 291 181 471 211 411 3.5 181 107 122 92 101 23 12 4.8 4.4 4.1 0.2 0.6 1.7 0.8 7.3 0.6 103 -

27.2 8 58 12.6 436 294 730 206 418 0.3 3.4 206 111 124 96 123 129 12.8 5.3 6 4.4 0.26 2.1 2.1 3.6 8.9 0.2 8.3 95 -

G 27.4 5.1 48 13.3 796 251 1045 171 76 nd nd 0.5 2.9 526 161 311 62 nd nd 50 28 nd 0.1 15 nd 6 8 9.1 0.5 7.6 1.7 6 10.1 0.8 22 nd nd 221 nd -

26.6 5.6 40 15.3 719 261 981 156 75 0.33 3.1 493 153 292 43 0.8 42 26 12.1 5.1 9 8 0.3 6.1 4.3 4.9 9.1 0.3 15 197 -

25.6 6.6 54 13.4 291 141 431 201 341 3.2 171 108 132 90 0.5 98 109 12.5 3.2 4.6 2.5 0.2 0.3 1.6 1.1 5 0.3 0.3 141 -

83 -

IV 26.3 7.3 54 12.8 462 305 764 210 353 3.2 241 121 164 96 0.2 120 114 12.6 4 6.2 3.1 0.2 2.8 2.9 2.2 5.9 0.3 0.8 163 -

DWIVEDI & CHOUREY, Curr. World Environ., Vol. 7(1), 125-131 (2012)

129

Table 4: Battery and Power Sources : Analysis of physico chemical characteristics of effluents Date SS→ →P 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41

28-Nov-05

10-Mar-06

20-Jun-06

I

II

III

IV

I

II

III

IV

I

II

G 27 4.8 62 12.2 2001 901 2901 302 nd nd 171 2.7 nd 175 471 201 216 nd nd 111 79 nd 0.8 21 nd nd 9 10 0.3 10 2 12 8 0.8 7 nd 0.02 100 nd nd

25.5 5.4 46 13.9 1582 981 2561 272 161 2.9 171 460 192 201 97 71 19 7.7 8 0.3 7 1.7 7.6 6 0.6 4.6 96 -

24.2 7.2 59 12.6 502 311 812 392 0 311 3.3 111 189 156 85 111 156 14.6 4.6 1.2 0.05 1 0.3 0.6 3 0.2 0.3 90 -

25 7.1 58 13.2 711 571 1281 405 327 3.3 111 189 173 104 123 162 16 6.9 1.9 0.2 2.8 0.9 3.2 3.6 0.3 2.1 102 -

T 28 4.9 49 13.5 2402 699 3100 606 427 1.8 nd 166 601 181 401 nd nd 152 321 nd nd 21 7 nd 5.4 8 1.3 9.1 3 12 20 0.5 0.9 nd 0.6 40 nd nd

26.2 5.2 49 13.5 2160 411 2561 578 416 2.1 148 566 136 380 131 286 16.8 5 4.5 5.9 1.2 6.2 2 8 16 0.3 7.1 0.02 28 -

26 6.9 58 13.2 1002 240 1240 411 382 2.4 121 185 173 110 183 201 14 6 4 1.2 0.9 2 0.4 0.5 5.6 6.1 49 -

26 6.8 55 13.2 1600 290 1893 465 392 1.9 1239 266 175 136 176 217 19.3 6.1 4.3 2.6 1 2.6 0.9 2.4 8.2 0.2 5.2 49 -

T 40 4.9 49 13.5 2604 128 2734 732 nd nd 492 2.1 nd 152 560 186 445 nd nd 149 352 nd nd 24 12 nd 5.6 6 0.8 7 1 9 25 0.9 13 nd 0.5 61 nd nd

40 6 49 13.5 2500 605 3100 501 470 1.8 138 520 164 210 131 313 21.6 8.3 5.2 4.6 0.5 4.3 0.6 4.3 18 0.4 7 0.3 50 -

20-Sep-06 III

IV

I

II

III

IV

G 39 38.9 31 30 28 27.6 6.5 6.6 4.6 6.2 7.9 7.9 53 52 53 -51 -40 -40 12.8 13.1 14.1 12.4 14.3 14.3 1201 1701 1601 1313 362 661 270 291 401 331 241 231 1461 1990 2003 1640 602 992 285 312 316 284 410 428 nd nd 384 397 211 196 340 372 2.8 2.4 3.1 3.2 3.7 3.7 - 0.82 116 127 186 176 109 122 181 271 511 495 185 244 171 178 162 153 146 148 151 165 162 149 89 92 nd nd 149 197 103 92 113 126 236 201 66 59 149 154 nd nd 14 15 27 25.2 10 13 6.4 6.5 nd 14 12.3 8 8.9 4.8 6 6 4.6 5 5.3 1 2.2 7 5.5 1.9 2.1 0.1 0.3 0.6 0.05 0.08 0.16 3.6 2.8 5 3.9 0.2 1.6 0.2 0.3 5.1 4 1 1.6 0.4 1.1 5 5 0.5 2.2 5.8 14.2 12 8.5 3.9 5.3 0.2 0.9 0.5 0.3 0.4 0.3 4.2 6 3.9 0.1 1.7 nd 0.2 0.02 42 47 180 181 161 180 nd nd -

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DWIVEDI & CHOUREY, Curr. World Environ., Vol. 7(1), 125-131 (2012)

values decreased largely in downstream. Ni was found in the range of 11.0.4 ppm, with a decreasing trend with season and year. Vanadium was identified from the residence of oil fired boilers and flue, liner, vanadium in water may be accounted for teaching from residence.

increased total solids in suspended form. Thus the dissolved solids increased total solids in April.

The discharge from battery industries related particularly with the recyclic activity, contributes the major fraction of the toxic materials to the water of river khan. The COD, values were high owing to in organic chemicals. DO & BOD values followed decreasing trend towards downstream.

Among cations chromium (o.5-30 mg/L) (0.3-13mg/L during Jan. 05-Nov. 05 and Nov. 05Sept. 06 respectively and cadmium (at source) ranged (1.9-21mg/L) during Jan. 05 - Nov. 06 and (0.5 - 12 mg/L) during Nov. 05 - Sept. 06. In downstream the concentrations of chromium were also found very high and may be explained in terms of high sulphates and due to the low sedimentation property of chromium. In contrast to chromium, cadmium reduced completely in downstream. The

The efficient acidic in nature having pH<4.4 Though the quantity of discharge is less but itâ&#x20AC;&#x2122;s effects are considerably harmful to aquatic biota. Among the major anions identified form the effluents were carbonated, sulphates, chlorides and phosphates. The organic content was found to be high which are characteristics of the TDC values depicted as in the table (2T1 - 2T8). Apart from these, phenols were identified from the effluent of transformer and polymer processing wastes which are dumped in the vicinity of river Khan and related site. Metal Plating/Refining Because of diversified applications the waste effluent from electroplating contributed a variety of toxic and hazardous anions viz. carbonates, chlorides, sulphates and also the cations viz. copper, cadmium, zinc and nickel etc. The effluents directly taken from source differ in appearance owing to different processes. Effluent was acidic in nature at source, which had slightly shifted to neutral after being discharged into the stream and at the downstream pH remained < 7.1. Concentrations of total solids existed high in the effluent. The concentration at the source was highest in April and March. About 75% of total solids was present in dissolved state and remaining is in suspended form. Thus the dissolved solids

The COD values increased with total solids while the BOD values does not reveal any significant observation.

P- Parameter 1. Color 2. Temperature °C 3. pH 4. Eh in MV 5. Specific Conductivity in MS 6. Dissolve Solids 7. Suspended solids 8. Total Solids 9 Alkalinity 10 Total Hardness 11 Acidity 12 T.O.C. 13 T.D.I.C. 14 D.O. 15 C.O.D. 16 B.O.D. 17 Chloride 18 Sulphate 19 Sulphite 20 Sulphide 41 Arsenic

SS-Sampling Site I to IV 21 Bicarbonate 22 Carbonate 23 Phenol 24 Phosphate 25 Total N 26 Nitrate-N 27 Nitrite-N 28 Organic-N 29 Iron 30 Copper 31 Nickel 32 Manganese 33 Cadmium 34 Zinc 35 Lead 36 Chromium 37 Magnesium 38 Vanadium 39 Calcium 40 Tin

Mean concentration (except colour, temperature & pH) expressed in Mg./L G - Gray, T - Turbid, Bf - Buff, n.d. - Not Detected

presence of ions in the source needs special attention as it concerts more Cr(VI) to Cr (III) resulting in high dissolved concentration of Cr (III). Apart from these, nickel and zinc were also contributed from other pools constituting a mined effluent.

DWIVEDI & CHOUREY, Curr. World Environ., Vol. 7(1), 125-131 (2012) The metal refining processor also discharge highly toxic forms of metallic species such as vanadium, lead etc. High levels of lead were detected in the out coming effluents. The results of analysis is given in table from (2T9-2T16).

131

CONCLUSIONS The effluents coming into water body (Pond) is characterized to be highly acidic in nature having pH<4.4. Though the quantity of discharge from industrial unit is less but itâ&#x20AC;&#x2122;s effects are considerably harmful to aquatic biota. The waste effluents from electroplating contributed a variety of toxic and hazardous anions as discussed on the basis of available date of study.

REFERENCES

1.

2. 3. 4. 5.

6. 7. 8.

U.S. Mineral year book Bureau of Mines. U.S. Govt. Printing Office, Washington D.C. (19601979). Niragu J.O. Fisher R.P. Nature, 279: 409-11 (1979). Toxic metals in Soil Plant System (Ede S.M. Ross). Wiky and Wons New York, 3-25 (1994). Zantoponlos N.V. Bull. Znviron, Contamin Toxicol. 62: 691-699 (1999). APHA Standard methods for examination of water and waste 20th Ed., American Public Health Association, Washington D.C., (1995). Meeker E.W. and Wagner E.C. 2nd Eng. Chem. Anal. Ed. 5: 396, (1993). Booth R.L. and Thomas R.F. Environ Sci. Tech. 7: 523 (1973). Tessier A et. al. Anal. Chem, 51: 844-51

9. 10.

11.

12.

13. 14.

(1979). Gupta V., Agrawal J., Purohit M., Res. J. Chem. Environ, 11(1): 40 (2007). Orhan, Y., and Byu-Kgungor The removal of Hearey Metals by using, Agricultural Waste Water, Water Sci, Technol, 28: 247 (1993). Larren L., and Aamand Degradation of herbicides in two sandy aquifers under different red ox conditions. 44(2): 231-236 (2001). V. Magarde, S.A. Iqbal, N. Iqbal and I. Zaafarany, Orient. J. Chem., 27(2): 703-711 (2011). P. Sannasi, S. Salmijah. Orient. J. Chem., 27(2): V. Magarde, S.A. Iqbal, S. Pani and N. Iqbal. Orient. J. Chem. 26(4): 1473-1477 (2010).

Current World Environment

Vol. 7(1), 133-138 (2012)

Physicochemical Determination of Pollutants in Wastewater in Dheradun SACHCHIDA NAND SINGH1, GAURAV SRIVASTAV and ARUN BHATT* Department of Chemistry S.G.G. ( P.G.) College, Dobhi, Jaunpur - 222 149 (India) Department of Biotechnology G.B. Pantt Engineering College Gurdahuri, Pauri Garhwal, (India). (Received: April 03, 2012; Accepted: May 13, 2012) ABSTRACT Wastewater was collected from the Dheradun industrial area situated in capital of uttrakhand. Samples were collected between the periods of November 2010 to Aug.2011 determine the following parameters, pH, temperature, turbidity, chemical oxygen demand (COD), Biological oxygen demand(BOD), dissolved oxygen (DO), conductivity, total dissolved solid (TDS), total suspended solid (TSS), sulphate, nitrate, nitrite and phosphate. In addition, metals (copper, cobalt Chromium, iron, manganese, magnesium, nickel cadmium, lead, sodium, potassium and calcium were determined. Levels of pH, conductivity, temperature, nitrate, nitrite, sulphate ,phosphate, TSS, TDS, DO, BOD and COD were higher than the maximum permissible limits set by Bureo of Indian Standard Delhi. The concentrations of the metals in the wastewater were higher limits set by W.H.O. and the maximum contaminant levels (MCL Thus, the wastewater around the Dheradun industrial highly polluted. Domestic and industrial waste should be properly disposed and or recycled. Relevant agencies should make continuous effort to control, regulate and educate populace on indiscriminate waste disposal from domestic and industries within the study area. Physicochemical Determination of Pollutants in Wastewater.

Keywords: Physicochemical, Pollutant, Industrial Wastewater, Dheradun. INTRODUCTION Heavy metals are present in food in very minute quantities; the existence is due to their role in body metabolism, it has been establish that whatever is taken as food might cause metabolic disturbance if it does not contain the permissible upper and lower limits of heavy metals. Thus, both deficiency and excess of essential micro-nutrients (iron, zinc and chromium) may produce undesirable effects (Konofal et al., 2004; Kocak et al., 2005). Effect of toxic metals on human health and their interactions with essential heavy metals may produce serious consequences (Abdulla and Chmielnicka, 1990).From this viewpoint, metals such as iron, lead, chromium, nickel, arsenic and cadmium are considered suitable for studying the impact of various foods on human health. Arsenic occurs naturally in food at concentration levels, which are rather essential. Wastewater discharge from sewage and industries are major component of water pollution,

Contributing to oxygen demand and nutrient loading of the water bodies, promoting toxic algal blooms and leading to a destabilized aquatic ecosystem (Morrison et al, 2001; DWAF and WRC, 1995). High or low pH values in a river have been reported to affect aquatic life and alter toxicity of other pollutant in one form or the other (DWAF, 1996c). Low pH values in a river for examples impair recreational uses of water and effect aquatic life. A decrease in pH values could also decrease the solubility of certain essential element such as selenium, while at the same time low pH increases the solubility of many other element such as Al, B, Cu, Cd, Hg, Mn and Fe (DWAF, 1996c).High nitrate concentrations are frequently encountered in treated wastewater, as a result of ammonium nitrogen. High nitrate levels in wastewater could also contribute to eutrophication effects, particularly in freshwater (OECD, 1982). Many workers have been reported to have potential health risk from nitrate in drinking water above threshold of 45 mg/ l, which may give rise to a condition known as methaemoglobinemia in infants and pregnant

SINGH et al., Curr. World Environ., Vol. 7(1), 133-138 (2012) women (Speijer, 1996).Biological oxygen demand (BOD) measure the amount of oxygen requires by bacteria for breaking down to simpler substances the decomposable organic matter present in any water, wastewater or treated effluent. It is also taken as a measure of the concentration of organic matter present in any water. The greater the decomposable matter present, the greater the oxygen demand and the greater the BOD values (Ademoroti, 1996; Standard methods, 1998). Electrical conductivity of water is a useful and easy indicator of its salinity or total salt content. Wastewater effluents often contain high amounts of dissolved salts from domestic sewage. High salt concentrations in waste effluents however, can increase the salinity of the receiving water, which may result in adverse ecological effects on aquatic biota (Ademoroti, 1996). Vegetables are staple part of human meals taken as food in raw and cooked forms In view of the continues used of wastewater for the irrigation of vegetable crops in these area of Dheradun, this study is aimed to assess the levels of some physicochemical parameters in wastewater samples from the Dheradun . MATERIALS AND METHOD Sample area and Sampling Points Wastewater samples were collected from the Dheradun industrial area for the analysis of physicochemical parameters. Measurement points for the sampling were designated as N1 to N4. Wastewater samples were collected at the discharge point from old ancient walled city designated as N1; 200metres away from the ancient walled city (N2); and at 500metres along the Sabon –Gari discharged point from the ancient walled city (N3); N4 was located at Selaqui Paonta sahib Road. Sample Collection Wastewater samples were collected in plastic containers previously cleaned by washing in non-ionic detergent, rinsed with tap water and later soaked in 10% HNO3 for 24 hours and finally rinsed with deionised water prior to usage. During sampling, sample bottles were rinsed with sampled water three times and then filled to the brim at a depth of one meter below the wastewater from each of the four designated

sampling Points (N1 to N4). The samples were labeled and transported to the laboratory, stored in the Refrigerator at about 4°C prior to analysis. Wastewater were also collected for Analysis. Samples were collected between the periods November 2010 to Aug.2011 Determination of Physicochemical pollutant indicators All field meters and equipment were checked and calibrated according to the manufacturer’s Specifications. The pH meter was calibrated using HACH (1997) buffers of pH 4.0, 7.0 and 10.0. Dissolved oxygen (DO) meter was calibrated prior to measurement with the appropriate traceable calibration solution (5%HCl) in accordance with the manufacturer’s instruction. The spectrophotometers (HACH DR2010) for anions determination were checked for malfunctioning bypassing standard solutions of all the parameters to be measured; Blank samples (deionized water) were passed between every three measurements of wastewater samples to check for any eventual contamination or abnormal response of equipment .The dependent variables analyzed were pH, temperature, dissolved oxygen, total dissolved solid, nitrate, sulphate, phosphate and heavy metals concentration. Standard methods were followed in determining the above variables (APHA, 1998). In-situ measurements for some of the parameters, pH and temperature (°C) were measured using WTW pH Electrode Sen Tix 41. Dissolved oxygen was measured with Jenway Model 9070 waterproof meter. Conductivity /TDS meter (Hach model C0150) was used to measure the conductivity and total dissolved solids of the water samples. The power key and the conductivity key of the conductivity/TDS meter were switched on, and the meter was also Temperature adjusted; the instrument was calibrated with 0.001M KCl to give a value of 14.7µS/m at25ºC. The probe was dipped below the surface of the wastewater and surface water. Time was allowed for the reading to be stabilized and reading was recorded. The key was then changed to TDS key and recorded. The probe was thoroughly rinsed with distilled water after each measurement. Levels of turbidity and total suspended solid of the wastewater samples were determined using standard procedures approved by AOAC (1998).The biological oxygen demand

SINGH et al., Curr. World Environ., Vol. 7(1), 133-138 (2012) determination of the wastewater samples in mg/l was carried out using standard methods described by Ademoroti (1996). The dissolved oxygen content was determined before and after incubation. Sample incubation was for 5 days at 20°C in BOD bottle. Physicochemical Determination of Pollutants in Wastewater Dheradun Industrial area.BOD was calculated after the incubation periods. Determination of chemical oxygen demand was carried out using closed reflux method as described by Ademoroti (1996). Digestion of Wastewater Samples for Heavy Metals Determination The wastewater samples were digested as follows. The sample, 100cm³ was transferred into a beaker and 5ml concentrated HNO3 was added. The beaker with the content was placed on a hot plate and evaporated down to about 20ml. The beaker was cool and another 5ml concentrated HNO3 was also added. The beaker was covered with watch glass and returned to the hot plate. The heating was continued, and then small portion of HNO3 was added until the solution appeared light coloured and clear. The beaker wall and watch glass were washed with distilled water and the sample was filtered to remove any insoluble materials that could clog the atomizer. The volume was adjusted to 100cm³ with distilled water (Ademoroti, 1996). Determination of heavy metals in the wastewater

samples was done using Atomic Absorption Spectrophotometer (AAS, Unicom 969) as described in the manufacturer’ instruction manual. Elemental Analysis of Digested Samples Determination of heavy metals (copper, cobalt chromium, iron, manganese, magnesium, nickel Cadmium, and lead) was made directly on each final solution using Perkin-Elmer Analyst 300 Atomic Absorption Spectroscopy (AAS) as described by Floyd and Hezekiah (1997). Flame emission Spectrometer (FES) Gallenkamp (FGA330) was used to determine sodium (Na), potassium (K) and Calcium (Ca). Determination of Nitrate, Nitrite, Sulphate and Phosphate in the Wastewater Samples The concentration of nitrate, nitrite, sulphate and phosphate were determined using DR/2010 HACH Por table Data Logging Spectrophotometer. The spectrophotometers were checked for malfunctioning by passing standard solutions of all the parameters to be measured; blank samples (deionized water) were passed between every three measurements of water samples to check for any eventual contamination or abnormal response of equipment. Nitrate as nitrogen was determined by the cadmium reduction metal method 8036[Standard Methods, 1976, DWAF, 1992]. The cadmium metal

Table 1: Concentration of Physicochemical Parameters in wastewater samples from Dheradun Industrial area waste water, Uttrakhand state Parameters Sampling Points

N1

N2

N3

N4

pH Temp(°C) Turbidity (NTU) COD (mg/l) BOD (mg/l) DO (mg/l) TDS (mg/l) TSS (mg/l) Conductivity (µScm-3) Sulphate (mg/l) Nitrate (mg/l) Phosphate (mg/l)

9.94±1.32 32.34±0.32 36.33±2.13 564.32±5.43 254.11±2.32 7.43±0.76 2321.23±33.23 1237.12±12.45 1123.41±10.21 172.32±0.83 223.21±1.21 110.45±0.42

8.94±2.03 31.11±0.11 34.23±2.32 512.45±7.21 223.43±4.23 6.22±0.23 2210.21±22.32 1131.23±14.32 1021.17±14.32 154.33±1.02 211.43±0.34 103.23±0.11

10.34±1.43 36.34±2.94 42.22±3.10 698.11±6.45 341.11±4.34 8.43±0.56 2655.43±16.33 2673.22±17.32 1534.21±12.43 252.21±1.32 284.33±1.74 164.22±0.56

9.54±0.54 33.34±1.44 33.34±2.01 531.05±9.23 245.22±2.77 6.56±0.49 2456.22±18.90 2673.22±17.32 1477.32±14.32 212.22±0.77 234.56±1.92 153.22±0.67

SINGH et al., Curr. World Environ., Vol. 7(1), 133-138 (2012) in the added reagent reduced all nitrate in the sample to nitrite; while sulphate was determined by using Sulfa Ver methods 8051 [Standard methods,1976., DWAF, 1992].126 J.C.Akan, F.I. Abdulrahman, G.A.Dimari and V.O.OgugbuajaThe levels of the physicochemical parameters are presented in Table 1. From the results of this study the levels of pH varied between 9.94±1.32 and 8.94±2.03 for point N1 and N2, and 10.34±1.43 to9.54±0.54 for point N3 and N4 in the wastewater respectively. Generally point N3 shows the highest concentration followed by N1, while point N2 shows the least concentration. The mean pH values recorded for all the sampling point were above the WHO pH tolerance limit of between 6.00 – 9.00 for wastewater to be discharged into channel into stream with exception of point N2. Physicochemical Determination of Pollutants in Wastewater along Dheradun Industrial waste water, Uttrakhand state. Temperature is basically important for its effect on other properties of wastewater. Average Temperature of wastewater under investigation is 42.34±0.32ºC for N1; 41.11±0.11ºC for N2; 46.34 ±2.94 ºC for N3 and 43.34±1.44 ºC for N4. The results indicate that some reactions could be speeded up by the discharge of this wastewater into stream. It will also reduce solubility of oxygen and amplified odour due to anaerobic reaction (less oxygen). These values were higher than WHO standard of 40°C for discharged of wastewater into stream. Similarly turbidity values were in the mean of36.33±2.13NTU for N1; 34.23±2.32NTU for N2; 42.22±3.10NTU for N3 and 33.34±2.01NTU for N4.The values obtained for turbidity in the entire sampling points under study were higher than WHO standard of 5 NTU for discharged of wastewater into stream. The conductivity values were 1123.41±10.21 µScm -3 for N1; 1021.17±14.32 µScm-3 for N2;1534.21± 12.43µScm-3 for N3 and 1477.32±14.32µScm-3 for N4 (Table 1). Conductivity of water which is a useful indicator of its salinity or total salt content is high in the wastewater from the dheradun industrial wastewater channel. This result is not surprising, since wastewater from domestic

sewage often contain high amounts of dissolved salts. The mean conductivity values for all the sampling point were higher than the WHO guideline values of 1000µScm -3 for the discharge of wastewater through channel into stream .The total suspended solids (TSS) concentrations were 1237.12±12.45 for mg/l N1;1131.23±14.32 mg/l for N2; 2673.22±17.32mg/l for N3 and 2673.22±17.32 mg/l for N4 (Table 1).Literature classified wastewater TSS as follows: TSS less than 100 mg/ l as weak, TSS greater than 100mg/l but less than 220 mg/l as medium and TSS greater than 220 mg/ l as strong wastewater. Results of the study show that wastewater from the wastewater channel can be classified as strong Wastewater and cannot be discharged into stream. The mean concentration of Total dissolved solid (TDS) in the Dheradun industrial wastewater channel wastewater channel are presented in Table 1. The concentration of TDS is 2321.23±33.23 mg/ l for N1; 2210.21±22.32 mg/l forN2; 2655.43±16.33 mg/l for N3 and 2456.22±18.90mg/l for N4. These values obtained for TDS in all the sampling points were higher than WHO standard of 2000 mg/l for the discharged of wastewater into surface water. The concentrations of nitrate, sulphate and phosphate in all the sampling points varied between211.43±0.34 to 284.33±1.74 mg/l for nitrate; 154.33±1.02 to 252.21±1.32 mg/l for sulphate and103.23±0.11 to 164.22±0.56 mg/l for phosphate respectively (Table 1). High concentration of nitrate, sulphate and phosphate were observed in point N3, while low concentrations were observed for pointN2. The levels of nitrate exceeded the WHO limits of 45mg/ l and South Africa guideline of 0.25 mg/l for nitrate in wastewater, while sulphate was below the WHO limit of 250 mg/l for the discharged of waste water into river. The levels of phosphate in the entire sampling point were higher than the WHO limit of 5mg/l for the discharged of wastewater into river. The levels of nitrate may give rise to128 J.C.Akan, F.I.Abdulrahman, G.A.Dimari and V.O. Ogugbuaja methaemoglobinemia, also the levels of nitrate reported in this study in addition to phosphate levels can cause euro phication and may pose a problem for other uses. Dissolved oxygen (DO) values obtained for point N1 to N2 varied between 6.22±0.23 to8.43±0.56 mg/l as shown in Table 1.

SINGH et al., Curr. World Environ., Vol. 7(1), 133-138 (2012) The DO is a measure of the degree of pollution by organic matter, the destruction of organic substances as well as the self purification capacity of the water body. The standard for sustaining aquatic life is stipulated at 5mg/l a concentration below this value adversely affects aquatic biological life, while concentration below 2mg/l may lead to death for most fishes (Chapman, 1997). The DO level at point N1 to N4 was above these levels .An indication of organic oxygen demand content of wastewater can be obtained by measuring the amount of oxygen required for its stabilization either as BOD and COD. Biological Oxygen demand (BOD) is the measure of the oxygen required by microorganisms whilst breaking down organic matter. While Chemical Oxygen Demand (COD) is the measure of amount of oxygen required by both potassium dichromate and concentrated sulphuric acid to breakdown both organic and inorganic matters. BOD and COD concentrations of the wastewater were measured, as the two were important in unit process design. The wastewater has an average COD concentration of 512.45±7.21 to698.11±6.45 mg/l for point N2 to N4 (Table 1). BOD concentration of the wastewater obtained for point N1 to N4 ranged between 223.43±4.23 to 341.11±4.34 mg/l respectively. The concentrations of BOD and COD in all the sampling point were higher than the WHO values of 50 mg/l and 1000mg/ l for the discharged of wastewater into stream. High COD and BOD concentration observed in the waste water might be due to the use of chemicals, which are organic or inorganic that are oxygen Demand in nature .The results for elemental concentration in wastewater samples from the dheradun industrial wastewater channel wastewater channel for different sampling points are presented in Figure 1. The composition of metals in the wastewater

samples ranged from 2.87 to 5.22 mg/l for Mn; 4.57 to 7.45 mg/l Mg; 2.32 to 3.78 mg/l Cu; 1.00 to3.58 mg/l Cd; 1.23 to 2.87 mg/l Pb; 2.34 to 5.23 mg/l Co; 14.56 to 21.45 mg/l Fe; 1.56 to 4.33 mg/l Cr;11.65 to 18.45 mg/l Ni; 20.91 to 32.94 mg/l Na; 19.43 to 27.34 mg/l K and 9.56 to 16.93 mg/l Ca for point N1 to N4. The concentrations of heavy metals in the wastewater channel are in the following order Na> K> Fe> Ni> Ca> Mg> Co> Mn> Cr> Cu> Cd> Pb. From the result of these study the concentrations of all the parameters study (Table 1) are in the following order N1>N2<N3>N4.This variation is due to the fact that point N1 is the discharged point from Bindal bridge and decrease towards point N2. While the high values at point N3 is due to the discharged of wastewater from Pharma city into the Dheradun industrial which might increase the concentration of these parameters, and finally decreases toward point N4 due to sedimentation and dilution .Physicochemical Determination of Pollutants in Wastewater along Dheradun Industrial waste water, Uttrakhand state. CONCLUSION From the data collected from this research, the physicochemical parameters monitored in point N1, N2, N3 and N4 showed high levels of all the parameters. This must be as a result of the nature of Wastewater from the Pharma city and Sara industry. Point N3 showed the highest concentration of the physicochemical parameter, while point N2 shows the lowest values. WHO, this high values is due to the used of untreated wastewater from the industrial area for the Irrigation of these vegetables. Accordingly, wastewater from all the sampling points are polluted as can be observed from the results obtained.

REFERENCES

1.

2.

Abdulla, M. and Chmielnicka, J. New aspects on the distribution on the distribution and Metabolism on essential trace elements after dietary exposure toxic metals. Biol. TraceElement Res. 23: 25-53 (1990). Ademoroti, C.M.A. Standard method for water and Effluents Analysis. Foludex press Ltd,

3.

4.

Ibadan pp. 22-23, 44-54, 111-112 (1996). Anikwe, M.A.N. and Nwobodo, K.C.A. Long term effect of municipal waste disposal on soil properties and productivity of sites used for urban agriculture in Abakaliki, Nigeria. Bioresources Technol. 83: 241-251 (2006). AOAC. Official methods of analysis of the

SINGH et al., Curr. World Environ., Vol. 7(1), 133-138 (2012)

5.

6..

7.

8.

9.

10.

11.

12.

13.

14.

15.

Association of Official Analytical Chemist. Alexandria, VA: Association of Official Analytical Chemists. 432-444 (1998). APHA. Standard methods for the examination of water and wastewater. 18th Edition. American Public health Association, Washington, DC pp 45-60 (1998). Chapman, D. Water Quality Assessment. A Guide to the use of Biota, Sediments and water in Environmental Monitoring. Second Edition. E& FN Spon, London. File: A// :\Hydrology and Water Quality of Lake Merced.htm (1997). DWAF Analytical Methods Manual, TR 151. Department of Water Affairs and Forestry, Pretoria (1992). DAWF and WRC (1995) South Africa Water Quality Guideline 1: Domestic water use (2nd edn) Department of Water Affairs and Forestry, Pretoria. DWAF, South Africa water quality Guidlines. 7: Aquatic Ecosystems (1st Edn) Department of water Affairs and forestry, Pretoria (1996c). Floyd, W.B. and Hezekiah .S. Analysis of coal ash by atomic absorption spectrometric and spectrophotometric methods. In: Method for sampling and inorganic Analysis of Coal. USA. Geological Survey Bulletin 1823 Golightly D.W and Simon F.O. (Ed). 1-20 (1997). HACH. Water Analysis Handbook, 3rd edition, HACH Company, Loveland, Colorado, USA (1997). Hunt, J. and Turner, M.K. A survey of nitrite concentrations in retail fresh vegetables. Food Additive and Contaminations. 11(3): 327-332 (1994). Kenneth Helrich, Official Method of Analysis of AOAC 5th Edition.AOAC Inc. Arlington USA Pp56-58. 22 (1990). Kocak, S., Tokusoglu, O. and Aycan, S. Some heavy metal and trace essential element Detection in canned vegetable foodstuffs by differential pulse polarography (DPP), Electronic J. Environ. Agric. Food Chem. 4: 871-878 (2005). Konofal, E., Lecendreux, M., Arnulf, I. and Mouren, M.C. Iron deficiency in children with attention-deficit/hyperactivity disorder. Arch.

16.

17.

18.

19.

20.

21.

22.

23.

24.

28.

Pediatr. Adolesc. Med. 158: 1113-1115 (2004). Liu, W.H., Zhao, J.Z., Ouyang, Z.Y., Soderlund, L. and Liu, G.H. Impacts of sewage irrigation on heavy metals distribution and contamination in Beijing, China. Environ. Int. J. 31: 805-812(2005). Morrison, G. O., Fatoki, O.S and Ekberg, A. Assessment of the impact of point source pollution from the Keiskammahoek sewage treatment plant on the keiskamma river. Water. SA., 27: 475-480 (2001). Muchuweti, M.J., Birkett, J.W., Chinyanga, E., Zvauya, R., Scrimshaw, M.D., and Lester, J. N. Heavy metal content of vegetables irrigated with mixture of wastewater and sewage sludge in Zimbabwe: Implications for human health. Agric. Ecosyst. Environ. 112: 41-48 (2006). OECD, Eutrophication of waters: Monitoring, Assessment and Control. Technical Report, organization for economic Co operation and Development, Paris (1982). Radojevic,M. and Bashkin, V.N. Practical Environmental Analysis. The Royal Society of Chemistry, Cambridge pp 466 (1999). Santamaria, P., Elia, A., Serio, F. and Todaro, E. A suevey of nitrate and oxalate content in retail fresh vegetables. J.Sci. Food. Agric. 79: 1882-1888 (1999). Sharma, R.K., Agrawal, M., and Marshall, F. Heavy metal contamination of soil and vegetables in suburban areas of Varanasi, India. Ecotoxicol. Environ. Safety. J. Doi: 10.1016/jecenv (2007). Speijers, G.J.A. Nitrate in Toxicological evaluation of certain foot additive and contaminats in food, ed, by WHO, Food Additive Series 35, Geneva, pp 325-360. Standard Methods. Standard method for the examination of water and wastewater (14thedn) Jointly published by the American Public Health Association, America Water Works Association and Water Pollution Control Federation, Washington, DC. Pp 68165 (1996). Zhou, Z.Y., Wang, M.J. and Wang J.S. Nitrate and nitrite contamination in vegetables in china. Food. Rev. Int. 16: 61-76 (2000).

Current World Environment

Vol. 7(1), 139-144 (2012)

Physico-Chemical Studies of Water Quality of Shahpura Lake, Bhopal (M.P) with Special Reference to Pollution Effects on Ground Water of its Fringe Areas TRIVEDI SONAL and H. C. KATARIA Department of Chemistry, Government Geetanjali Girls PG (Autonomus) College, Bhopal (India). (Received: March 15, 2012; Accepted: April 15, 2012) ABSTRACT Indiscriminate and wasteful water consumption and improper waste disposal practices have led to deterioration in the water quality be it surface or ground water. Shahpura is an in-land urban surface water body which is fed by Bhopal city waste water and effluent from adjoining Shahpura and Chunabhatti townships thereby converted into a polluted lake. This is a maiden attempt to highlight the spread of polluted surface water into the ground water aquifer which is supports the drinking water supplies to a large population of Bhopal.

Key words: Groundwater, Physico-chemical analysis, Pollution, Sanctuary, Water Quality.

INTRODUCTION Fresh Water is essential to existence of life. Water of acceptable quality is essential not only for drinking and domestic purposes but also for agriculture, industrial and commercial uses. Surface water is collection of water on the ground or in a stream, river, lake, wetland, or ocean. Surface water is naturally replenished by precipitation and naturally lost through discharge to evaporation and sub-surface seepage into the groundwater. A lake is a large body of water surrounded by land and inhabited by various aquatic life forms. Lakes are subjected to various natural processes taking place in the environment, such as the hydrological cycle. Due to tremendous population growth of the city (from just over 0.1million in 1951 to about 1.8 millions in 2007) and rapid urban development, lakes are facing various environmental problems resulting in deterioration of its water quality. The area of the study selected, to estimate the water quality and levels of water pollution, is the Shahpura lake of Bhopal city. It is located in the southern part of the city. It is manmade reservoir formed in 197475, under the Betwa irrigation project. The waste water inflow keeps the lake perennial and the over flowing water flows through a nala to join kaliyasot

river which flows into river Betwa. Various physicochemical parameters were studied to assess the water quality status and the extent of deterioration in the water quality of lake. The degradation of lake has occurred not only due to waste water effluent inflow but also by saltation, domestic sewage, immersion of idols and other activities around the lake. Thus the lake is subjected to enormous anthropogenic stress; the overall impact has resulted in the deterioration of the water quality, accumulation of toxic chemicals and sediments, shrinkage of lake area and above all, loss of the aesthetic value. It is well known that hydrologic environment is composed of two interrelated phases; ground water and surface water. Impacts initiated in one phase eventually affect the other system. The polluted lake water may enter into aquifer or ground water body of fringe areas, specially the downstream areas by percolation and influent seepage. The natural quality of hand pumps, bore wells and drinking water resources tend to be degraded in the fringe areas of lake. Several investigations and research studies have been made on water quality and increasing pollution level of the water body. They all indicate the alarming contamination of the lake which is very high as compared to the standard guidelines, revealing that

301.8 252 245.6 237.1 277 277 290.0 175.5 276.7 204.1 259.9 274.0 259.2 0.00 1.8 0.00 2.81 4.13 0.00 2.6 4.15 3.5 3.83 7.9 8.16 6.13 54 78 68.0 60 62 77 35 54 61 67 46 55 49 87 108 98.0 98 102 92 82 69 87 85 82 104 106 36.0 26.0 21.8 22.4 24.5 24.5 25.8 21.4 27.2 10.7 22.4 26.2 19..4 67.0 70.3 75.0 78.4. 76.0 75.5 71.0 49.0 73.6 73.2 72.2 73.0 79.2 320 280 275 295 292 298 284 220 290 230 280 290 273 All the surface water samples showed positive tests for microorganisms (Coliforms).

4.0 0.8 4.2 3.6 5. 24 7.0 6.3 6.0 5.0 5.5 4.00 5.5 5.4 130 74 22.0 8.0 25.2 36.0 67.0 14.0 41.0 12.0 26.0 24.0 22.0 0.10 1.00 1.9 1.00 0.20 0.8 0.30 0.5 0.5 0.20 1.00 0.40 0.5 0.5 1.0 0.5 0.9 0.7 0.9 0.2 0.1 0.20 0.10. 0.4 0.5 0.4 0.35 0.35 0.18 0.22 0.11 0.20 0.34 0.23 0.15 0.15 0.15 0.13 0.15 4.7 7.6 5.0 4.0 2.2 8.00 4.5 2.4 5.5 4.0 5.2 5.0 5.1 9.00 10.00 4.00 0.12 1.00 0.37 0.05 1.00 0.05 2.00 0.05 0.05 0.05 445 580 500 488 500 469 481 369 474 461 501 499 490 788 980 780 810 780 850 750 655 740 720 780 878 765

COD Tot.P fluori Iron Nit. TDS Ammo

7.6 7.9 7.5 8.2 8.1 8.2 8.0 8.3 8.0 8.1 8.4 8.3 8.4

The physico-chemical data collected from different sampling stations Table 1 and 2.

SW1 SW2 SW3 SW4 SW5 SW6 SW7 SW8 SW9 SW10 SW11 SW12 SW13

RESULTS AND DISCUSSIONS

EC

To study the water quality status of Shahpura lake, thirteen surface water quality monitoring stations were chosen at different points of the lake and sixteen ground water quality monitoring stations in the fringe area (where source water is mainly ground water) were finalized. The methods of water analysis were used as prescribed by APHA (American Public Health Association) water environment federation and National Environment Engineering Research Institute (NEERI), Nagpur. Water samples were collected during the winter season, 2011 from the selected stations. The analysis of the following physico-chemical parameters was carried out: pH, Electrical Conductivity(EC - µmho/ cm), Total Dissolved Solids(TDS - mg/L), Ammonia (mgNH3-N/L), Nitrate (mgN/l), Total Phosphorus (mgP/L), Iron (mg/L), Fluoride (mg/L), Chemical Oxygen Demand (COD - mg/L), Dissolved Oxygen (DO – mg/L ), Total Hardness (T.Hard. - mgCaCO3/ L), Calcium (mg/L), Magnesium (mg/L), Chloride (mg/L), Sulphate(mg/L), Carbonate (mg/L), Bicarbonate (mg/L) and Coliforms.

ph

METHODS

Station

nutrient load in the lake is very high and hypereutrophic conditions are prevailing. Hence periodic monitoring and preventive measures are required to save the lake from eutrophication. Although, few work has been done to understand the status of the lake, no study has been made on the pollution effects of the lake on the ground water quality of the adjoining areas. The polluted lake water may enter into aquifer or ground water body of fringe areas specially the downstream areas by percolation and influent seepage. At least sixty thousand population resides in the fringe area and is dependent on the ground water, moreover the Chunabhatti area acts as a ground water sanctuary for the town as the drinking water is supplied to the different parts of the city through the water tankers filled from the tube wells daily. Therefore the assessment and monitoring of its water quality is very important. Hence a serious need is felt for the study of the water quality which could prove beneficial for the large number of people.

D O T.Hard. calciumagnesi chlo sulpha carbo Bicarb

TRIVEDI & KATARIA, Curr. World Environ., Vol. 7(1), 139-144 (2012)

Table 1: Water quality results – Surface water shahpura lake

140

pH

8.3 8.2 8.0 8.3 8.4 8.2 7.7 8.3 8.0 8.3 8.0 7.8 7.8 8.3 8.3 8.4

Statio

GW1 GW2 GW3 GW4 GW5 GW6 GW7 GW8 GW9 GW10 GW11 GW12 GW13 GW14 GW15 GW16

840 804 816 792 1250 840 670 714 940 638 586 845 745 1020 824 666

EC

538 452 512 507 736 480 429 429 602 408 328 546 477 653 528 427

TDS 10.1 4.1 4.9 0.2 3.8 2.5 2.5 1.0 4.2 4.9 0.9 2.7 1.7 6.2 7.6 8.4

Nitr 0.00 0.20 0.17 0.10 0.00 0.00 0.10 0.20 0.00 0.90 0.20 0.00 0.00 0.10 0.10 0.00

TotalP 0.040 0.350 0.350 0.160 0.292 0.150 0.132 0.070 0.050 0.040 0.110 0.030 0.156 0.126 0.127 0.135

Iron 0.43 0.26 0.88 0.78 0.16 0.43 0.18 0.52 0.22 0.31 0.38 0.00 0.32 0.41 0.48 0.22

Fluori 32.2 1.2 6.0 22.0 1.2 24.0 1.0 1.0 22.0 39.9 38.4 2.6 7.1 4.8 1.0 1.0

COD 387 312 298 393 390 312 304 322 362 322 186 358 262 468 424 240

104.5 80.5 80.0 76.0 113.6 67.0 70.4 70.4 95.0 89.6 41.6 108.8 58.4 104.8 120.0 68.0

30.0 26.7 23.5 49.0 36.2 35.0 31.1 35.5 30.1 23.8 19.9 20.9 28.2 50.0 30.1 41.3

T.Har Calciu Magn

Table 2: Water Quality results - Ground water of fringe area

80 72 80 88 154 84 62 88 118 37 68 72 108 142 62 36

Chl 33 52 66 74 124 50 45 33 58 43 29 86 82 45 45 34

Sul 14.4 5.4 0.00 12.20 10.5 5.0 1.49 4.20 0.00 5.41 3.09 0.00 1.38 5.80 14.69 4.29

Chl

318.4 290.5 346.5 314.3 339.5 274.7 250.5 281.7 385.4 288.5 164.8 361.1 32.5 459.2 343.5 287.5

Bicar

+ve -ve -ve -ve +ve -ve -ve +ve +ve +ve +ve +ve +ve -ve -ve -ve

T coli.

TRIVEDI & KATARIA, Curr. World Environ., Vol. 7(1), 139-144 (2012) 141

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Fig. 1: Description of sampling stations Sampling stations - Surface water of Shahpura lake S.NO Sampling Location station 1 SW1 Main untreated kotra drainage(Source water ,upstream of lake) 2 SW2 Confluence point of drainage nalla from charimli area behind PCB 3 SW3 Near Dhobighaat behind PCB(high algal growth) 4 SW4 Near slum area Infront of academy of administration(slum area) 5 SW5 Near Shahpura park 6 SW6 Confluence of shahpura sewage nala 7 SW7 Near Waste weir(outlet) 8 SW8 The shahpura lake(near fishing point) 9 SW9 Near amrapali Residential colony 10 SW10 Near hanuman temple (downstream of waste weir) 11 SW11 Near Earthen bund(Downstream of lake) 12 SW12 earthern dam(near Sluice gate) 13 SW13 waste weir Nalla downstream of lake ,near canal Sampling stations - fringe areas of the Shahpura lake 1 GW1 Tubewell of BSNL premises (upstream of lake) 2 GW2 Tubewell of NCHSE premises (upstream of lake) 3 GW3 Behind PCB (upstream of lake) 4 GW4 Building upstream catchment area (eastern side of lake) 5 GW5 Tubewell of rainbow treat restaurant, MP tourism, Manisha market 6 GW6 Shallow dugwell (near waste weir, downstream of earthen dam) 7 GW7 Tubewell, C- sector, shahpura 8 GW8 Tubewell, Kashish restaurant, Kolar road 9 GW9 Sardarji Tube well, chunna bhatti (100m from SW-11) 10 GW10 Dugwell , Jugal kishore, chuna bhatti village 11 GW11 Tubewell, Jugal kishore, Chunabhatti village 12 GW12 Tubewell,aranyawali colony ,800m from SW-11(fringe area) 13 GW13 Tube well amaltas phase I(100m from SW-12)downstream 14 GW14 Tubewell,amaltas phase I-(250m from SW-12)downstream 15 GW15 Tubewell amaltas phase II (500m fromSW-11)fringe area 16 GW16 Tubewell,,new friends colony(near canal ,,chunabhattt II)

TRIVEDI & KATARIA, Curr. World Environ., Vol. 7(1), 139-144 (2012) pH pH range of 6.5 to 8.5 is normally accepted as per guideline suggested by WHO. In this study pH values were found in the range of 7.5 to 8.5 in the water samples. This shows that pH was observed to be slightly alkaline. Higher pH favors the fish production in reservoir. Electrical conductivity- Higher the concentration of acid, base and salts in water, a higher will be the EC. In this study the value of EC was found above the maximum permissible limit of 500Âľmho/cm, in drinking waters as recommended by WHO. Total dissolved solids- It is an important parameter in drinking water quality standard. It develops a particular taste to the water and at higher concentration reduces its potability Water with more than 500mg/l TDS usually has a disagreeably strong taste. High TDS levels generally indicate hard water, which can cause scale buildup in pipes, valves and filters..Similar high TDS values were found in ground water layers of Bhanpur ,Bhopal by Manisha Sonel et al.TDS values in all the samples was found above the WHO permissible limit of 200mg/l .It can be concluded that water is hard at these locations, which necessitates the softening of water prior to its use. In this study The groundwater samples have shown higher values of hardness. Dissolved oxygen and COD-maximum permissible limit for DO as per WHO is 4.6-6.0mg/l it was found within the admissible limit in all the water samples. In the present study high COD values were found which depicts the pollution of water source due to pollutants of organic origin. Nitrate and Phosphate. The world health organization(WHO) has recommended the limit of 10mg/l nitrate nitrogen(NO3-N) for drinking water which is equivalent to about 45mg/l of nitrate (N03)and the same is also accepted in India by the ICMR In a previous study, by Dixit S., et al., the lake was found to be highly eutrophic. The Phosphate content of the lake water studied was found in the range of 6.05 to 9.21 ppm. The Nitrate content of the water was found in the range 2.02 to 15.22ppm. Sharp rise in nitrate content was found from 2003 to 2004, showing the increasing anthropogenic influence on the lake. The raw sewage is the source of nitrates and phosphates in the water. The United States Public Health Standards limit for phosphates in drinking water is 0.1ppm(De,2002,p.p231-232). The phosphate content in the lake water is alarming

143

and very high as compared to the standard guidelines, which reveals that nutrient load in the lake is very high and hypereutrophic conditions are prevailing Fluoride, Chloride and Sulphate. The value of 0.8 to1.0mg/l of F has been recommended by WHO (1970.) Values in all the sample was found in the permissible range. It was observed that the chloride and sulphate concentration in all the samples collected was below the recommended concentration of 250mg/l and150mg/l respectively. CONCLUSION In general the surface water of shahpura lake has shown lesser values of the parameters pH, total hardness, EC, TDS in comparison to the groundwater samples. However, the nitrates and microorganisms (coliform bacteria) showed very high values in lake water. Studies carried out in present investigation revealed that one of the most important causes of water pollution is unplanned urban development without adequate attention to suitable management of sewage and waste material. It is summarized that propagation of pollution front in groundwater aquifer of the fringe area of Shahpura Lake is governed by the hydraulic gradient enhancing influent seepage from Shahpura Lake. The alarm bell therefore rings at the doorstep with the fear of polluting the ChunaBhatti groundwater sanctuary which supports tens of hundreds of water takers from the tube wells of the fringe area of Shahpura lake for water supply in different parts of Bhopal city. Also the entire population of ChunaBhatti Township depends on the water supply from Tubewells/ Borewells. It is therefore, recommended that this groundwater supply from Tube wells should be used as drinking water only after pre-treatment. It may also not be out of context that all the in-lets of city effluents/waste water should be suitably treated before flowing into Shahpura lake. ACKNOWLEDGEMENT I am grateful and indebted to chemists of Ground water survey, water quality Laboratory, Kolar road, Bhopal for providing lab facilities and guidance time to time.

144

TRIVEDI & KATARIA, Curr. World Environ., Vol. 7(1), 139-144 (2012) REFERENCES

1.

2.

3.

4.

5.

6.

7.

8.

Adholia,U.N., Studies on hydrology of river Betwa and its fishery resources. PhD Thesis,vikram university, Ujjain (1981). APHA.Standard method for examination of water and waste water American public health association, Washington.D.C. (1989) Dixit.S and Tiwari.S. Impact assessment of Heavy metal pollution of Shahpura lake, Bioline international-International Journal of Environmental research, university of Tehran, 2(1): 37-42 (2008). Dixit Savita, Gupta S.K, Tiwari Suchi.,Nutrient overloading of fresh water lake of Bpl. India., EGJ-Electronic green Journal, 1(21) UCLA Library, UC Los Angeles (2005). Dhote Savita. Role of macrophytes in improving water quality of an aquatic ecosystem,shahpura lake,Bpl. J. Applied. Science. Envion. Manageme. 2(4):133-135 (2005) Jain.S.K,et al ,Assessment of quality of ground water pollution arising from various sources. Journal of Indian water resources society. 28(3): 9-13 (2008). Handa.B.K.Water,Groundwater contamination in India,. National workshop on Environmental aspects of groundwater development, Kurukshetra, India., (1994). Kataria,H.C.et al., Studies of water quality of Dahod dam, India, Poll Res.,25(3): 553-556 (2006).

9.

10. 11.

12.

13.

14.

15.

16.

17.

Kataria,H.C., A biochemical analysis of drinking water of Raisen district (M.P). Asian. J. Chem. Revs. 5(1-2): 66-68 (1994). Kudesia V.P. Water pollution, Pragati prakashan, Meerut, (1995). Lunkad.s.k,Kurukshetra university,Rising nitrite levels in ground water and increasing N-fertilizer consumption,BHU-JAL news, journal of CGWB, 9(1): 4-10 (1994). Manisha Sonel,et al ,Physico-chemical and bacteriological studies of ground water layers in Bhanpur, Bhopal(M.P).,Current World Environment, 5(2): 379-382 (2010) Nayar Renu and Tiwari Deepak. Studies on the physico-chemical characteristics of ground water of korba. Current world Environment.J., 3(1): 175-180(2008) NEERI, Manual on water and waste water analysis. National Environmental Engineering Resources Institute, Nagpur. 340 (1986). Savita Dixit and suchi Tiwari,Effect of religious practices on water quality of Shahpura Lake, M.P, India, Water International., 32(1): 889-893 (2007) Available online-24 feb 2011. Anoop-Chandra, P.N. Saxena, Sayeida Ghazala Imam and Geetesh Chandra, Orient. J. Chem. 27(3): 1193-1198 (2011). Abdul Rahim and Syed Hussain, Orient. J. Chem. 27(3): 1273-1275 (2011).

Current World Environment

Vol. 7(1), 145-150 (2012)

Analysis of Pesticide Residues in Winter Fruits RAVI KANT KANNAUJIA*, CHITRA GUPTA, FAROOQ WANI and ROHIT VERMA Department of Chemistry , Budelkhand University Jhansi - 284 128 (India). (Received: May 08, 2012; Accepted: June 20, 2012) ABSTRACT Fruit samples of winter fruits (apple, grapes, banana cheeku, papaya, lemon) for pesticideresidues employing a multiresidue analysis by gas liquid chromatography.All the fruit samples showed the presence of residues with one or other group of pesticides.Some samples exceeded the quantification limit.The increasing interest in the pesticides in fruit samples is justified from the enological point of view.In this paper pesticide mobility on fruit samples was studied.Out of nine pesticides tested for most of the sample show very high levels of malathion ,while other pesticides residues are with in the established tolerance,BHC endosulphan dieldrin are with in limits.thus consumer intake of pesticides from fruit samples studied in this work should be reduced bywashing fruits with water .In this paper multiresidue determination of pesticides are discussed using GLC.HNMR.IR.

Key words: Pesticides GLC HNMR IR fruits residues.

INTRODUCTION A pesticide is a chemical substance used for preventing, destroying, repelling or mitigating a pest, which can be an insect; rodent, bind, weed or fungus, as well as micro organism like bacteria and viruses. Pesticides can be broadly classified as insecticides, herbicides, fungicides, rodenticides, and antimicrobials, with many subclasses. The major insecticide groups are the organochlorines, organophosphates, carbonates and pyrethroids. Pesticides are considered hazardous chemicals and improved the regulation of pesticides particularly in developed countries, a health risk remains. Both the potency of primary factor affecting the level of risk. The use of pesticides provided an important socioeconomic benefit to the areas of agriculture and food productions. Pesticide production is market driven with high investment in industrialized countries. In the U.S, 77% of all pesticides are used. In developing countries, public health programs represent an important use of pesticides in the control of vector borne diseases like malaria. Countries in Africa, Asia and central

South America are highly dependent on pesticides. Other areas in which pesticides are used include forestry, gardening and lawn care horticulture and livestock and to a large extent domestic use in home. In the U.S pesticides are used in around 70 million homes. Usage of OCPâ&#x20AC;&#x2122;s have been prohibited in most of countries, but 70% of banned pesticides low cost, in India DDT was banned for use in agriculture in 1985, but still 7500 metric tons per year is used here. The problems of pesticides residues in crops has been attracting growing attention the use of organic insecticides for the control of insect on crops has become common during the past few years. The detection and identification of pesticides in our environment is a problem of increasing public interest. Pesticides residues in food has become a consumer safety issue. The consumer has a right to know how much pesticide gets in corporate in the food he eats. At many laboratories expanded research programmers have been instituted to

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understand and control more fully the varied effects of pesticides like:1) The appraisal of the potential carcinogenicity of ingested substances. 2) Palatability and organoleptre evaluation of fruits, meats and vegetables. 3) Assimilation of detailed data on acute and chronic toxicity for all compounds. 4) Nature of plant surfaces and the chemical modes of penetration subsequent

5)

translocation, distribution and metabolic fate in plants and exudation of regulating compounds into the soil. Establishment of safety threshold levels within a human being without immediate or future harm. The short as well as long term impact of the use of pesticides on biological systems is being evaluated continuously in an effort to minimize.

Table 1 Pesticide

Chemical Name

Molwt.

Trale Name

Chemical Class

ADI mg/Kg/ Day

BHC α,β,γ,δ

1,2,3,4,5,6-

290.85

Organochlorine

0.008

DDT

Hexachlorocy 354.41 clohexane1,1(2,2,2-trichloro ethylidene) bis [4chlorobenzene] 0,0-dimethye 0-4263.21 Nitrophenyl Phasphorothioate Diethyl (Dimethoxy 330.36 Thiophas Phosphorylthio succolnate 0,0 dimethye S229-28 methylcarbo mouylemethyl phosphoridithiote 0,0,0,1,01-tetraethyl, 384.48 s-s1 methyloe bis (phosphorodithioate) 6,7,8,9,10,10406.96 hexachloro 1,5a,6,9,9ahexahydro 6,9methano-2,4,3 benzadioxathiepin 3-oxide 1,2,3,4,10.10380.9 Hexachloro 6,7 expoxy 1,4,-4a,5,6,7,8,8a, octahydro-1,4,5,8dimetanophthalene

HCH, Grammexane Anofex, Cesarex, Digmar, Gezarex

Organocholorine

0.02

Matafos, metacide, dalf, Gearphas Carbophos,

Organophasphate

0.02

Organophasphate meldison

0.02

Cygon400, Demos, Dicap, rogor

Organophasphate

0.01

Acithion, Ethanox, Hylmox Hexasulfan, Afidan, Cyclodan Beosit

Organophasphate

.002

Methyl Parathion Malathion

Dimethoate

Ethion

Endsulfan

Dieldrin

Mercaptothion

Dieldriti, Octalox Panoram D-31

Organochlorine

Organochlorine Dieldrex,

.006

KANNAUJIA et al., Curr. World Environ., Vol. 7(1), 145-150 (2012)

147

sodium sulphate was added to it. The solution thus obtained was filtered and concentrated again. To this 5 ml of hexane was added and the sample thus prepared was analyzed for the presence of 9 pesticides by gas chromatograph (Perkin ElmerAuto system XL) with the selective electron-capture detector (ECD). This detector allows the detection of contaminants at trace level concentration in the lower ppm range in the presence of multitude of compounds extracted from the matrix to which these detectors do not resend. The column used was PE17, length 30m. ID 0.25 film 0.25 mm with a 2 ml/ min flow. The carrier gas and the make up gas was nitrogen employing the splitting mode. The oven temperature was kept at 190-2800C with a ramp of 50c/min. The lam plies were calibrated (retention time, are a count) against a 10 ppm standard mixed solution of all 9 pesticides. Each peak is characterized by its retention time and the response factor in ECD. Sample results were quantitated in ppm automatically by the GC software.

Potential or latent hazards while maximizing the benefits derived by marking form increased agricultural production and communicable disease eradication. The use of pesticides has not permitted the control of diseases transmitted by insects but also has led to increased food production and better health. EXPERIMENTAL Selection of fruit samples were based on their availability in winter. The samples were purchased in Jhansi. The fruits sold here are bought from the near bus stand in Jhansi. The fruit samples was analyzed in the form, that is offered to the consumer. For example apple, Cheeku, Papaya and grapes were analyzed with peels whereas banana, pomegranate and coconut were analyzed without peels. Lemon was analyzed with peals as it is used in making pickles in the form each sample size taken 1 kg out of which a representative substance weighting 20gram was randomly taken and the pesticides were extracted for 8-10 hr at the rate (4-5) cycles per hr, in hexane in a soxhelt extractors. The rotary evaporators. The concentrate contained aqueous as well as organic residue.

One GC injection (30 min) was required in order to cover all 9 pesticides included in a analysis. Hamilton micro syringes injection of the pesticide dissolved in hexane as solvent were made directly onto the coated silanized column solid support, there by eliminating the possibility of catalytic degradation by metallic surfaces. Pesticides were identified according to their retention time. For accurate result the concentration

The organic part was extracted in hexane with the help of a separating funnel and a pinch of

Table 2: Pesticide residues, in water fruits mg/Kg. Sample

Apple Pomegranate Black grapes Green Grapes 0.01 Banana Papaya 0.01 Cheeku Coconut Lemon

α BHC

β and γ BHC

dimetha noate

δ BHC

-

0.05 0.01

-

-

-

2.46 1.70

-

-

0.02 -

0.03 -

0.01

0.02 -

-

2.37 3.05

0.10

0.02 -

0.01

-

0.02

-

-

1.03 4.19

-

-

0.01 0.03

-

4.34 3.25 5.66

Methyl Malathion Endsuffan DDTDieldrin Parathion -

0.01 0.31

0.01

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of the standard was kept same. The multiresidue method which can detect all 9 pesticides in one analytical run was preffered. This method is characterized by a broad scope of application good recoveries and sensitivity and low solvent consumption, coupled with good analytical quality control. The presence of marathon, DDE in the respective sample were further confirmed by HNMR (Joel, 400 MHZ) and IR (Bruker) Spectral studies. HNMR and IR spectra of the standard pesticide was taken separately and compared with that of the sample containing those particular pesticides. The study including the following parameters Fruit sample, place of origin, Methods used and Pesticides tested for Table 1 and concentrations found for each pesticides table 2. Where the No. of Pesticides1) a BHC 2) g and b BHC 3) Dimethanoate 4) Methyl Parathion 5) Malathion 6) Endosulphama 7) DDE 8) Dieldrin

9) 10)

Ethion DDT CONCLUSION

The high levels of malathion is alarming. We have analyzed for only 9 pesticides where as the presence of many others can not be ignored. Out of necessity the field of residue analytical chemistry has emerged as a devoted specifically to the determination of sub microgram concentration levels of pesticides to confirm the tolerance established by law for pesticides in or on agricultural forage and food crops and animal products. The area associated with the nature, persistence and concentration level of pesticides residues on produce need to be critically examined by academic, industrial and government agencies to ensure manâ&#x20AC;&#x2122;s future well being. ACKNOWLEDGMENTS Authors are thankful to Dr. Rekha Lagarkha (Co-ordinator), Department of Chemistry Bundelkhand University, Jhansi for providing the necessary fulfill facilities.

REFERENCES

1.

2.

3.

4.

5.

Agency for Toxic substance and Disease Registry (ATSDR). Toxicological profile for HCB Atlanta, GA USA: U.S Department of Health and Human Services, Public Health Service, ATSDR, (1997). Agency for Toxicsubstance and Disease Registry (ATSDR). Toxicological profile for HCB. Atlanta, GA, USA: US department of Health and Human services, Public Health Service, A TSDR, (2002). Agnihotri N.P Dewan RS Dixit A.K Residu of insecticides in food commodities in food commodities from Delhi. 1. Vegetables. Indian J. Entromal 36: 160-162 (1974). American Cancer Society. Cancer facts and figures. Available at Bailey RE. Global Hexachlorobenzene emissions chemosphere, 2001; 43: 167-82 (2003). Ballschmitter K, Wittlinger R. interhemispheric exchange of

6.

7.

8.

9.

hexachlorocyclohexanes, Hexachlorobenzene, polychlorobiphenyls, and 1,1,1,-trichloro 2,2-bis (pchlorophenyl) ethane in the lower troposphere environ Sci. Technol., 25: 1103-1(1991). Barber J. Sweetman A, Jones K Hexachlorbenzene, sources, environmental fate and risk characterization. Euro Chlor. Barkatina E.N., and Zastenskaya I.A organo chlorine pesticides and polychlorinated biphenyls in fish and fish products consumed by the poplutation of the republic of Belarus. Benazon N. Hexachlorobenzene emission / releases inventory for Ontario 1988, 1998 and 2000., Draft Report for environment Canada, (1999). Bounias M. Etilogical factors and mechanism inolved in relation ships between pesticide exposure and cancer., J environ Biol, 24 (2003).

KANNAUJIA et al., Curr. World Environ., Vol. 7(1), 145-150 (2012) 10.

11.

12.

13.

14.

15.

16. 17.

18.

19.

20.

Braune BM. Norstorm RJ. Dynamics of organo chlorine compounds in hearing gulls. III: tissue distribution and bioaccumulation in Lake Ontario gulls. Environ Toxicol Chem. 9; 8: 957-68 (1989). Brook G. Hunt G. Source assessment for hexachlorobenzene Radian corporation, final report prepared for the U.S. EPA, Research Traingel Park. NC, USA, (1984). Budavari S, ed. Merck Index: An encyclopedia of chemicals, drugs, and biological, 11th edition. Rahway, NJ, USA: Merck & Co, Inc, (1989). Burns JE, Miller FM, Gomes E, Albert R: hexachlorobenzene exposure from contaminated DCPA in vegetables spraymen. Arch Environ Health, 29: 1924(1974). Cohen M, Commoner B, Eisl H, Bartlett P, Dickar. A, Hill C, et al. Quantitative estimation of the entry of dioxins, furans and Hexachlorobenzene into the Creat Lakes from, airborne and waterborne sources. May, In: Deposition of Air pollutants to the Great Waters-3rd Report to Congress. Office of Air Quality planning and standards. Research Triangle Park, NC, USA: U.S EPA, (1985). (Cited in/4/) Companhia de Technologia e Sanemento Basico de Sao Paulo (Sao Paulo State Company for Sanitation and technology) CETESB (2001). Compendium of common pesticide names. Classified list of pesticides. Currier MF, Mc claims CD, Barna-Lloyd G. Hexachlorobenzene blood levels and the health status of men in the manufacture of chlorinated solvents. J Toxicol Health 6: 36777 (1980). Davis DL, Bradlow HL can environmental estogens cause breast cancer? Sci am , 243 (1995). Dellinger B; Taylor PH; Tirey DA. Minimization and control of hazardous combustion biproducts, cincinnati, OH, USA: U.S. Environmental Protection Agency, Risk Reduction Laboratary (EPA 600/S2-90/039), (1991). Deutscher RL, Cathro KJ. Organochlorine formation in magnesium electrowinning cells

21.

22.

23.

24.

25.

26.

27.

28.

29.

30.

31.

149

chemosphere; 43:147-55 (2001). Dr. L martin Jerry WHO collaborating Center for Cancer Control Calgary, Canada Cancer: A global concern. The epidemiology of cancer. Ecobichon DJ. Toxic effect of pesticides in; Klassen DC, Doull J, eds. Casarett and doull’s tozicology; the basic science of poisons. 5th Edition, New york, NY USA; Mc Graw-Hill, 689 (1996). Ecobichon DJ. Toxic effects of pesticides. In : Klassen CD, Doull J, eds. Casaett and Doull’s toxicology. The Basic of Poisons. 5th Edition. New York, NY, USA: McGraw-Hill., 643- 689 (1996). FAO/WHO, joint FAO/WHO food standards programme. Codex maximum limits for pesticide residue. Vol. XIII. 2nd ed Romeltaly , (1986). Food and Agriculuture Organization /World health organization. Hexachlorobenzene evalution session of the codex committee on pesticide residues (JMPR), (1970). Government of Canada. Hexachlorobenzene. Priority substance list assessment report. Canadian Environmental Protection Act,(1993). Grimalt JO, Sunyer J. Moreno V.. Amaral OC, Sala M, Rosell A, et al. Risk excess of sontissue sarcoma and thyroid cancer in a community exposed to airborne organochlorinated compound mixtures with a high hexachlorobenzen content. Int J Cancer 1994: 56 (2003). Gullett BK, Touati A, Hays MD. PCDD/F, PCB. HxCBZ, and PM emission factors for fireplace and wood stove combustion in the San .1996 Francisco Bay Region. Environ Sci. technol 37: 1758-65 (2003). IARC’s mission cancer research for cancer control available at Information from the website the pesticide management education programmes (PMPS) at edu/ profiles/inse………amphus/). International program on chemical Safety (IPCS). Hexachlorobenzene Environmental Health Criteria 195. Geneva, CH: WHO (1997). International Register of potentially Toxic chemicals (I RPTC). Treatment and disposal

150

32.

KANNAUJIA et al., Curr. World Environ., Vol. 7(1), 145-150 (2012) methods IRPTC, Program Jaga K.

for waste chemicals. Geneva, CH: United Nations Environment 985: 102. what are the implications of the

interactions between DDT and estrogen receptors in the body? Med hypotheses (2002).

Current World Environment

Vol. 7(1), 151-156 (2012)

Seasonal Variation in Ground Water Quality at North Zone of Chalisgaon Taluka, Dist. Jalgaon (Maharashtra) P.J. PARMAR Department of Chemistry, Nanasaheb Y.N.Chavan College, Chalisgaon - 424 101 (India). (Received: May 20, 2012; Accepted: June 27, 2012) ABSTRACT This study deals with assessement of Physico - Chemical Characterisations of ground water around Chalisgaon Taluka of Jalgaon district in Maharashtra. The study has been carried out to examine its suitability for drinking, irrigation and industrial purpose. Rapid urbanization which caused ground water pollution has affected the availability and quality of ground water due to its over exploitation and improper waste disposal. Groundwater pollution caused by human activities like runoff fertilizers, pesticides used in agricultural field, release of industrial waste water, percolation of surface water etc. In the present study, attempts were made to investigate some Physico - Chemical Parameters of groundwater samples collected from seven wells at a distance of five to ten kms along north side of right Girna canal and Girna river from different locations of seven villages of Chalisgaon Taluka were studied in the span of June 2010 to Feb. 2012. The parameters pH studied includes temperature, electrical conductivity, total alkalinity, total hardess, calcium, magnessium, chloride, free CO2 total dissolved solid, dissolved oxygen. The study was carried out in each season for two consecutive years. The range of pH was found to be 7.45 to 9.19 which indicates that the water is alkaline. Other parameters are in the normal range but show variations drastically with the change in season. Detail variation in the range of values of parameters and possible causes are discussed. In case of underground water it was found that, conductivity, alkalinity and hardness were high and much over the permissible limits. The effect of long term continuous extensive irrigation by underground water and application of increasing amount of chemical fertilizers and insecticides over years on water and soil quality on this area have been discussed.

Key Words: Physico-Chemical Characters, Underground water, Well water and Canal water.

INTRODUCTION From the literature survey it is known that no investigation has been done on the quality of underground water in Chalisgaon Taluka of Jalgaon District of Maharashtra State. Seven villages are selected for this study situated in North - East of the Jalgaon district on the right bank of Girna river at a distance of 12 Kms from Chalisgaon town on state highway No. 211. The area under investigation is a notable cotton, sugarcane & banana producing centres and all the crop fields of this area are being irrigated by Girna right canal surface water and underground water as per availability of water resources Generally double and at some places

triple cropping are possible due to adequate irrigation facility for certain crops. The people of this locality reported that, for increasing the yield, the application of fertilizers and pesticides is also increasing since last 15 years, but the yield is not satisfactory and thus deterioration of underground water quality can not be ruled out. Hence present study has been under taken in order to assess the underground water quality of these villeges near the girna right canal. EXPERIMENTAL Seven villages of Chalisgaon blocks on the sides of Girna (right) canal and Girna river are

3.5 12.9 221.5 508.18 42.50 28.85 47.55 2.8 12.5 190.6 705.4 46.26 96.29 50.58 6. 7. 8. 9. 10. 11.

-March 2011 to June 2011 Summer Season

3.5 6.3 18.47 550.2 23.75 27.25 135.4 12.7 3.0 13.9 6.1 317 18.39 575.35 599.6 29.20 22.35 44.56 35.5 35.70 109.16 8.6 13.5 314 475.2 46.00 20.52 23.65 12.6 13.7 300 508.18 36.40 30.46 47.92 9.0 13.9 200.6 870 58.98 37.7 11.82 3.0 12.7 244 710.6 41.90 28.85 46.43

400 800 500 200 5.

selected for the present study namely 1 Dadpimpri 2 4 Umberkhede 3 Mehunbare Bhaur 5 6 7 Vadgaonlambe Dhamangaon and Khedgaon.

Results in mg /L, pH logarithanic Scale, Conductivity ( mmho /cm ) Temperature 0C ND - No detection. Rainy Season -July 2010 to October 2010 Winter Season -November 2010 to February 2011

4.8 8.1 8.2 8.3 5.7 1.5 12.7 6.7 6.9 6.8 6.4 6.5 ND 13.9 26.75 22.04 19.24 19.5 20.17 18.47 317 625.6 532.8 508.18 592.4 570.1 475.35 870 26.31 24.27 21.55 29.15 27.22 19.24 58.98 38.47 32.34 34.08 40.08 35.7 20.52 96.29 189.03 151.03 183.71 143.54 157.10 11.82 207.69

800 200 600 300 600

700

700

800

600

700

800

700

28.9 9.19 1800 26.0 7.45 100 28.9 9.15 110 28.9 8.77 120 28.7 8.98 100 28.8 8.94 120 28.7 9.13 140 26.9 7.54 110 27.1 7.45 110 1. 2. 3. 4.

Temperature 26.2 26.4 26.0 26.6 26.3 26.8 27.5 PH 8.42 8.25 8.56 8.22 8.31 8.23 8.49 Conductivity 1700 1500 1100 1800 1600 1800 1400 Total Dissolved Solids 800 700 700 800 700 700 800 Dissovled Oxygen 1.8 1.6 1.9 1.8 1.5 1.4 1.5 Free CO2 1.67 1.59 1.57 ND 1.67 1.67 1.65 Total Hardness 104 115 138 124 102 119 113 Total Alkalinity 590.4 550.3 580.8 624.3 562.4 627.1 565.2 Magessium 20.14 18.5 25.6 24.12 19.24 26.21 22.7 Calcium 33.66 32.50 29.66 30.64 28.05 31.12 28.70 Chloride 195.85 205.15 157.67 188.01 207.69 193.03 197.11

27.0 8.17 120

27.2 7.48 130

27.0 7.5 100

27.0 7.62 140

27.1 7.57 140

28.6 9.12 150

28.8 9.19 130

4 3 2 6 5 4 3 5 4 3 1

2

Rainy Season Sample Station

6

7

1

2

Winter Season Sample Station

7

1

Summer Season Sample Station

5

6

7

Max. Min.

PARMAR, Curr. World Environ., Vol. 7(1), 151-156 (2012)

S. Parameter No.

Table 1: Seasonal Variation in the underground water quality at North side Girna Canal (Right), Chalisgaon Taluka Dist. Jalgaon, Maharashtra State June 2010 to Feb. 2011.

152

The selection of wells from these villeges were at a distancd of about 05 Kms from each sampling point along the north side of the canal. The underground water samples were collected from deep wells from these villeges on the basis of their agricultural importance. While collecting the samples; the electrical pumps were run for one minute and then water sample was collected in screw cappled polythene can previously cleaned and washed with deionised water and again rinsed with the same water sample several times. The Underground water samples collected in the spell of June 2010 to Feb. 2012 in each rainy, winter and summer seasons. The water from wells of at a distance of about 5 to 6 km. north to the canal which on irrigation given good yield was also collected for reference. RESULTS AND DISCUSSION Various water samples are collected from different sampling stations during every season was analysed. Eleven Physico- Chemical Parameters of water samples were determined and recorded. The termperature of the sample was noted at the sample spot during collection. At the same time the dissolved oxygen was fixed by the Chemical Process Methodology for water analysis by Dr. Mohan S. Kodarkar (1992). Other parameters like electrical conductivity, pH, total alkalinity, total dissolved solids, Total hardness, calcium, magnessium, chloride, free CO2 were measured with in time span of three hours from sampling. The parameters were analysed by prescribed standard method given in (APHA and AWWA 1995, Trivedi & Goel 1986,Jackson 1958, & Kotaian and Sreedhar Reddy 2003). A complete chemical analysis may determine the suitability of ground water for drinking agriculture irrigation and industrial purpose. The analysis of ground water sample includes the determination of concentration of the inorganic constituents present in addition to the measurement of pH. electrical conductance, total dissolved solids

Dissovled Oxygen

Free CO2

Total Hardness

Total Alkalinity

Magessium

5.

6.

7.

8.

9.

7

1

2

3

4

5

6

7

1

2

3

4

5

6

7

8.24 8.42 8.31 8.26 8.47

8.1

8.0

115

1.3

0.4

700

800

120

1.7 117

1.4

1.98 1.81

700

119

1.3

1.2

800

600

500

140 400

130 300

140 600

130 700

110 700

100

109

1.2 107

1.6

8.2

2.48 2.40

8.1

8.2

9.1

8.7

298 244.1 194.3 321

11.5

1.25 1.70 13.4 12.5 12.3 13.8 13.8 12.7

800

3.10

8.8

8.8

800

150

120

8.3

8.4

700

110

115

8.4

8.1

300

140

119

4.3

8.9

800

100

121

3.2

8.3

600

110

100 700

600

1700

131

1.2

124

11.5

127

4.5

1.25 13.89 8.5

800

120

800

1700

110

1.2

321

11.5

1.25 13.89

300

100

7.92 7.88 8.23 8.44 8.51 8.63 8.21 8.57 7.88 8.75 7.75 8.75 8.30 8.37 7.88 8.75

33.86 32.95 29.95 29.75 29.95 30.70 37.10 58.60 40.55 43.25 57.24 58.80 35.45 35.0 36.10 35.60 35.44 29.75 58.80 32.7 34.10 29.75 58.80

653.4 575.2 624.3 593.4 625.5 570.7 569.1 701.9 721.9 735.0 860 753.7 713.12850.0790.4 601.2 635.5 974.4 589.3 528.2 750.4 528.2 774.4

110

1.9

2.11

700

1600 1000 1500 1700 1400 1300 1600

-

-

-

Rainy Season

Winter Season

Summer Season

March 2012 to June 2012

November 2011 to February 2012

July 2011 to October 2011

Results in mg /L, pH logarithanic Scale, Conductivity ( mmho /cm ) Temperature 0C ND - No detection.

91.18 11.7 106.7 190.45 171.3 164.1 150.2 68.34 135.7 121.4 131.71141.97196.41175.3 102.14 174.4 145.6 181.78149.4 141.64139.268.34190.45

Total Dissolved Solids

4.

6

29.24 30.5 32.16 28.01 27.45 31.38 28.3 49.56 35.2 27.29 22.56 21.24 15.4 14.22 27.25 29.5 36.11 33.44 37.02 35.04 30.2 14.22 49.56

Conductivity

3.

5

Min. Max.

27.8 27.7 28.0 28.3 27.8 28.1 27.5 25.9 25.7 25.8 26.0 25.0 26.2 26.1 28.1 28.5 28.6 28.2 28.3 28.4 28.7 25.0 28.7

4

Sample Statio

Summer Season

11. Chloride

PH

2.

3

Winter Season Sample Station

10. Calcium

Temperature

1.

2

No.

1

Rainy Season Sample Station

S. Parameter

Chalisgaon Taluka Dist. Jalgaon, Maharashtra State June 2011 to Feb. 2012

Table 2 : Seasonal Variation in the underground water quality at North side Girna Canal (Right),

PARMAR, Curr. World Environ., Vol. 7(1), 151-156 (2012) 153

154

PARMAR, Curr. World Environ., Vol. 7(1), 151-156 (2012)

and other minor constituents. Each of these properties is useful in evaluating the chemical character of underground water. This water quality is also influenced by meteorological factors such as rainfall, evaporation etc. Therefore, it needs a constant monitoring of chemical parameters through out the year. In the present study, underground water from seven wells tapping various aquifer formation in area have been sampled and analysed for a period of two years in rainy, winter and summer season. The variation in the concentration of mejor ion is shown in table 1 and 2 From these figures it is evident that the concentration of all the ions in winter season were low and exhibiting increasing trend in rainy and summer seaons. The reason for these changes could be the dissolution of salts and minerals which are present in soil due to the rise in water table during winter period. Kripanidhi (1984) have reported similar trends in ground water of a typical hard rock terrain and pollution in villages well in Karnataka State, India respectively. Physico - Chemical Parameters of ground water samples of north side of canal from various sampling points are given in table -1 along with miniumum and maximum values while these of water sample of a long distance towards north side of canal are given in Table 2. It was found that the termperature of wells of the villeges of Chalisgaon Taluka varies within about 30C during June 2010 to Feb. 2012 and average temperature of seven wells was 27.420C in all seasons for both the years. Various chemical and biological reactions in water depends to great extent on temperature. The observed values of temperature indicates that the water quality would be certainly affected by this parameter. The pH of water varies between 7.45 to 9.19 . It is observed that except in winter, pH.of all remaining samples was high particularly in summer, but on an average pH of all samples was in desirable limit as prescribed for drinking water standard (ICMR pH = 8.5). The average pH of all water samples from sampling stations were within the maximum permissible limit. It is known that pH of ground water does not reported by causes any severe health hazard reported by (Pujan & Sinha 1999)

The specific conductivity of samples under study varies between 100 to 1800m mho / cm. the maximum permissible limit of this parameter for drinking water is 300m mho / cm but average specific conductivity exceeds this limit because of itâ&#x20AC;&#x2122;s high values during each rainy season. In rainy season due to floods containing high electrolytes in water the conductivity of samples increases drastically ( reported by - Pujari & Sinha 1999). The sandard TDS in the water should below 1000 mg / L to consider it as non saline and values of water above this limit makes its nonpalatable ( reported by - Pujari and Sinha 1999). The permissible limit of TDS of drinking water is 500 mg / L ( WHO). This observation shows that the TDS is higher in comparision to WHO recommendation but was non saline and palatable. According to (kudesia 1985) good water quality have solubility of oxygen 7.0 and 7.6 mg / L at 3o0C and 350C respectively but except in rainy season all the sample showed higher values of D.O. Low values of D. O. in rainy season can be due to high values of conductivity of water. Free CO2 content in well water is due to rain from plant roots and decaying vegetation ( reported by - Pujari and Sinha 1999). The factors responsible for solubilisation of CO2 are temperature, pressure, pH and total alkalinity ( reported by - Johnson 1996) The free CO2 contents of water of different wells varies from 0 to 13.9 mg / L. However, the permissible limit of free CO2 has not yet been prescribed. Hardness has no known adverse effect on health ( reported by - Pujari and Sinha 1999) However maximum permissible level has been prescribed for drinking water is 500 mg / L by WHO According to same classification water having hardness upto 75 mg / L is classified as soft water 76-150 mg / L is moderately soft water, 151-300 mg / L as hard water (reported by - Twort 1974) on the basis of this observations the results shows that, 1. All the water samples in rainy season were moderately soft. 2. Most of the observation in winter season showed that water was of moderately hard

PARMAR, Curr. World Environ., Vol. 7(1), 151-156 (2012)

3.

level. In summer of 2010-2011 the observation showed that the water samples were soft but in summer of 2011-2012 water was moderately soft.

The total alkalinity of well water in terms of CaCO3 varied between 475.35 to 870. These values of total alkalinity were comparatevely large in quantity as compared to those reported by and Pujari and Sinha in 1999. Rajaramohanpur and Silguri (2003), but it itself is not harmful to human health rather it provide buffering action. The water for domestic use having alkalinity less than 100 mg / L is safe ( reported by - Goel & Trivedi 1986). The high content of alkalinity is evident in this particular area. Present investigation shows the concentration of calcium in the water samples in the range of 20.52 to 96.29 mg / L. during year June 2010 to Feb. 2011 and in the ragne of 14.22 to 49.56 during June 2011 to Feb. 2012. According to Ohle W. (1956), the waters above. Calcium values 25 mg. / L are classified as calcium rich. Thus as per the recommendations of ohle w. most of the water samples are ‘Calcium rich’. The observed values of magnessium were between 19.24 to 58.98 mg / L during June 2010 to Feb. 2011 and 29.75 to 58.80 mg / L. during June 2011 to Feb. 2012. This observations shows that maximum content of magnessium occured during winter. According to ISI and WHO standards the desirable maximum permissible values of magnessium content s for drinking water prescribed by 80 mg / L, 50mg / L and 30 mg / L 150 mg / L respectively Results of present investigation shows that the magnessium contents in mejority of samples does not exceed the limit as prescribed by ISI as well as WHO. Chlorine contents in water samples were in small quantity in rainy season and in very small quantity in winter season. According to WHO, the maximum permissible limit for chloride is 500 mg / L and since the values observed in present study are well below this level it has not imparted the test for water. This investigation of Physico- Chemical Parameters of water samples indicate that

155

Dissolved oxygen is well below the permissible limit but total alkalinity and total specific conductivity exceed the permissible limit. All remaining parameters are well within the limit. This indicates that no doubt water is contaminated but contamination is not of greater extent so far due to the agricultural practices followed by the people. Hence on the basis of above favourable results, water from these area are best suited for drinking irrigation & industrial application. A study of Physcio- Chemical charcterisation of underground water at a distanced of 5 to 10 Km. north to canal taken in winter season shows the correlation with the data of winter season of underground water from sampling sites near the canal. This study indicates that north side of underground water does not have any impact of canal on its Physico - Chemical Characters. Mechanism controlling the chemistry of ground water Conway (1984), Garham (1961), Garrels and Christ (1965, 1966), Gibbs (1970) and Ramesam and Barua (1973) have discussed in detail the mechanism controlling the chemistry of fresh water. The hydrochemical studies are being used to establish the relationship of water composition to aquifer litholgoy. This helps not only to explain the origin and distribution of disssolved constituents but also to elucidate the factors controlling the groundwater chemistry. As per the classification of Gibbs (1970), the major natural mechanisms controlling world surface ground water chemistry are admospheric preciptitation, rock weathering evalovation and fractional crsytalization. ACKNOWLEDGEMENTS Auther is thankful to the Management of R.S.S.P. Mandal Ltd., Chalisgaon, Dist. Jalgaon Sanstha’s Nanasaheb Y. N. Chavan Arts, Science, and Commerce College, Chalisgaon, Dist. Jalgaon (424101), for providing necessary laboratory facilities. Thanks are also due to The Management and Principal of the same college for overall help and constant encouragement throughout the present investigation.

156

PARMAR, Curr. World Environ., Vol. 7(1), 151-156 (2012) REFERENCES

1.

2.

3. 4.

5.

6.

7. 8. 9. 10.

11.

12. 13.

14. 15.

APHA and AWWA, Standard methods for the examination of water and water and waste water, 16th edition, Washington D.C. (1995) Bandela N. N, Physico - chemical projects of Barual Dam of Kandhar, Theiss submitted to Dr. B. A. M. University, Aurangabad. (1998) Kotaish B and Sreedhar Reddy S, Indian J. Environ. and Ecoplanm. 7(1): 43-46 (2003) Conway E. J, Mean geo-chemical data in relation to oceanic evolution. Proc. Irish Acad., 48: 119-159 (1984). Garham E, Factors influencing suply of major ions to inland water special reference to atmospheric; Bull Geo Soc Amer, 72: 795480 (1965) Garrels R. M. and Christ C. L. Solutions Minerals and Equilibria, Harper row, New York (1965) Gibbs R.J., Machanism Controlling water chemistry, 170: 1088-1090 (1970) Gopal Krishna Pujari and Sinha B. K, Journal of Env. and Pollution, 71-76 (1999) ICMR standards, standard methods for examination of water (1985) ISI and WHO, Indian Standards of drinking water specification, Bureau to Indian Standards New Delhi, 2-4, BIS 10500 (1992) Jackson M. L., Soil Chemical Analysis, Prentice Hall Pvt. Ltd., New Delhi, India. (1958) Kudesia V. P., Water Pollution, Pragati Prakashan, Meerut (1985) Kripanidhi K. V. J. R. Mechanism of Ground water pollution in village wells, Geological Society of India, 25: 301- 302 (1984) Mohan S. Kodarkar, Methodology of water analysis., (1992) Ohle W, â&#x20AC;&#x2DC; Bioactivity production and engergy utilization of lakesâ&#x20AC;&#x2122; Limnal and Ocenog., 1: 139-149 (1956).

16. 17.

18.

19.

20.

21.

22.

23.

24.

25.

26. 27.

Raja Rammohanpur Siliguri, J. Environ Biol, 24(2): 125-133 (2003). Trivedi R. K and Goel P. K, Chemical and Biological methods for water pollution studies, Environment publications, Karad (1986) Twort, A.C., Hoather R.C and Law F. M. Water supply, Edward Ornold Pub. Ltd., Londan (1974). WHO, Guideline for drinking water quality, recommendation World Health Organization, Geneva 1: (1984). Chavan T. P., Physico - Chemical Characteristics of Water and Soil, Ph.D. Thesis Dr. B. A. M. University, Aurangabad (2000). Shah, A. R., Physico- Chemical aspects of pollution in river Jhelum (Kashmir) during (1981-83). In Trivedy, R. K. Edited Ecology and Pollution of Indian rivers 163- 207 (1988). Raymahashay, B.C. Geochemistry of biocarbonates in river water, Great Soc. of India, 27: 114-118 (1986) Pujari and Sinha B. K. Journal of Environment and Pollution, 6(i): 71-76 (1999). (Technoscience Publication ) Prasad, B.V. and Rameshchandra P., Ground Water Quality in an Industrial Zone. A case study, Poll. Res. 16(2) : 105-107, (1997) Pandhe, G. M., Dhembare A.J. and Patil R. P., The Physichemical Characteristic and quality of water from the Pravara area, Ahemadnagar District, Maharashtra, J. Aqua. Biol. 10(1) : 43-48 (1995). G.S. Kabwania and Radhey Shyam. Orient. J. Chem. 28(1): 547-552 (2012). K.C. Gupta and Jagmohan Oberoi. Orient. J. Chem. 26(1): 215-221 (2010).

Current World Environment

Vol. 7(1), 157-161 (2012)

A Comparative Study on the Toxicity of a Synthetic Pesticide, Dichlorvos and a Neem based Pesticide, Neem-On to Labeo rohita (Hamilton) BILAL AHMAD BHAT1*, IMTIYAZ AHMAD BHAT1, SANTOSH VISHWAKARMA1, ALOK VERMA2 and GEETA SAXENA1 šDepartment of Zoology, Govt. Science and Commerce College Benazir, Bhopal - 462 008 (India). ²Department of Zoology, Govt. College Lateri vidisha - 464 114 (India). (Received: February 15, 2012; Accepted: March 29, 2012) ABSTRACT Fish and other organisms are affected by pesticides which pollute the natural water through agricultural runoff. Fishes are common bioindicators of water pollution. In the present study bioassay of synthetic pesticide, Dichlorvos and a plant origin natural pesticide, Neem-On was separately done on Labeo rohita. Data obtained from the toxicity tests were evaluated using the Probit Analysis Statistical Method. The 96h LC50 of Dichlorvos and Neem-On was found to be 16.71ppm, 42.66ppm respectively. The fish exhibited erratic swimming, copious mucus secretion, loss of equilibrium and hitting to the walls of test tank prior to mortality. In this study, Neem-On was less toxic to fish as compared to Dichlorvos. Plant based pesticides are biodegradable and are target specific than the highly persistent broad spectrum synthetic chemicals. Therefore, use of plant based pesticides is less disastrous and more ecofriendly.

Key words: Dichlorvos, Neem-On, Labeo rohita, Toxicity, 96h LC50

INTRODUCTION Increased used of pesticide results in the excess inflow of toxic chemicals, mainly in to the aquatic ecosystem (Baskaran et al., 1989; Kalavanthy et al., 2001). The aquatic environment is currently under threat by the indiscriminate use of synthetic pesticides by the human activities and causing high risk to non-target organisms (Kumar et. al., 2010). Among different classes of pesticides, organophosphates are more frequently used, because of their high insecticidal property, low mammalian toxicity, less persistence and rapid biodegradability in the environment (Singh et al., 2010). Dichlorvos is recommended for application as a high or a low volume spray on crops such as paddy, wheat, soyabean, apple, sugarcane, mustard, sunflower and cashew. The Environment Protection Agency (EPA) has classified dichlorvos as toxicity class 1 highly toxic (URL: 1). Several species of fish are susceptible to deleterious effects

when exposed to heavy metals, pesticides and other environmental stressors (Khangrat et al., 1988; Areechon and Plump, 1990). To overcome the hazardous effects of these organic pesticides, recent emphasis is on the use of natural pesticides, which are usually of plant origin. Some plants contain compounds of various classes that have insecticidal, piscicidal and molluscicidal properties. Unlike synthetic chemical pesticides, which leave harmful residues in the aquatic environment (Koesomadinata, 1980; Cagauan, 1990; Cagaun and Arce, 1992) botanical insecticides are believed to be more environmentally friendlier because they are easily biodegraded and leave no residues in the environment. Azadirachtin derived from neem (Azadirachta indicaA. Juss) is a very effective and extensively used pesticide. Pesticides based on azadirachtin may have direct adverse effects on aquatic organisms and their toxicity depends on

158

BHAT et al., Curr. World Environ., Vol. 7(1), 157-161 (2012)

various factors. It has been reported that neem extracts in aquatic environments are lethal to benthic populations and drastically decrease the number of organisms in the food web and nutrient cycling process (Goktepe et al., 2002; El-Shazly et al., 2000). Pesticides containing bioactive compounds from the neemplant, Azadirachta indica Juss are reported to be target specific and comparatively less toxic. However little work has been done on the toxic effect of neem based pesticides on fish. It is possible to substitute organic pesticides with the pesticides of plant origin. Hence the present study was carried out to evaluate the comparative effect of organophosphate pesticide Dichlorvos and neembased pesticide Neem-On to Labeo rohita (Ham.). MATERIAL AND METHODS Healthy and active adult Labeo rohita were obtained from Patra fish farm barkhedi Bhopal (M.P). They weighed 55g±1g and their length was in the range 15cm±1. They were brought to laboratory carefully in oxygen filled polythene bags in card board boxes to avoid any injury and disinfected by giving a bath for five minutes in KMno4 solution. Thereafter, they were transferred to glass aquariums filled with dechlorinated water. The fishes were acclimated to the laboratory conditions for at least 20 days prior to the experiment. During acclimatization fishes were fed daily with commercial fish food which was given at morning hours. Water was replaced every 24h after feeding in order to maintain a healthy environment for the fish during acclimation and experimental period.

This ensures sufficient oxygen supply for the fish and the environment is devoid of any accumulated metabolic wastes. Dead fishes when ever located were removed immediately to avoid fouling of the water. Water quality characteristics were determined and maintained. Nuvan (dichlorvos 76% EC) manufactured by Syngenta India ltd. 14, J. Tata road, Mumbai and Neem-On Manufactured by Jai Kissan Agro Pvt. Ltd., Sangam nagar, Indore, (M.P.) purchased from local market were used for evaluation of their toxicity to fish. . For determining LC50 concentration different stock solutions were prepared, separate glass aquariums were taken and different concentrations of Dichlorvos and Neem-on were added from the stock solution. Simultaneously a control set was run with the experiment. During assay no food was administered to fishes. The LC 50 concentration for 96h was calculated by probit analysis method of Finney’s (1971). The control, Neem-On and Dichlorvos exposed fish were kept under continuous observation during experimental periods. RESULTS The 96h LC50 value of Dichlorvos and Neem-On was found to be 16.71ppm and 42.66ppm respectively. The LC50 concentration for 96h was calculated by probit analysis method of Finney’s (1971). Table 1 and 2 shows the relation between the Dichlorvos, Neem-On concentration and the mortality rate of Labeo rohita and the graphs below show the plot of Finney’s probits against log10 conc. for calculating LC50 value of both the pesticides.

Table 1: For Dichlorvos

Conc.(mg/L) 14 15 16 17 18 19

Log10Conc. 1.1461 1.1761 1.2041 1.2304 1.2553 1.2788

Total No. 10 10 10 10 10 10

No. Dead 0 16 3 6 8 10

%Mortality 0% 10% 30% 60% 80% 100 %

Probit. 3.72 4.48 5.25 5.84 -

159

BHAT et al., Curr. World Environ., Vol. 7(1), 157-161 (2012) Table 2: For Neem-on Conc.(mg/L) Control 40 41 42 43 44 45

Log10Conc.

Total No.

No. Dead

%Mortality

Probit.

1.6021 1.6128 1.6232 1.6335 1.6435 1.6532

10 10 10 10 10 10 10

0 0 1 3 6 8 10

0 0 10 30 60 80 100

3.72 4.48 5.25 5.84 -

medium which can be viewed as an escaping phenomenon. They often spiral rolled at intervals and finally the fishes sank to bottom with their least operculum movements and died with their mouth opened. However, the behavioral changes were more prominent for the synthetic pesticide Dichlorvos as compared to Neem-on.

Probit Value

After exposure of both the pesticides, the Labeo rohita showed behavioral changes, they aggregated at one corner of aquarium, irregular, erratic and darting swimming movements and loss of equilibrium. They slowly became lethargic, hyper excited, restless and secreted excess mucus all over their bodies. The fish exhibited peculiar behavior of trying to leap out from the pesticide

Log10 concentration

Probit Value

Graph of Neem-0n

Log10 concentration

Graph of Dichlorvos

160

BHAT et al., Curr. World Environ., Vol. 7(1), 157-161 (2012) 13.1ppm for 24h (K.S Tilak and Swarna Kumari 2009).

DISCUSSION Newer biological pesticides are developed to replace deleterious chemical pesticides. Even though chemical pesticides are target specific and effective, their impact on the environment is mostly deleterious. Plant based pesticides contain active principles with low halflife period and their effects on the environment are not too detrimental (Sharma et al., 1995). In the present study, the pesticide containing azadirachtin is less toxic to fish compared to Dichlorvos. The 96h LC50 of Dichlorvos is 16.71 ppm. Whereas azadirachtin is much higher 42.66ppm indicating the less toxic nature of the plant based pesticide. Das et al., 2002 have studied the acute toxicity of neem in the fingerlings of Indian major carps i.e., Labeo rohita, Catla catla and Cirrhinus mrigala and the 96h LC50 values were found to be 2.36, 2.04 and 2.78ppm respectively. Hassanein et al., 2007 reported the 96h LC50 value of a neem biopesticide (Triology) on the grass carp fish, Ctenopharyngodon idella and was found to be 112ppm. Cagauan et al. (2004) showed that the lethal concentration of neem to Nile tilapia Oreochromis niloticus L. was 12.4 ml/L and mosquito fish Gambusia affinis Baird and Girard was 8.31 ml/L and the corresponding 96 h LC50 values were 2.57 and 3.0 ml/L ). The LC50 values of Dichlorvos has been reported by various workers as in Cyprinus carpio 6gm it was 0.34ppm for 96h (Verma et al., 1981) in Cirrhinus mrigala it was 9.1ppm for 96h (Velmurugan et al., 2009) and in Ctenopharyngodon idella it was

Comparison of the LC50 values clearly indicates that the plant based pesticide is less toxic compared to the chemical one. To reduce the chemical load on the environment, it is suggested that use of plant based pesticides should be encouraged (Schmutterer, 1990). However, care should be taken to use even the plant based pesticide at moderate levels. Furthermore, plant based pesticides disintegrate easily into constituent elements without leaving any indelible impression in different regions of the environment (Khan and Ahmed, 2000). It is advocated that more and more plant products should be developed with proper and targeted action and this eventually helps in keeping the environment free from hazardous chemicals. From the present study, it could be concluded that Dichlorvos contamination is dangerous to aquatic ecosystems, and this fact should be taken into consideration when this insecticide is used in agriculture or in the control of mosquito populations. It can be also concluded that although neem based pesticides are considered as less toxic and environmental friendly, but precautions must be taken when it is used in fish inhabiting areas since the excess application can affect the life of organisms. This type of study can also be useful to compare the sensitivity of the various species of aquatic animals and potency of chemicals using LC50 values and to derive safe environvimental concentration by which there is no lethality and stress to the animals.

REFERENCES

1.

2.

3.

Areechon, N. and Plump, J.A., Sub lethal effects of Malathion on channel cat fish, Ictalaurus punctatus. Bull. Environ. Contam. Toxicol., 44: 435-442 (1990). Baskaran, P., Palanichamy, S., Visalakshi, S. and Balasubramanian, M.P. Effects of mineral fertilizers on survival of the fish Oreochromis mossambicus. Environ. Ecol., 7: 463-465 (1989). Cagauan, A.G., The impact of pesticides on rice fields vertebrates with emphasis on fish. In: P.L. Pingali and P.A. Roger (Eds.), Impact

4.

. of pesticides on farmer health and the rice environment. International Rice Research Inst., Kluwer Academic Publ., Phillipines: 203-248 (1990). Cagauan, A.G. and Arce, R.G., Overview of pesticides use in rice-fish farming in South East Asia. In: C.R. Dela cruz, C. Lightfood, B. Coasta pierce, V.R. Carangal and M.P. Bimbao (Eds.), Rice-fish research and development in Asia. International Centre for Living Aquatic Resources Management (ICLARM) Conf. roc., Philippines: 24: 217-

161

5.

6.

7.

8.

9.

10.

11.

BHAT et al., Curr. World Environ., Vol. 7(1), 157-161 (2012) 233 (1992). Caguan, A.G., Galaites, M.C. and Fajardo, L.J., Evaluation of botanical piscicides on Nile tilapia Oreochromis niloticus L. and mosquito fish Gambusia affinis Baird and Girard. Proceedings on ISTA, 12-16 September. Manila, Phillipines: 179-187 (2004). Das, B. K., Mukherjee, S. C., and Murjani, O. Acute toxicity of neem (Azadirachta indica) in Indian major carps. Journal of Aquaculture in the Tropics, 17: 23-33 (2002). El-Shazly, M.M. and El-Sharnoubai, E.D. , Toxicity of a neem (Azadirachta indica) insecticide to certain aquatic organisms. Journal of the Egyptian Society of Parasitology, 30(1): 221-231. Finney, D.J., Probit analysis, 3rd (Ed.), Cambridge University Press, London, 333 pp (1971). Goktepe, I. and Pihak, L.C., Comparative toxicity of two azadirachtin â&#x20AC;&#x201C; based neem pesticides to Daphnia pulex. Environmental Toxicology and Chemistry, 21(1): 31-36 (2002). Hassanein, H. M. A; Okail, H. A. and Mohamed, N.K. Biochemical changes in proteins and DNA in Ctenopharyngodon idella due to environmental pollution with the biopesticide (Trilogy). 10 ICCA, Garyounis University, Benghazi, Libya: 1821 (2007). Kumar A., Prasad, M.R., Srivastava, K.,

12.

13.

14.

15.

16.

17.

Tripathi, S. and A.K., Srivastava., Branchial Histopathological Study of catfish Heteropneustes fossilis following exposure to purified Neem Extract, Azadirachtin. World journal of zoology. 5 (4): 239-243 (2010). Kalavathy, K., Sivakumar, A.A. and Chandran, R., Toxic effect of the pesticide Dimethoate on the fish Sarotherodon mossambicus. J. Ecol. Res. Bioconserv., 2(1-2): 27â&#x20AC;&#x201C;32 (2001). Khan, M.F. and Ahmed, S.M., Toxicity of crude neem leaf extract against housefly Musca domestica L. adults as compared with DDVP, Dichlorvos. Turk. J. Zool., 24(4): 219-223 (2000). Khangarot, B.S., Ray, P.K. and Singh, K.P. Influence of copper treatment on the immune response in an air breathing teleost Saccobranchus fossilis. Bull. Environ. Contam. Toxicol., 41: 222-226 (1988). Koesomadinata, S., Pesticide as a major constraint in integrated agricultureaquaculture farming system. In: R.S.V. Pullin and Z.H. Shehadeh (Eds.), Integrated Agriculture - Aquaculture Farming Systems. (ICLARM) Conf. Proc., 4: 45-51 (1980). Schmutterer, H., Properties and potential of natural pesticides from the neem tree, Azadirachta indica. Ann. Rev. Entomol., 35: 271-297 (1990). Sharma, S.K., Dua, V.K. and Sharma, V.P., Field studies on the repellent action of neem oil. Southeast Asian. J. Trop. Med. Pub. Helth., 26: 180-182 (1995).

Current World Environment

Vol. 7(1), 163-167 (2012)

Studies in River’s Bottom Sediments in Swarnarekha River around Jamshedpur and Ghatsila for Metallic Pollution H.S. MISHRA1 and S.K. JHA2* 1

Department of Chemistry, Jamshedpur Co-operative College, Jamshedpur (India). 2 *Department of Chemistry, J.S.M. College, Jamshedpur (India). (Received: April 28, 2012; Accepted: June 10, 2012) ABSTRACT

Studies of heavy metals namely Iron, Chromium, Manganese, Cobalt, Nickel, Copper, Zinc, Cadmium and lead as pollutants in river water and waste water discharge samples of rivers around steel plants of Jamshedpur and Ghatsila, East Singhbhum, Jharkhand, was carried out from February,2012 to March, 2012. Atomic Absorption spectrophotometric analysis of nonfilterable residue of bottom sediments for the heavy metals were made. The fractionation analysis of the adsorption and/or ion exchangeable, oxide coating, organic solids and crystalline phase was carried out. Total metals concentration was also determined. The sum of the concentration of metals in adsorbed, oxide coating and organic solid phases is available to biota. The crystalline phase is not available to biota. The results have been discussed and the conservation of metal available to biota have been estimated.

Key words : Metal transport phases, Bottom sediments, Pollutants, biota, Atomic Absorption spectrophotometer (AAS) and Self purification.

INTRODUCTION

EXPERIMENTAL

The chemical composition of the bottom sediments and its variation of different sites in the river Swarnarekha receiving the treated and untreated waste water from domestic and industrial sources have a profound impact on the water quality of the river basin. Water chemistry only assesses the effluent impact at the time of sampling while the bottom sediments geo-chemistry gives a cumulative assessment of pollution. Bottom sediments analysis has been used to trace pollutant inputs and to anticipate the effects of their pollutants on water quality.

Sampling Sites. (i) Swarnarekha River (Near Nirmal nagar, Sakchi) in February, 2012 Site IA – Discharge Sample Site IB – River Water Sample (1 Km away from discharge) (ii) Swarnarekha River (Near Ghatsila) in March, 2012 (iii) Site II A – Discharge Sample (iv) Site II B – River Water Sample (1 Km away from discharge)

In this work, the bottom sediments from different sites on the river Swernarekha around Steel City of Jamshedpur and Ghatsila was analysed for their multi-element composition with a view to establish the relationship between the pollution of rivers and the discharge of domestic and industrial waste waters.

Partitioning of waste water discharge sample The sample was transferred into two 1 litre measuring flasks separately and then filtered through Whatman filter paper (No.-42) separately. Filtrate in all the cases were rejected. The residues in the above two cases were collected separately and treated as follows :

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Residue-I The residue obtained after filtration of the waste water discharge sample along with the filter paper was treated with 20 ml aqua regia and heated for 0.5 hours over water bath. It was then filtered through Whatman filter paper (No.-42) and the volume was made up to 500 ml with distilled water in a volumetric flask. The metals determined in this filtrate were the total metal concentration in this sample. Residue-II The residue obtained after filtration of 1 litre of waste water discharge sample along with the filter paper was leached with 50ml of 0.5 N MgCl2. 6H2O solution for 7 hours stirring from time to time and it was then filtered through Whatman filter paper (No.-42). The filtrate was then made upto 500ml with distilled water in a volumetric flask for the determination of adsorbed and/or ion exchangeable heavy metals (Eisenreich-1980). The residue left over on the filter paper along with the filter paper itself was then leached with 0.4 N sodium pyrophosphate solution for 10 hours stirring from time to time and then filtered. The filtrate was then made upto 500ml and heavy metals associated with organic solid were estimated from this filtrate. The residue along with filter paper was treated with 50ml 0.3 N HCl solution and heated at 90oC for 0.5 hr and then filtered. The filtrate, was then made, upto 500ml. Heavy metals in oxide coating were determine in the filtrate. The residue along with the

filter paper was then treated with 20ml aqua regia and heated over water bath for 0.5 Hrs. It was then filtered and the volume of the filtrate was made upto 250ml. The metals determined in this last filtrate were designated metals in crystalline state. Partitioning of river Water Sample Similar procedure was followed for the determination of total concentration of heavy metals and concentration of heavy metals in different phases. The samples obtained as above were analysed for estimation of heavy metals such as Fe, Mn, Cr, Ni, Co, Cu, Zn, Cd and Pb by Atomic Absorption spectrophotometer. RESULTS AND DISCUSSION Among the heavy metals, iron occurs in much higher concentration at site IA & IIA (discharge sample) 18.52 to 16.857 ppm. At site IB & IIB (river water sample) the concentration is 11.67 to 6.402. Total Mn content in the sample as determined by Atomic absorption spectrophotometer were 0.85 to 0.429 ppm at the point of discharge and in river water sample it is 0.259 to 0.16 ppm. Ni in discharge sample were estimated to be 0.919 ppm to 0.766 ppm where as in river water sample it is 0.183 ppm to 0.1 ppm. Total Zn metal concentration in discharge sample was found to be 1.61 to 1.34 ppm and in river water sample was estimated to be 1.15 to 0.84

Table 1: Waste water discharge sample (At the point of discharge) site-IA in the month of February, 2012 of Swarnarekha river, Nirmal nagar, Jamshedpur (By Atomic Absorption Spectrophotometer) Heavy metal concentration in difference phase in mg/liter or ppm Elements

Fe Mn Ni Zn Pb Cd Co As

Total Concern

Adsorbed Solid

Organic Phase

Oxide Phase

Crystalline Phase

18.521 0.85 0.766 1.34 0.26 0.010 Nf Nf

11.659 0.78 0.27 0.14 Nf Nf Nf Nf

0.024 Nf Nf 0.11 0.101 Nf Nf Nf

2.02 0.041 0.026 0.069 0.009 Nf Nf Nf

5.894 0.45 0.397 1.045 0.124 0.007 Nf Nf

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165

Table 2: Heavy metal concentration in different phase in mg/litre or ppm (1 Km away from discharge) of Swarnarekha river site â&#x20AC;&#x201C; IB (Feb, 2012) Elements

Fe Mn Ni Zn Pb Cd Co As

Total Concern

Adsorbed Solid

Organic Phase

Oxide Phase

Crystalline Phase

6.402 0.259 0.10 0.84 0.017 0.702 Nf Nf

2.989 0.197 0.07 0.56 0.006 0.042 Nf Nf

1.291 0.065 0.013 0.27 nf 0.062 nf nf

0.499 0.062 Nf 0.14 nf 0.011 nf nf

2.88 0.108 0.028 0.33 0.023 0.031 Nf Nf

Table 3: Waste Water River sample (At the point of discharge) Site-IIA in the Month of March, 2012 of Swarnarekha River, HCL, Moubhandar, Ghatsila. Heavy metal concentration in different phase in mg/litre or ppm(By Atomic Absorption Spectrophotometer). Elements

Fe Mn Ni Zn Pb Cu Co As

Total Concern

Adsorbed Solid

Organic Phase

Oxide Phase

Crystalline Phase

16.657 0.429 0.919 1.61 0.158 0.048 Nf Nf

0.846 0.187 0.26 0.55 0.031 0.004 Nf Nf

0.114 0.14 0.027 0.34 0.017 Nf Nf Nf

3.861 0.052 0.019 0.094 Nf Nf nf nf

13.988 0.284 0.328 1.16 0.092 0.0246 Nf Nf

Table 4: Heavy metal concentration in different phase in mg/litre or ppm (1 Km away from discharge point) of Swarnarekha River, Site-IIB (March, 2012) Elements

Fe Mn Ni Zn Pb Cu Co As Nf : not found.

Total Concern

Adsorbed Solid

Organic Phase

Oxide Phase

Crystalline Phase

11.67 0.16 0.183 1.15 0.201 1.54 0.008 Nf

6.55 0.0617 0.069 0.513 0.078 0.646 Nf Nf

3.96 Nf Nf Nf 0.008 0.054 Nf Nf

2.39 0.0171 Nf 0.027 0.012 0.039 Nf Nf

5.24 0.0447 0.07 0.62 0.085 0.845 0.006 Nf

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ppm. Lead metal concentration was found to be 0.26 to 0.158 ppm in discharge sample and in river water sample it was 0.201 to 0.017 ppm. Higher concentration of Pb-metal in River water is probably due to domestic discharge in the River water.

while not found in oxide phase. The variation of concentration of Ni metal in sample IB was adsorbed>crystalline>organic while not found in oxide phase whereas in others it was crystalline> adsorbed>organic>oxide form. Partioning of

The partioning of Iron in different forms show that the dominant phase is the crystalline one for transportation of iron. This finding is similar to the finding of Roy and Mishra (1988) and Mishra & Tiwary but it is contrast to that of Roy and Upadhyaya (1985) found in their studies.

Pb-metal in different phases were found as crystalline>adsorbed>organic>oxide wherein concentration of metal is very low. However, oxide phase and organic phase was found to be almost nil in some of the samples. CONCLUSIONS

The more common transport phase behavior for iron in the river water in Swarnarekha river is adsorbed>crystalline>oxide>organic solid but at site IIA the trend is crystalline> adsorbed> oxide>organic solid. Mn concentration in different phases as analysed by Atomic absorption spectrophotometer in Swarnarekha river is adsorbed>crystalline> oxide>organic except for site IIA where crystalline> adsorbed>oxide>organic. These finding are different from Dr.Mishra & Tiwary. Zn concentration in different phase were estimated and found to be adsorbed>crystalline> oxide>organic solid in site IB while in the rest it was found to be crystalline>adsorbed>organic>oxide

There data about the occurrence of Fe, Mn, Cu, Cr, Ni, Zn and Pb in the various available and unavailable metal phases would help in determining the effect of these metals on the crops and other biota. The higher concentration of these heavy metals in water prevents the self purification of water and thereby produces adverse effect for aquatic lives. General standard for discharge of environmental pollutants (inland surface water) such as Fe = 3.0mg/L, C-2.0 mg/L, Cu-3.0 mg/L, Zn = 5.0 mg/L, Ni = 3 mg/L. However it needs further study on the co-relation of the concentration of these metals in the various phases and their toxilogical and other effects.

REFERENCES 1.

2.

3.

4.

5.

APHA Standard methods for examination of water and waste water (12th edn; part I). American public Health Association, New York 317-320 (1967). S.J. Eisenreich, M.R. Hoffman, D. Rastetter, E. Yost and W.J. Maier, ACS symp Ser. 189: 135 (1980). H.S. Mishra, Studies in metal transport phases in rivers around Jamshedpur Ph.D., Thesis, Ranchi (1988). N.N. Roy, and N.P. Upadhyaya Toxicological and environmental Chemistry, 10: 285-298. (1985). V.R. Sub. Naniu. Van Grieken and I, vant dacka Env. Geolr water Sci. 9(2): 93-103, (1987).

6.

7.

8. 9.

10. 11.

A.I. Vogel, A text book of quantitative inorganic analysis (4th edn.). The English Language Book society and Longman, London (1978). W. Stummn and J.J. Morgan Aquatic Chemistry (2nd edn) John Wiley and Sons. New York. (1981). M.M. Reddy, Environmental International (1979). R.M. Chattopadhyaya, Studies in river sediments around Jamshedpur. Ph.D. Thesis, Ranchi University, Ranchi (1985). H.S. Mishra and P.B. Tiwary J. Chemtracks 6: 69 (2004). W. Schott, Dtsch. Labensmitt Rdsch, 48: 6263 (1952).

MISHRA & JHA, Curr. World Environ., Vol. 7(1), 163-167 (2012) 12. 13.

14.

M.J. Stiff, Water res, 5(8): 585-599 (1971) A.I. Kadukin, V.V. Krasintseva, G.I. Romanova and L.V. Tarasonko, Gidribiol Zh, 18(1): 7982 (1982). H.S. Mishra & P.B. Tiwary â&#x20AC;&#x153;Studies in monitoring and Control of chemical Pollution due to heavy metalsâ&#x20AC;?, Jchemtracks., 10(1&2):

15.

16.

167

121-128 (2008). A.S. Waznah, B.Y. Kamaruzzaman, M.C. Org. S.Z. Rina and S.M. Zahir. Orient. J. Chem. 26(1): 39-44 (2010). V. Magarde, S.A. Iqbal, S. Pani and N. Iqbal. Orient. J. Chem. 26(4): 1473-1477 (2010).

Current World Environment

Vol. 7(1), 169-173 (2012)

Physico-Chemical Analysis of Underground Drinking Water in Morbi-Malia Territor B. M. BHESHDADIA1*, M. B. CHAUHAN2 and P.K.PATEL1 1*

Department of Chemistry, M. M. Science College, Saurashtra University, Rajkot, Gujarat, Morbi - 363 642 (India). 2 Department of Chemistry, J. & J. College of Science, Nadiad, Gujarat University, Ahmedabad, Gujarat (India). (Received: April 03, 2012; Accepted: May 03, 2012) ABSTRACT Physico-chemical analysis such as temperature, salinity, alkalinity, total hardness, phosphate, sulphate, nitrate, pH, electrical conductivity, T.D.S., turbidity, dissolved oxygen, fluoride, chloride of bore-well water was carried out from twenty five sampling stations of Morbi-Malia territory during May-2010 (before monsoon) and October-2010 (after monsoon) in order to assess water quality index.

Key Words: Physico-chemical analysis, Bore-well drinking water, Morbi-Malia, Gujarat.

INTRODUCTION In continuation of earlier studies on borewell water1-3, here we have investigated intensively the Physico-Chemical analysis of drinking water of Morbi-Malia territory, located in Rajkot district of Gujarat state. Bore-well water is generally used for drinking and other domestic purposes in this area. The use of fertilizers and pesticides, manure, lime, septic tank, refuse dump etc. is the major sources of bore-well water pollution4. In the absence of fresh water supply people residing in this area use borewell water for their domestic and drinking purpose. In order to assess water quality index, we have conducted the physico-chemical analysis of borewell drinking water. EXPERIMENTAL In the present study bore-well water samples from twenty five different areas located in and around Morbi-Malia territory were collected in brown glass bottle with necessary precautions5. All the chemicals were used of AR grade. Double distilled water was used for the preparation

of reagents and solution. The major water quality parameters considered for the examination in this study are temperature, pH, D.O., turbidity, electrical conductivity, T.D.S., salinity, alkalinity, phosphate, sulphate, nitrate, fluoride, total hardness and chloride contents6. Temperature, pH, D.O., turbidity, electrical conductivity, T.D.S., salinity, phosphate, nitrate and fluoride value were measured by water analysis kit, portable D.O. meter and manual methods. Total hardness of water was estimated by complexometric titration methods 7-8 . Chloride content was determined volumetrically by silver nitrate titrimetric method using potassium chromate as an indicator and was calculated in terms of mg/ l. Alkalinity of water samples were measured volumetrically by titrimetric method7-8. Sulphate content was determined by volumetric method7. RESULTS AND DISCUSSION Temperature In the present study, temperature in May2010 ranged from 29.6 to32.60C and temperature in October-2010 ranged from 29.1 to 31.80C.

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D.O. In the present study, D.O. in May-2010 ranged from 3.9 to 7.3 ppm. The minimum tolerance range is 4.0 ppm for drinking water. But the D. O. was found lower in sample station Nos. 8. In October-2010 D.O. ranged from 4.1 to 8.3 ppm. pH In the present study, pH in May-2010 ranged from 7.10 to 8.90. The tolerance pH limit9 is 6.5 to 8.5. The sample station No. 1, 5, 6, 7, 8, 11, 12, 13, 15, 16, 17, 20, 21, 23, 24 and 25 showed higher pH than prescribed range. In October-2010 pH ranged from 7.67 to 9.02. The sample station No. 8, 12, 15, 16, 17, 20, 21 and 23 showed higher pH than the prescribed range. Turbidity In the present study, Turbidity in May-2010 ranged from 0.08 to 2.35 NTU and in October-2010 Turbidity ranged from 0.15 to 4.60.The tolerance range for Turbidity is 5 NTU10. So all the sample station Nos. have shown lower NTU values than the prescribed range. Electrical conductance In present study, Electrical conductance in May-2010 ranged from 0.74 × 10-3 to 6.15 × 10-3 mho/cm, while in October-2010 Electrical conductance ranged from 0.51 × 10-3 to 4.97 × 10-3 mho/cm. T.D.S. In the present study, TDS in May-2010 ranged from 399 to 3070 ppm. According to WHO9 and Indian standards10, TDS value should be less than 500 ppm for drinking water. The sample station Nos. 1 to 25 except 10 and 21 showed higher ranges compare to prescribed WHO and Indian standards. In October-2010 TDS ranged from 247 to 2460 ppm. But sample station Nos. 1 to 25 except 10, 20, 21 and 24 showed higher range than prescribed range. Salinity In the present study, Salinity in May-2010 ranged from 390 to 3060 ppm and in October-2010 Salinity ranged from 240 to 2450 ppm.

Alkalinity In the present study, Alkalinity in May-2010 ranged from 100 to 650 ppm while in October-2010 Alkalinity ranged from 110 to 710 ppm. Phosphate In the present study, Phosphate in May2010 ranged from 13 to 41 mg/l and in October2010 Phosphate ranged from 10 to 39 mg/l. The evaluated value of phosphate in the present study is higher than the prescribed value14. The higher value of phosphate is mainly due to the use of fertilizers and pesticides by the people residing in this area. If phosphate is consumed in excess, phosphine gas is produced in gastro-intestinal tract on reaction with gastric. Nitrate In the present study, Nitrate in May-2010 ranged from 85 to 445 mg/l and in October-2010 Nitrate ranged from 92 to 423 mg/l. The tolerance range for Nitrate is 20-45 mg/l. Nitrate nitrogen is one of the major constituents of organism along with carbon and hydrogen as amino acids proteins and organic compounds in the bore-well water15. If the nitrate reduces to nitrite then it causes methaemoglobinaemia in infants 16-18 and also diarrhea. Sulphate In the present study, Sulphate in May-2010 ranged from 130.28 to 362.07 mg/l and in October2010 Sulphate ranged from 109.25 to 359.55 mg/l. The tolerance range of Sulphate is 200-400 mg/l12. Total hardness In the presence study, Total hardness in May-2010 ranged from 115 to 960 ppm and in October-2010 Total hardness ranged from 85 to 820 ppm. The tolerance range for Total hardness11 is 300-600 ppm. Chloride In the present study, Chloride in May-2010 ranged from 122.2 to 1465.7 mg/l and in October2010 Chloride ranged from 68.9 to 1257.5 mg/l. While the tolerance range for chloride is 200-1000 mg/l10.

Name of Sample Station

Shri Ram Society Yadunandan Society Panchavaty Society Jain Derasar Gayatri Nagar Bhagvati Park Science College Relif Nagar Bhuvneshwer Park Kenal Road Matam Chock Bhisti Vad Rail. Station Road Kharivadi Ramji Mandir Chock Jetpar Aniyari Khakharechi Sarvad Mota Dahishara Khakharada Jodhapar Nadi Chachapar Nani Vavadi Nichi Mandal

S. No:

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25

30.4 30.2 31.7 29.6 31.5 31.0 32.6 30.8 31.5 30.1 31.7 30.7 31.3 31.8 31.5 30.8 31.4 31.5 31.9 31.4 32.2 30.8 31.3 32.3 31.9

Temp (0C)

4.1 5.5 4.4 4.5 6.8 6.6 4.9 3.9 5.4 7.3 6.9 5.5 6.7 5.8 5.9 5.3 5.8 6.4 5.8 5.2 5.6 6.3 5.5 6.5 5.4

D.O. (ppm)

8.70 7.10 8.42 8.48 8.59 8.75 8.56 8.66 8.37 8.39 8.62 8.77 8.71 8.29 8.78 8.81 8.90 8.28 8.28 8.58 8.58 7.85 8.68 8.69 8.69

PH

0.22 0.23 0.08 0.39 0.15 0.10 0.35 0.18 0.15 0.31 0.18 0.17 0.11 0.13 0.41 0.17 0.40 0.21 0.18 1.75 0.49 0.29 2.35 0.37 0.17

Turb. (NTU)

2.10×10-3 2.47×10-3 1.71×10-3 2.20×10-3 6.15×10-3 3.37×10-3 1.82×10-3 2.37×10-3 2.23×10-3 0.98×10-3 6.06×10-3 4.35×10-3 3.33v10-3 5.10×10-3 3.46×10-3 4.11×10-3 3.49×10-3 1.37×10-3 5.21×10-3 1.78×10-3 0.74×10-3 1.87×10-3 1.88×10-3 1.11×10-3 1.39×10-3

Cond. (mho /cm) 1010 1280 855 1110 3070 1670 940 1225 1165 460 3040 2110 1690 2610 1820 2110 1820 730 2580 880 399 940 1020 515 670

1000 1270 845 1090 3060 1660 930 1210 1150 455 3030 2100 1680 2595 1810 2100 1810 720 2570 870 390 930 1010 510 660

650 510 250 250 370 600 100 350 110 150 390 600 600 130 310 640 330 240 130 430 150 210 430 230 290

16 20 21 30 20 41 20 18 19 36 20 34 38 16 20 35 21 20 17 16 13 15 20 26 17

158.18 292.25 265.33 275.02 230.55 142.18 168.62 220.47 321.44 198.21 230.48 229.28 151.12 261.36 290.21 225.25 283.23 130.28 260.48 259.01 138.51 264.41 362.07 275.28 149.32

441 87 420 265 191 417 445 135 415 330 205 285 416 129 85 299 87 400 135 430 350 307 413 380 415

1.1 1.0 0.9 1.1 1.2 1.1 1.0 0.9 1.2 1.0 1.2 0.8 1.1 1.0 1.2 0.9 1.2 1.0 1.0 0.9 1.1 0.9 1.0 1.2 1.0

115 305 610 512 960 438 734 360 690 305 950 205 440 350 250 197 255 270 340 125 200 560 175 198 221

162.5 298.9 305.2 285.2 1465.7 440.3 398.7 395.1 452.6 145.6 1450.7 688.4 445.7 1324.5 666.6 667.3 667.2 151.4 1326.3 155.8 135.3 394.1 306.6 122.2 196.4

T.D.S. Salinity Alkali- Phosh Sulp- Nitrate Flouride Total Chloride nity phate hate (mg/I) (mg/I) Hardnes (mg/I) (ppm) (ppm) (ppm) (mg/l) (mg/I) (ppm)

Table 1: Analysis result of the samples collacted from morbi-malia territory in May - 2010

BHESHDADIA et al., Curr. World Environ., Vol. 7(1), 169-173 (2012) 171

Name of Sample Station

Shri Ram Society Yadunandan Society Panchavaty Society Jain Derasar Gayatri Nagar Bhagvati Park Science College Relif Nagar Bhuvneshwer Park Kenal Road Matam Chock Bhisti Vad Rail. Station Road Kharivadi Ramji Mandir Chock Jetpar Aniyari Khakharechi Sarvad Mota Dahishara Khakharada Jodhapar Nadi Chachapar Nani Vavadi Nichi Mandal

S. No:

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25

29.2 29.1 30.6 29.2 30.3 30.1 31.8 29.6 30.2 29.2 30.7 30.2 30.2 30.6 30.4 30.3 30.4 30.4 30.7 30.5 31.2 30.3 30.3 31.1 31.2

Temp (0C)

4.1 5.4 5.8 5.5 7.6 7.5 5.8 4.9 6.3 8.3 7.9 6.6 7.4 6.5 6.5 6.3 6.5 7.2 6.7 6.3 6.7 7.2 5.8 7.2 6.4

D.O. (ppm)

8.15 7.67 8.49 8.48 8.31 8.40 8.35 8.90 8.35 8.47 8.27 8.66 8.49 8.29 8.58 8.69 8.58 8.30 8.35 8.73 8.55 8.27 9.02 8.23 8.19

PH

0.30 0.59 0.97 0.49 0.44 0.17 0.52 0.51 0.57 0.38 0.44 0.36 0.20 1.20 0.54 0.37 0.52 0.15 1.27 0.31 0.82 0.65 4.60 0.58 0.59

Turb. (NTU)

1.88x10-3 990 2.35x10-3 1140 1.32x10-3 720 1.88x10-3 910 4.97x10-3 2460 2.25x10-3 1380 1.28x10-3 510 1.58x10-3 780 1.27x10-3 580 0.95x10-3 460 4.85x10-3 2440 2.12x10-3 1020 2.24x10-3 1360 4.40x10-3 2190 3.10x10-3 1560 2.12x10-3 1050 3.14x10-3 1550 1.48x10-3 740 4.38x10-3 2195 0.88x10-3 444 0.51x10-3 247 1.25x10-3 650 1.70x10-3 830 0.77x10-3 384 1.80x10-3 890 980 1130 710 900 2450 1370 490 770 570 450 2430 1010 1350 2180 1550 1040 1540 730 2180 440 240 640 820 380 870

710 650 430 350 590 670 590 450 210 330 570 430 670 110 470 430 450 290 130 220 170 210 520 350 370

10 13 22 27 19 35 18 15 19 32 20 35 34 16 20 39 22 23 17 15 13 15 25 29 18

109.25 180.23 187.32 222.30 208.57 139.35 141.72 192.37 285.45 175.25 200.48 211.25 131.15 239.48 271.72 210.21 278.23 115.39 232.58 235.11 138.51 245.12 359.55 276.38 148.21

341 95 411 232 179 367 412 110 359 318 172 290 370 117 94 291 92 377 137 423 345 333 421 371 401

0.9 1.0 0.9 1.0 1.1 1.0 0.9 1.0 1.1 1.0 1.0 0.9 1.0 1.2 1.0 1.0 1.1 1.1 1.1 1.0 1.2 0.9 1.0 1.2 1.2

95 270 480 390 820 330 614 150 320 320 800 195 347 320 250 180 220 260 310 130 170 350 85 135 295

240.2 245.8 211.1 245.3 1170.7 341.5 308.7 177.8 178.7 130.2 1161.5 348.9 342.5 1257.5 612.2 349.1 620.9 141.1 1245.2 148.7 71.5 259.5 248.8 68.9 342.4

Cond. T.D.S. Salinity Alkali- Phosh Sulp- Nitrate Flouride Total Chloride (mho nity phate hate (mg/I) (mg/I) Hardnes (mg/I) /cm) (ppm) (ppm) (ppm) (mg/l) (mg/I) (ppm)

Table 2: Analysis result of the samples collacted from morbi-malia territory in oct - 2010

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ACKNOWLEDGMENTS

Fluoride In the present study, Fluoride in May-2010 ranged from 0.8 to 1.2 mg/l and in October-2010 Fluoride ranged from 0.9 to 1.2 mg/l. While the tolerance range for Fluoride is 1.0 to 1.5 mg/l10. The study has shown that the essential elements in water like TDS, Salinity, Phosphate, Nitrate, pH, Total hardness, Chloride are higher than tolerance range. There fore, the bore well water in this territory is not drinkable.

The Principle Investigator is thankful to UGC for financial assistance in the form of Minor Research Project [F No. 47-550/08 (WRO) Dated:15/01/2009]. The Principle Investigator is also thankful to The Sarvodaya Education Society, Morbi and the Principal, M. M. Science College, Morbi, for providing necessary facilities.

REFERENCES

1.

2.

3.

4. 5.

6.

7. 8. 9.

Rana A.K., Kharodawala M.J., Patel J. M, Rai R.K., Patel B.S. and Dabhi, Asian J.Chem., 14: 1209 (2002). Rana A.K., Kharodawala M.J., Dabhi H.R., Suthar D.M., Dave D.N., Patel B.S. and Rai R.K., Asian J. Chem., 14: 1178 (2002). Bhoi D.K., Raj D.S., Mehta Y.M., Chauhan M.B. and Machhar M.T., Asian J.Chem., 17: 404 (2005). Hamilton P.A. and Helsel D.K., Ground Water, 33: 2 (1995) Broun E., Skovgstd M.W. and Fishman M.J., Method for Collection and Analysis of water Samples for Dissplved Minerals and Gases, 5: (1974) Manivasagam N., Physico-chemical Examination of water, Sewage and Industrial Effluents, Pragati Prakashan, Meerut (1984). Vogel A.I., Text Book of Quantitative Inorganic Analysis, 4th Edn., ELBC, London (1978). H.C. Kataria and Shalini Sharma, Orient J. Chem. 26(1): 337-338 (2010). APHA: American Public Health Association, Standard Methods for Examinnation of water and Wastewater, 16th Edn., APHA-WPCF-

10. 11. 12. 13.

14.

15. 16.

17. 18.

AWWA, Washington (1985). International Standard for Drinking Water, 3rd Edn., WHO, Geneva (1971). The Gazette of India: Extraordinary, Part-II, 3: 11 (1991). Dhembare A. J., Pondhe G.M. and Singh C.R., poll. Res., 17: 87 (1998). Mekee J.E. and Wolf H.W., Water Quality Criteria. The Resources Agency of Californina State Water Quality Control Board (1978). APSFSL, Andhra Pradesh State Forensic Science Laboratories, Annual Report (1988). Miller D.G., Nitrate in Drinking Water, Water Research Centre, Medmenham (1981). NEERI: National Environment Engineering Research Institute, Disinfection of Small Community Water Supplies, Nagpur (1972). White J.W. and Agri J., Food Chem., 23: 886 (1975). Mushtaq Hussain, T.V.D. Prasad Rao, H. Ali Khan and M. Satyanarayan. Orient. J. Chem. 27(4): 1679-1684 (2011).

Current World Environment

Vol. 7(1), 175-178 (2012)

Acute Toxicity and Behavioural Responses of Labeo rohita (Hamilton) to a Biopesticide “NEEM-ON” IMTIYAZ AHMAD BHAT1*, BILAL AHMAD BHAT1, SANTOSH VISHWAKARMA1, ALOK VERMA2 and GEETA SAXENA1 1

Department of Zoology, Government Science and Commerce College Benazir, Bhopal - 462 008 (India). 2 Department of Zoology, Government College Lateri, Vidisha - 464 114 (India). (Received: January 01, 2012; Accepted: February 27, 2012) ABSTRACT

The objective of this study was to determine the toxicity of the neem biopesticide azadirachtin (NEEM-ON, Brand name) on the freshwater fish ‘Labeo rohita’. Fishes were exposed to various concentrations of botanical insecticide azadirachtin for 96 h and the percent mortality was recorded. The 96h LC50 value determined by Finney’s Probit Analysis Method was found to be 42.66 ppm. Behavioural patterns were observed critically during the whole experiment. The test fish exhibited erratic swimming, increased surfacing, decreased rate of opercular movement, reduced agility and inability to maintain normal posture and balance with increasing exposure time.

Key words:Toxicity, Azadirachtin, NEEM-ON, Labeo rohita, LC50, Behavioural changes.

INTRODUCTION Neem (Azadirachtin indica) is a traditional and highly esteemed medicinal tree for the people of Indian sub-continent.It is one of the most promising medicinal plant, having a wide spectrum of biological activity, well known for its insecticidal properties (ICAR, 1993). Biological activities and medicinal properties of neem have been extensively reviewed by Biswas et al (2002). Azadirachtin (a tetranotriterpenoid) is one of the major components (Kraus et al., 1981; Broughton et al., 1986) of neem, which have pesticide property. In view of the environmental problems caused by the use of synthetic chemicals and the growing need for alternative methods of pest control that minimize this damage, there has been extensive research on pest control by substances from plants. One of the most promising natural compounds is azadirachtin, an active compound extracted from the neem tree. Recently neem based pesticides are popularised due to their effectiveness, cheaper price and comparatively safe for users, which is used widely in several states of India. However,

neem has been found to be toxic to non-target organisms where it induces marked alterations in experimental animals (Mahboob et al., 1998; Anjaneyulu et al., 1999; Mondal et al., 2007). Fishes are considered as good indicators of aquatic pollution. They are highly sensitive to the alterations in the quality of water. Labeo rohita was selected as the test species. The present study was aimed to determine the 96h LC 50 value and behavioural response of a neem based pesticide “NEEM-ON” to the freshwater fish Labeo rohita. MATERIAL AND METHODS Biopesticide NEEM-ON (Manufactured by Jai Kissan Agro Pvt. Ltd., Sangam nagar, Indore, M.P.) was used in this study. It is based on neem seed kernel extract containing a minimum of 0.15% EC (1500PPM) of azadirachtin as active ingredient. Test animal Labeo rohita weighing 58±3g and

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average length of 15cm were collected from the Patra Fish Farm, Berkhedi, Bhopal, Madhya pradesh. The fishes were acclimatized to the laboratory conditions for 15 days. They were fed daily with commercial fish pellets.Water was renewed after every 24hrs. Physio-chemical characteristics of water were determined and maintained. Experimental procedure The experiments were conducted in a series of glass aquariums (30 litre capacities) filled with 20 litre tap water. The stock solution was prepared and the required quantity of azadirachtin was drawn from this stock solution to find out the LC50 value for 96 h. Different concentrations were prepared and for each concentration a control was maintained. Ten acclimatized fishes of uniform size were exposed to each concentration. Preliminary tests were carried out to find out the median lethal concentration (LC50) of the fish to azadirachtin for 96h by Fenneyâ&#x20AC;&#x2122;s Probit Analysis Method. The control and the exposed fish were aerated frequently to prevent hypoxic condition of the medium.The control and azadirachtin exposed fish were kept under continuous observation during the experiment period. Feeding to fishes was stopped during the experiment. Behaviour of the test fishes was observed and the dead fishes were removed and recorded from time to time during 96 hr exposure period. The water in the containers was changed every 24 hr and a constant concentration of Neemon was maintained during the period of exposure.

RESULTS The maximum concentration at which zero percent mortality and minimum concentration at which 100% mortality of Labeo rohita were observed was at 40 ppm and 45ppm respectively. The determination of 96h LC50 value of Neem-on to Labeo rohita was found to be 42.66ppm by Finneyâ&#x20AC;&#x2122;s Probit Analysis Method (1971) and is depicted in the graph. In this study, Labeo rohita was subjected to various concentrations of Neem-on and its behavioral changes were observed. The behavioral and the swimming patterns of the fish were normal in case of control group and there was no mortality. After the exposure of fishes to Neem-on, various behavioral changes were observed. First the schooling of fishes starts disrupting and then abnormal swimming behavior increases. The fishes were observed to hit the aquarium walls. The opercular movement initially increases and then decreases with rising toxicant concentration in the exposed fishes. Vertical and downward swimming patterns were observed. Loss of balance increased and the color of the fish were observed to get lighter with an increased secretion of mucus. Surfacing frequency and gulping of surface water with occasional coughing increases remarkably in exposed fishes. Defecation was increased and more fecal matter was found at the bottom of the aquarium than control. Finally due to complete loss

Table 1: The graph showing linear curve between probit mortality of fish against log concentration in L. rohita on exposure to Neem-on. Conc. (ppm) Control

Log10 Conc.

No.of Fishes 10

No. of Dead (96h) 0

Mortality (%) 0

40 41 42 43 44 45

1.6021 1.6128 1.6232 1.6335 1.6435 1.6532

10 10 10 10 10 10

0 1 3 6 8 10

0 10 30 60 80 100

Probit

3.72 4.48 5.25 5.84

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Probit Value

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Log10 concentration Fig. 1: of balance, fishes sank to bottom with their ventral side facing upwards. After 96h exposure of pesticide to fishes, at 45ppm hundred percent mortality was observed. DISCUSSIONS The acute toxicity values of several neem products for different fish species have been reported earlier by many workers. Das et al., 2002 have studied the acute toxicity of neem in the fingerlings of Indian major carps i.e., Labeo rohita, Catla catla and Cirrhinus mrigala and the 96h LC50 values were found to be 2.36, 2.04 and 2.78ppm respectively. Hassanein et al., 2007 reported the 96h LC50 value of a neem biopesticide (Triology) on the grass carp fish, Ctenopharyngodon idella and was found to be 112ppm. In the present study, the 96h LC50 value of Neem-on on the Labeo rohita was found to be 42.66ppm. The variation in the LC50 values is due to its dependence upon various factors viz., sensitivity to the toxicant, its concentration and duration of exposure; type and size of the test animal and so on. Behavioral changes are the most sensitive indication of potential toxic effects. Impact of different pesticides on the behavior of Labeo rohita have been studied by various workers (Marigoudar et al., 2009; Anita et al., 2010; Nagaraju et al., 2011).

Fishes exhibited a number of behavioral changes when they were exposed to different concentrations. The opercular movement of fishes initially increases and then gradually decreases. Decreased opercular movement probably helps in reducing absorption of pesticide through gills. Abnormal swimming and loss of balance was caused by the decifiency in nervous and muscular coordination which may be due accumulation of acetylcholine in synaptic and neuromuscular junctions (Rao et al., 2005). A thick coat of mucus was observed all over the body of the fish, making the fish slimier. The fish were swimming with the belly upwards and in zig zag motion. There were also erratic and parallel movements observed in the fish, indicating loss of equilibrium while in control, the fish was swimming normally without loss of equilibrium. The fish sometimes becomes highly excited and was observed to hit the aquarium walls at a very fast speed. Due to this hyperexcitibility bleeding from the snout was observed in some fishes. Neem-on, a biopesticide is an ecofriendly product used against different pest species but its effect on non-target organisms can not be ruled out. So, neem based pesticides should be used cautiously.

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BHAT et al., Curr. World Environ., Vol. 7(1), 175-178 (2012) REFERENCES

1. 2.

3.

4.

5.

6.

7.

8.

9.

ICAR: World Neem Conference Souvenir ICAR, Bangalore, India (1993). Biswas, K., Chattopadhyay, I., Banerjee, R. K. and Bandyopadhyay, U. Biological activities and medicinal properties of neem (Azadirachta indica). Current Science, 82: 1336-1345 (2002). Kraus, R.K., R.Cramer and G.Sawitzki. Tetranortriterpenoids from the seeds of Azadirachtin indica. Phytochemistry, 20(1): 117 (1981). Broughton, H.B., S.V.Ley, A.M.Z. Slawin, J.D. Williams and E.D.Morgan: X-ray crystalographic structure determination of detigloyldihydroazadirachtin and reassignment of the structure of the limionoid insect antifeedent azadirachtin .J.Chem.Soc. Chem. Commun., 391-401(1986). Mahboob, M., J. Siddiqui and K. Jamil: The effect of subacute administration of a neem pesticide on rat metabolic enzymes. J. Environ. Sci. Hlth., 33: 425â&#x20AC;&#x201C;438 (1998). Anjaneyulu, G.V.S.R. and K.D.Mishra. Acute toxicity of Neemax (Neem Seed Powder) to a freshwater fish, Puntius ticto Ham. Pollution Research . 18(4): 391-394 (1999). Mondal, D.; Barat, S. and Mukhopadhyay, M. K.: Toxicity of neem pesticides on a fresh water loach Lepidocephalichthys guntea (Ham.) of Darjeeling district in west Bengal. J. Environ. Biol. 28(1): 119-122 (2007). Finney, D.J.: Probit Analysis, 3rd Edn. Cambridge University Press, London (1971). Das, B. K., Mukherjee, S. C., and Murjani, O.

10.

11.

12.

13.

14.

Acute toxicity of neem (Azadirachta indica) in Indian major carps. Journal of Aquaculture in the Tropics, 17: 23-33 (2002). Hassanein, H. M. A; Okail, H. A. and Mohamed, N.K. Biochemical changes in proteins and DNA in Ctenopharyngodon idella due to environmental pollution with the biopesticide (Trilogy). 10 ICCA, Garyounis University, Benghazi, Libya: 1821 (2007). Marigoudar S.R., R.Nazeer Ahmed and M.David. Impact of Cypermethrin on behavioural responses in the freshwater teleost, Labeo rohita (Ham.). World Journal of Zoology. 4(1): 19-23, (2009). Anita S, K.Sobha and K.S.Tilak. A study on acute toxicity, oxygen consumption and behavioural changes in the three major carps, Labeo rohita, Catla catla and Cirrhinus mrigala exposed to Fenvalerate. Bioresearch Bulletin. 33-40 (2010). Nagaraju B, Sudhakar P, Anitha A, Haribabu G and Rathnamma V.V.: Toxicity evaluation and behavioural studies of freshwater fish Labeo rohita exposed to Rimon. International Journal of Research in Pharmaceutical and Biomedical sciences. ISSN., 2229-3701 (2011). Rao, J.V., G.Begum, G. Pallela, P.K.Usman and R.N.Rao. Changes in behavior and brain acetylcholinesterase activity in mosquito fish Gambusia affinis in relation to sublethal exposure of chlorpyrifos. Int. J. Environ. Res. Public Health, 2(3-4): 478-483 (2005).

Current World Environment

Vol. 7(1), 179-182 (2012)

Evolution of Child Development in the Multimedia Environment ASHVINI JOSHI and VINITA BHATNAGAR Sri Satya Sai College of Engineering, Bhopal (India). (Received: March 20, 2012; Accepted: May 27, 2012)

INTRODUCTION

The role that information technologies are playing and will continue to play in the area of education , explains the ways that these forms of mass media are being applied in education to make it a more accessible, more effective, and more efficient. It illustrates that these forms of media hold a great deal of potential, and will become more and more important to education, multimedia teaching strategies allow for people to become educated and trained, who in the past would not have been given such an opportunity.

technological tools that are available today we have been able to enhance learning and teaching at the same time. As a teacher, facilitator reading or speaking out the information to the students is not sufficient. A class or a session is like a presentation, and the presenter (teacher) needs to plan and prepare his/her session. Along with rendering information, it is the learning outcome to be achieved that has to be kept in mind. Technology helps and aids teachers to enhance this learning outcome. It looks at the argument that multimedia can educate children by entertaining and keeping their interest while they learn. Multimedia is a tool that can be used to increase the learning outcome of a session. In fact, it is a combination of multiple techniques, Today’s children and those of the future will grow up immersed in the multimedia environment. I anxiously wait to see how these children will integrate the various media into their environments, creating and expanding their cognitive, social, physical, and creative capacities. The “wall” of information and technology that divided adults and children in the past is now not so thick, as children are now able to access all types of information easily using these technologies. They are also able to engage themselves in many types of virtual experiences which will allow them to broaden their skills and imagination. However, the question of how these children should best utilize, to their fullest potential, multimedia technologies and how adults who guide these children should scaffold them still remains unclear.

Advantages of Multimedia The impact of technology on Education has been tremendous. By adopting the various

Multimedia Encourages New Learning Styles “Students must be the change they want to bring in world”

Education is not preparation for life; education is life itself. The time it takes to earn the degree in education today is based on an increasingly outdated model: so many hours in a classroom entitle a student to a receipt in the form of a grade, and so many receipts can be redeemed for a credential in the form of a degree... Education today is just beginning to think of shifting the basis of certification from time served to skills and knowledge obtained. Multimedia holds great promise for improving the quality of education because multimedia provides the ability to illustrate ideas with visual, audio, text or any combination of media so learners can create new ways of communicating ideas.

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Modern computer and communication technology is becoming common place in a growing number of schools. Add to this the multimedia capabilities of the web and students literally have the world of information at their fingertips, with much of this information available to them in ways easy for them to grasp. As new media are used by students both as their source of raw information and as the tools through which they express their mastery, the role of educator changes. Instead of teachers providing “content” to students, they now are freed to help students find “context” and meaning in their studies. Multimedia as the catalyst “Education’s purpose is to replace an empty mind with an open one.” Education has historically prepared most students to live productive lives in a family within a society. This technology can serve as a catalyst to help educators capitalize on the unique skills which each learner brings to the classroom. Multimedia technology can support an education environment in which ´ All children can learn-the computer can enhance the learning process, from enabling communication for a child who is severely disabled, to providing insight and new ways of dynamically visualizing concepts for children who have special talents. ´ Cultural heritages are valued and nurturedtechnology can help teachers provide learning environments that are not only culturally sensitive to the heritage of each of their students, but culturally affirmative and rich in varied language experiences. ´ Learning is a lifelong process-the computer can engage both parent and child and encourage learning for both through intergenerational sharing of language and experience. ´ Families can become more self-sufficientcomputer technology can provide individualized programs in basic skills, literacy, health and nutrition, and career development, not only in formal education environments, but in community centers, museums, libraries, and the home.

“One’s destination is never a place but rather a new way of looking at things” Our goal must be to harness technology to provide the most engaging and dynamic system ever used in education, so that school once again embraces culture and learning in our society. The process of education must deal with the needs of students to develop both macro and micro strategies for dealing with their world. One effect of the worldwide information processing capability is that work can now move to wherever skilled labor is available. Countries are now linked financially, economically, socially, culturally, and politically as never before, and this linkage is constantly growing. This can create new income and demand for more goods and services in countries which have educated their populations to deliver the skills in demand for the information age; it can rapidly drain countries whose citizens do not develop skills to keep pace with the emerging work opportunities “The surest way to grow the global market for educational media is to grow the global audience of educated people.” Benefits of multimedia technology Multimedia technology is intended to improve education over what it would be without technology. Some of the claimed benefits are listed below: Easy-to-access course materials Instructors can post the course material or important information on a course website, which means students can study at a time and location they prefer and can obtain the study material very quickly Student motivation Computer-based instruction can give instant feedback to students and explain correct answers. Moreover, a computer is patient and nonjudgmental, which can give the student motivation to continue learning. Students usually learn more in less time when receiving computer-based instruction and they like classes more and develop more positive attitudes toward computers in computer-based classes

JOSHI & BHATNAGAR, Curr. World Environ., Vol. 7(1), 179-182 (2012) Wide participation Learning material can be used for long distance learning and are accessible to a wider audience Improved student writing It is convenient for students to edit their written work on word processors, which can, in turn, improve the quality of their writing. According to some studies, the students are better at critiquing and editing written work that is exchanged over a computer network with students they know Subjects made easier to learn Many different types of educational software are designed and developed to help children or teenagers to learn specific subjects. Examples include pre-school software, computer simulators, and graphics software “An educational system isn’t worth a great deal if it teaches young people how to make a living but doesn’t teach them how to make a life.” Knowledge is innately free and rightly belongs in the public domain. We just want learning to be easy, personalized. Technology is an increasingly influential factor in education. Computers and mobile phones are used in developed countries both to complement established education practices and develop new ways of learning such as online education (a type of distance education). This gives students the opportunity to choose what they are interested in learning. Technology offers powerful learning tools that demand new skills and understandings of students, including Multimedia, and provides new ways to engage students, such as Virtual learning environments. Technology is being used more not only in administrative duties in education but also in the instruction of students. The use of technologies such as PowerPoint and interactive whiteboard is capturing the attention of students in the classroom. Technology is also being used in the assessment of students. One example is the

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Audience Response System (ARS), which allows immediate feedback tests and classroom discussions. Information and communication technologies (ICTs) are a “diverse set of tools and resources used to communicate, create, disseminate, store, and manage information.” These technologies include computers, the Internet, broadcasting technologies (radio and television), and telephone. There is increasing interest in how computers and the Internet can improve education at all levels, in both formal and non-formal settings. Older ICT technologies, such as radio and television, have for over forty years been used for open and distance learning, although print remains the cheapest, most accessible and therefore most dominant delivery mechanism in both developed and developing countries. Yesterday’s impossible is today’s normal. What we want is to see the child in pursuit of knowledge, and not knowledge in pursuit of the child.” “Education is a weapon, whose effect depends on who holds it in his hands and at whom it is aimed.” It also exposes the other side of the argument— that children are merely being entertained, learning how to passively watch, while developing shorter attention spans and the need for quick stimuli , also study the difference between training and critical thinking with the use of multimedia. This does not mean, however, that any program filled with rich media elements is automatically valuable. Our task in education is to engage, not entertain, the learner. Our new tools provide the potential to do this, but the art of software development still requires careful thought about both the pedagogy and curriculum.

REFERENCES 1.

Apple, Multimedia demystified. New York: Random House (1994).

2.

Anderson, J. R., Cognitive psychology and its implications. New York: W.H. Freeman

182

3. 4.

5. 6.

7.

8.

9.

10.

11.

JOSHI & BHATNAGAR, Curr. World Environ., Vol. 7(1), 179-182 (2012) (1990). Barrett, E. & Redmond, M., Contextual media. Cambridge, MA: MIT Press (1995). Biocca, F. & Levy, M.R., Communication in the age of virtual reality. Hillsdale, NJ: Lawrence Erlbaum (1995). Blattner, M.M.., In our image: Interface design in the 1990s. IEEE Multimedia, 25-36 (1994). Clark. R.E., Reconsidering research on learning from media. Review of Educational Research, 53: 445-459 (1983). Dannenberg, R. & Blattner, M., The trend toward multimedia interfaces. In Blattner, M. and Dannenberg, R. (Eds.) Multimedia Interface Design. New York: ACM Press (1992). Davenport, G., Seeking dynamic, adaptive story environments. IEEE Multimedia, 3: 913 (1994). Davenport, G. Seeking dynamic, adaptive story environments. IEEE Multimedia, 3: 913. (1994). Davenport, G., Evans, R. & Halliday, M., Orchestratingdigital micromovies. Leonardo, 26: 4 (1993). Eberts, R.E. User interface design.

12.

13.

14.

15. 16. 17.

18.

19. 20.

Englewood cliffs, NJ: Prentice-Hall (1994). Erickson, T.D., Working with interface metaphors. pp65-73 in Laurel, B. ed. Art of human computer interface design. Reading, Massachusetts: Addison Wesley (1990). Falk, D., & Carlson, H., Learning to Teach with Multimedia. T.H.E. Journal, pp. 96-101 (1992). Farah, M.J., Knowledge from text and pictures: A neuropsychological perspective. In Mandl, H. & Levin, J.R. (Eds.) Toffler, Alvin (1990) Powershift (1989). Utz, Peter. All You Need is LV (1994). Van Tassel, Joan., Advanced Television Systemsl. Newton, MA: Focal Press (1996). Waern, Y., Cognitive aspects of computer supported tasks. Chicago, John Wiley (1989). Waring, Becky., Video Scan Converters: Not as Simple as they Seem. New Media Magazine, pp. 37-42 (1994). Wilson, S. Multimedia design with hypercard Prentice Hall. Wimberly, D. & Samsel, J., Interactive writerâ&#x20AC;&#x2122;s handbook. Los Angeles: Carronade Group (1995).

Current World Environment

Vol. 7(1), 183-186 (2012)

Analysis of Pesticide Residues in Winter Fruits CHITRA GUPTA¹, ROHIT VERMA¹*, RAVI KANT KANNAUJIA¹ and FAROOQ AHMEDWANI² ¹Department of Chemistry , Bundelkhand University Jhansi - 284 128 (India). ¹Department of Chemistry, APS University Rewa - 486 003 (India). (Received: February 20, 2012; Accepted: May 27, 2012) ABSTRACT Fruit samples of winter fruits (apple, grapes, banana cheeku, papaya, lemon) for pesticideresidues employing a multiresidue analysis by gas liquid chromatography.All the fruit samples showed the presence of residues with one or other group of pesticides.Some samples exceeded the quantification limit.The increasing interest in the pesticides in fruit samples is justified from the enological point of view.In this paper pesticide mobility on fruit samples was studied.Out of nine pesticides tested for most of the sample show very high levels of malathion ,while other pesticides residues are with in the established tolerance,BHC endosulphan dieldrin are with in limits.thus consumer intake of pesticides from fruit samples studied in this work should be reduced bywashing fruits with water .In this paper multiresidue determination of pesticides are discussed using G.C.

Key words: Pesticides,GC, Fruits residues.

INTRODUCTION A pesticide is a chemical substance used for preventing, destroying, repelling or mitigating a pest, which can be an insect; rodent, bind, weed or fungus, as well as micro organism like bacteria and viruses. Pesticides can be broadly classified as insecticides, herbicides, fungicides, rodenticides, and antimicrobials, with many subclasses. The major insecticide groups are the organochlorines, organophosphates, carbonates and pyrethroids. Pesticides are considered hazardous chemicals and improved the regulation of pesticides particularly in developed countries, a health risk remains. Both the potency of primary factor affecting the level of risk. The use of pesticides provided an important socioeconomic benefit to the areas of agriculture and food productions. Pesticide production is market driven with high investment in industrialized countries. In the U.S, 77% of all pesticides are used. In developing countries, public health programs represent an important use of

pesticides in the control of vector borne diseases like malaria. Countries in Africa, Asia and central South America are highly dependent on pesticides. Other areas in which pesticides are used include forestry, gardening and lawn care horticulture and livestock and to a large extent domestic use in home. In the U.S pesticides are used in around 70 million homes. Usage of OCP’s have been prohibited in most of countries, but 70% of banned pesticides low cost, in India DDT was banned for use in agriculture in 1985, but still 7500 metric tons per year is used here. The problems of pesticides residues in crops has been attracting growing attention the use of organic insecticides for the control of insect on crops has become common during the past few years. [1] The detection and identification of pesticides in our environment is a problem of increasing public interest. [2-4]

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Pesticides residues in food has become a consumer safety issue. The consumer has a right to know how much pesticide gets in corporate in the food he eats. At many laboratories expanded research programmers have been instituted to understand and control more fully the varied effects of pesticides like:1) The appraisal of the potential carcinogenicity of ingested substances. 2) Palatability and organoleptre evaluation of fruits, meats and vegetables. 3) Assimilation of detailed data on acute and chronic toxicity for all compounds. 4) Nature of plant surfaces and the chemical modes of penetration subsequent translocation, distribution and metabolic fate in plants and exudation of regulating compounds into the soil. 5) Establishment of safety threshold levels within a human being without immediate or future harm. The short as well as long term impact of the use of pesticides on biological systems is being evaluated continuously in an effort to minimize. Potential or latent hazards while maximizing the benefits derived by marking form increased agricultural production and communicable disease eradication. [5] The use of pesticides has not permitted the control of diseases transmitted by insects but also has led to increased food production and better health. EXPERIMENTAL Selection of fruit samples were based on their availability in winter. The samples were purchased in Jhansi. The fruits sold here are bought from the near bus stand in Jhansi. The fruit samples was analyzed in the form, that is offered to the consumer. For example apple, Cheeku, Papaya and grapes were analyzed with peels whereas banana, pomegranate and coconut were analyzed without peels. Lemon was analyzed with peals as it is used in making pickles in the form6. Each sample size taken 1 kg out of which

a representative substance weighting 20gram was randomly taken and the pesticides were extracted for 8-10 hr at the rate (4-5) cycles per hr, in hexane in a soxhelt extractors. The rotary evaporators. The concentrate contained aqueous as well as organic residue. The organic part was extracted in hexane with the help of a separating funnel and a pinch of sodium sulphate was added to it. The solution thus obtained was filtered and concentrated again. To this 5 ml of hexane was added and the sample thus prepared was analyzed for the presence of 9 pesticides by gas chromatograph (Perkin ElmerAuto system XL) with the selective electron-capture detector (ECD). This detector allows the detection of contaminants at trace level concentration in the lower ppm range in the presence of multitude of compounds extracted from the matrix to which these detectors do not resend.[7] The column used was PE-17, length 30m. ID 0.25 film 0.25 mm with a 2 ml/min flow. The carrier gas and the make up gas was nitrogen employing the splitting mode. The oven temperature was kept at 190-2800C with a ramp of 50c/min. The lam plies were calibrated (retention time, are a count) against a 10 ppm standard mixed solution of all 9 pesticides. Each peak is characterized by its retention time and the response factor in ECD. Sample results were quantitated in ppm automatically by the GC software. One GC injection (30 min) was required in order to cover all 9 pesticides included in a analysis. Hamilton micro syringes injection of the pesticide dissolved in hexane as solvent were made directly onto the coated silanized column solid support, there by eliminating the possibility of catalytic degradation by metallic surfaces. Pesticides were identified according to their retention time. For accurate result the concentration of the standard was kept same.[8] The multiresidue method which can detect all 9 pesticides in one analytical run was preffered. This method is characterized by a broad scope of application good recoveries and sensitivity and low solvent consumption, coupled with good analytical quality control. The presence of marathon, DDE in the respective sample were further confirmed by HNMR (Joel, 400 MHZ) and IR (Bruker) Spectral studies.

GUPTA et al., Curr. World Environ., Vol. 7(1), 183-186 (2012)

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Table 1 Pesticide

Chemical Name

Molwt.

Trale Name

Chemical Class

ADI mg/ Kg/Day

α,β,γ,δ BHC DDT

1,2,3,4,5,6-

290.85

Organochlorine

0.008

Hexachlorocyclohexane 1,1-(2,2,2-trichloro ethylidene) bis [4chlorobenzene] Methyl 0,0-dimethye 0-4Parathion Nitrophenyl Phasphorothioate Malathion Diethyl (Dimethoxy Thiophas Phosphorylthio succolnate Dimethoate 0,0 dimethye Smethylcarbo mouylemethyl phosphoridithiote Ethion 0,0,0,1,01-tetraethyl, s-s1 methyloe bis (phosphorodithioate) Endsulfan 6,7,8,9,10,10hexachloro 1,5a,6,9,9ahexahydro 6,9-methano2,4,3 benzadioxathiepin 3-oxide Dieldrin 1,2,3,4,10.10Hexachloro 6,7 expoxy 1,4,-4a,5,6,7,8,8a, octahydro-1,4,5,8dimetanophthalene

354.41

HCH, Grammexane Anofex, Cesarex, Digmar, Gezarex Matafos, metacide,dalf, Gearphas Carbophos, meldison Mercaptothion

Organocholorine

0.02

Organophasphate

0.02

Organophasphate

0.02

263.21

330.36

229-28

Cygon400,Dem os, Dicap, rogor

Organophasphate

0.01

384.48

Acithion, Ethanox, Hylmox Hexasulfan, Afidan, Cyclodan Beosit

Organophasphate

.002

Organochlorine

.006

Dieldriti, Dieldrex, Octalox Panoram D-31

Organochlorine

406.96

380.9

Table 2: Pesticide residues, in water fruits mg/Kg. Sample

Apple Pomegranate Black grapes Green Grapes Banana Papaya Cheeku Coconut Lemon

α BHC β and γ dimethanoateδ δ BHC Methyl MalathionEndsuffan DDT BHC Parathion 0.02 0.01 -

0.05 0.01 0.03 -

0.01 0.02 0.01 0.03

0.02 -

-

2.46 1.70 2.37 3.05 1.03 4.19 4.34 3.25 5.66

0.10

0.02 -

Dieldrin

0.01 0.01

0.01 0.31

0.01

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HNMR and IR spectra of the standard pesticide was taken separately and compared with that of the sample containing those particular pesticides. The study including the following parameters: Fruit sample, place of origin, Methods used and Pesticides tested for Table 1 and concentrations found for each pesticides table 2. Where the No. of Pesticides1) αBHC 2) α and β BHC 3) Dimethanoate 4) Methyl Parathion 5) Malathion 6) Endosulphama 7) DDE 8) Dieldrin 9) Ethion 10) DDT

CONCLUSION The high levels of malathion is alarming. We have analyzed for only 9 pesticides where as the presence of many others can not be ignored. Out of necessity the field of residue analytical chemistry has emerged as a devoted specifically to the determination of sub microgram concentration levels of pesticides to confirm the tolerance established by law for pesticides in or on agricultural forage and food crops and animal products. The area associated with the nature, persistence and concentration level of pesticides residues on produce need to be critically examined by academic, industrial and government agencies to ensure man’s future well being. ACKNOWLEDGMENTS Authors are thankful to Dr. Rekha Lagarkha (Co-ordinator), Department of Chemistry Bundelkhand University, Jhansi for providing the necessary fulfill facilities.

REFERENCES

1.

2.

3.

4.

Agency for Toxicsubstance and Disease Registry (ATSDR). Toxicological profile for HCB. Atlanta, GA, USA: US department of Health and Human services, Public Health Service, A TSDR (2002). Agnihotri N.P Dewan RS Dixit A.K Residu of insecticides in food commodities in food commodities from Delhi. 1. Vegetables. Indian J. Entromal 36: 160-162 (1974). American Cancer Society. Cancer facts and figures 2003. Available at Bailey RE. Global Hexachlorobenzene emissions chemosphere, 43: 167-82 (2001):. Burns JE, Miller FM, Gomes E, Albert R: hexachlorobenzene exposure from contaminated DCPA in vegetables spraymen. Arch Environ Health 29: 192-4 (1974).

5.

6.

7.

8.

Currier MF, Mc claims CD, Barna-Lloyd G. Hexachlorobenzene blood levels and the health status of men in the manufacture of chlorinated solvents. J Toxicol Health 6: 36777 (1980). Deutscher RL, Cathro KJ. Organochlorine formation in magnesium electrowinning cells chemosphere 43: 147-55 (2001). FAO/WHO, joint FAO/WHO food standards programme. Codex maximum limits for pesticide residue. Vol. XIII. 2nd ed Romeltaly , (1986). Gullett BK, Touati A, Hays MD. PCDD/F, PCB. HxCBZ, and PM emission factors for fireplace and wood stove combustion in the San Francisco Bay Region. Environ Sci. technol 37: 1758-65 (2003).

Current World Environment

Vol. 7(1), 187-190 (2012)

A Culturing of Fungi for Phytase Production by Solid State from Different Sources JYOTSNA VIHNUDAS 1*, MALATHI JOJULA2 and M.A. SINGARACHARYA3 1

Department of Pharm. Biochemistry, Sri Shivani College of Pharmacy, Warangal (India). Department of Pharm. Microbiology, Sri Shivani College of Pharmacy, Warangal (India). 3 Department of Microbiology, Kakatiya University, Warangal (India).

2

(Received: June 03, 2012; Accepted: June 29, 2012) ABSTRACT Supplementation with phytase is an effective way to increase the availability of phosphorus in seed- based animal feed. Fifteen different types of themophilic fungi such as Aspergillus fumigatus, Curvalaria, Pencillium Sp, Mycrothecicum, Helimenthosporium, Fusaruim Throderna, Alternaria Spices were majorly found during our study they were classified based on the morphological characterization and staining methods This isolates were isolated from the compost moderf various localities. Among all isolates, Aspergillus sp wasfound to be the best isolate for the phytase production. Three different types of materials(rice bran, Poultry soil, Kudithi) were evaluated as growth substratefor phytase production by Sporotrichum thermophile. Of all the sources tested, rice bransupplemented with diluent containing (g/L); (NH4)2SO4; 5.0, KH2PO4; 1.0, Yeast extract; 2.0 gavemaximum production (4.16 U/mL/min) when 4% volume of the 250 mL conical flask was used after 96 hrs spore inoculation at 45°C using solid-state fermentation.

Key words: Phytase, Kali, Kudithi.

INTRODUCTION A phytase (myo-inositol hexakis phosphate phosphohydrolase) is any type of phosphatase enzyme that catalyzes the hydrolysis of phytic acid (myo-inositol hexakisphosphate) — an indigestible, organic form of phosphorus that is found in grains and oil seeds— and releases a usable form of inorganic phosphorus 1 . While phytases had been found to occur in animals, plants, fungi and bacteria, phytases had been most commonly detected and characterized from fungi 2. In modern age of biotechnology, enzymes have proved their market demand over other products of biotechnology with annual sales close to 2.0 billion dollars. Phytases (EC 3.1.3.8), phosphatases that catalyze the hydrolysis of phosphate moieties, have a big share in enzyme business due to its widespread application as a feed supplement3- 6. The phytases enhance the bioavailibility of minerals, protein and phosphorus in monogastric animals. They reduce the phosphorus pollution in areas of intensive livestock production 7, 8. The

thermostability of phytase suggests potential biotechnological applications in the pulp and paper industry as a biological agent to remove plant phyticacid. The enzymatic degradation of phytic acid will not produce toxic by-products, so it is environmental friendly 10. A large number of microbes including bacteria, yeast and filamentous fungi has been used for phytase production. Selection of particular microbe depends on the nature of substrate, environmental conditions and desired final product. Thermophilic fungi havecomplex or unusual nutritional requirements and well-known microbes to producephytase11-14. In view of increasingdemand for phytase it is essential to produce phytase in a cost-effective manner. Phytase required for commercial feed preparation must meet following specifications i.e., thermo stability and activity over wider pH range, which is only possible withthermophilic fungi. Poultry manure is a useful nutrient source supplies phytase and high available phosphorous corn diets on the solubility and plant uptake of P, Cu, and Zn in poultry manure and soils amended with

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manure.Therefore, the present study was conducted with the aim to isolate apotent strain of thermophilic fungi from local habitat and optimize after screening for theproduction of phytase. Aims and objectives 1. To isolates and characterize the fungal organism, which hydrolyses phytase enzyme in high amounts. 2. To estimate the amount of Phytase enzymeproduced from fungal microorganisms from open natural fermenters and from soil near poultry farms. 3. Optimization of the condition for the activity of the enzyme phytase. MATERIAL AND METHODS Source of samples Soil sample from Poultry farm waste, 2 Kali is a fermented waste water of rice and this is used by villagers to cook cereal food. These liquid feed of cattle are a good source of microbes,contributing to vitamins and enzymes in food. They contain a lot of bran – derived materials including phytase. Isolation of organisms Three different samples were used to isolate fungi which have the ability to produce phytase enzyme during the growth cycle. The poultry soil, kali and kudith samples were collected from Warangal and its surrounding areas. Samples were processed by serial dilution method 15. Soil samples of poultry farms were collected in sterile polythene bags. One gram of sample was suspended in 100 mL of sterilized distilled water and allowed to settle ove r n i g h t a t r o o m t e m p e ra t u r e. T h e s o i l suspension was further diluted up to 104-106 times. One millilitre of this dilute suspension was then transferred to ndividual Petri plates containing potato dextrose agar medium. The fungal cultures were further purified from bacterial contaminants by using 10 mg/L combination of penicillin and streptomycin (1:1 ratio) in the Petri plate medium. Two other samples Kudithi and Kali were collected in sterile bottles from different cattle sheds and from different houses of suburban locatlities of Warangal town.

Morphological appearance All the isolates of fungi were identified by microscopic examination 16,17,18 . Independent colonies of each identified isolate were picked up and transferred to potato dextrose agar (PDA) slants for culture maintenance. The cultures were stored in a refrigerator at 4°C for further studies. Inoculum The spores from 3-5 days old slant culture were wetted by adding 10 mL ofsterilized 0.005% Monoxal O.T (diacetyl ester of Sodium sulphosuccinic acid) to eachslant. The spores were scratched with sterilized inoculating needle and the tubes wereshaken gently to break the clumps of spores. sporesl suspension was used as aninoculum. Inoculum size was measured by measuring the density of spore(number of spore per unit volume) with Haemacytometer, Neubauer improved; precicdor HBG, Germany (Tiefe depth profondeur 0.10 mm and 0.0025mm2 area). Phytase assay Phytase activity was assayed after some modification of 12 and 13 methods using Sodium phytate as substrateand the inorganic phosphorus released was measured spectrophotometerically by usingthe Taussky-Schoor reagent. Half milliliter of Sodium phytate (0.00682M) was added to0.1 mL of MgSO4 (0.05M) and 0.1mL of Sodium acetate buffer (0.2M). Enzyme solution(0.1 mL) was added to above mixture and the mixture was incubated at 50°C for 30minutes. After incubation, 1.0 mL of 10% tricarboxylic acid (TCA) was added along with2.0 mL of distilled water. Mixed well and 5.0 mL of Taussky-Schoor reagent was added.TausskySchoor reagent was prepared when 10.0 g Ammonium molybdate was mixedwith 10.0 mL H2SO4 (10N) and further diluted with 70.0 mL of deionized water. Then 5.0g of ferrous sulphate heptahydrate (FeSO4.7H2O) was added and made the final volumeupto 100.0 mL. Absorbance was measured at 660 nm by using spectrophotometer andliberated inorganic phosphate was estimated after comparing the absorbance with known concentration of KH 2 PO 4 using same assay conditions instead of enzyme. One unit ofphytase activity is defined as “the amount of enzyme that liberates one µmol of inorganicphosphate at temperature (50°C) and pH (5)”.

VIHNUDAS et al., Curr. World Environ., Vol. 7(1), 187-190 (2012) Statistical analysis Duncan’s multiple range tests in the form of probability <p> valueswere used to find out the significant difference among replicates. Treatment effects werecompared after Snedecor & Cochrane (1980) using computer software Costat, 3.03Berkeley, CA 94701. RESULTS AND DISCUSSION Both Kudithi and Kali contained microbes which had ability of producing phytase. Fungi Seven strains of five different thermophilic fungi such as Aspergillus fumigatus,Humicola insolens, Rhizomucor miehei-I & II, Sporotrichum thermophile, Thermomyceslanuginosus-I & II were isolated from compost soil and were screened for phytaseproduction. Aspergillus fumigatus produced 0.04 U/mL/min of phytase while Humicolainsolens, Rhizomucor miehei-I & II, Sporotrichum thermophile, Thermomyces lanuginosus-I & II gave 0.22, 0.20, 0.76, 2.20, 0.20 and 0.53 U/mL/min respectively. Of the seventhermophilic fungal strains screened for phytase production, Sporotrichum thermophile wasfound to produce higher extracellular phytase when grown on solid state wheat bran (Table1). Chadha et al., (2004) isolated and screened out thermophilic fungi and found ninethermophilic strains having the potential of phytase production like Rhizomucor pusillus,Humicola grisea, Sporotrichum

189

thermophile, Humicola insolens, Thermomyceslanuginosus-I, Thermomyces lanuginosus-II, Rhizomucor miehei-I, Rhizomucor miehei-IIand Aspergillus fumigatus. Singh & Satyanarayana (2008) also investigated thatSporotrichum thermophile has the potential for enhanced production of phytase.The main product of a fermentation process often determines the choice of carbonsource, particularly if the product results from the direct dissimilation of it. It is commonpractice to use carbohydrates as carbon source in microbial fermentation processes. Themost widely CONCLUSIONS Phytase which is liberated during the growth cycleof microbes especially fungi and bacteria, thephytase enzyme play a vital role in improving the nourishment of plants which is a rich sourceof carbon source, the study was based on the background of Indianvillage feeds for animals which is rich source Of Proteins and carbohydrates this components are been utilized by the fungi when they grow in kali and kudhithi and release phytase enzyme. This phyatatic kali and kudhithi was been used as feed for animals but there is a complication in digestion of phyatses by animals this is liberated out as indigested produted in to environment. Execrates of animals can be used as manure in fields.

REFERENCES 1.

2.

3.

4.

Mullaney EJ, Daly CB, Ullah AH . “Advances in phytase research”. Adv Appl Microbiol 47: 157–199 (2000). doi: 10.1016/S00652164(00)47004-8. PMID 12876797. Mullaney EJ, Ullah AH. “The term phytase comprises several different classes of enzymes”. Biochem Biophys Res Commun ., 312(1): 179-184. doi:10.1016/ j.bbrc.2003.09.176. PMID 14630039 Becerra, M. and M.I.G. Siso. Yeast bgalactosidase in solid state fermentation. Enzyme Microb. Technol., 19: 39-44 (1996). Bogar, B., G. Szakacs, J.C. Linden, A. Pandey and R.P. Tengerdy. Optimization of phytaseproduction by solid substrate

5.

6.

7.

fermentation. J. Ind. Microbiol. Biotechnol., 30(3): 183-189 (2003). Chadha, B.S., H. Gulati, M. Minhas, H.S. Saini and N. Singh, Phytase production by thethermophilic fungus Rhizom Rhizomucor pusillus, World J. Microbiol. Biotechnol., 20: 105-109 (2004). Ciofalo, V., N. Barton, K. Kretz, J. Baird, M. Cook and D. Schanahan., Safely evaluation of aphytase, expressed in Schizosaccharomyces pombe, intended for use in animal feed. Regul. Toxicol. Pharm., 37(2): 266-292 (2003). Clark, W.D., K.E. Wohlt, R.L. Gilbreath and P.K. Zajar. Phytate phosphorus intake

190

8.

9.

10.

11.

12.

13.

14.

VIHNUDAS et al., Curr. World Environ., Vol. 7(1), 187-190 (2012) anddisappearance in the gastrointestinal tract of high producing dairy cows. J. Dair. Sci., 69: 3151-3155 (1958). Cooney, D.G. and R. Emerson. Thermophilic fungi: An account of their biology, activitiesand classification. W.H. Freeman & Co., San Francisco, Calif. (1964). Domsch, K.H., W. Gams and T.H. Anderson. Compendium of soil fungi. Academic press,New York, Toronto, San Francisco. (1980). Ebune, A., S. Al-Asheh and Z. Duvnjak. Production of phytase during solid statefermentation using Aspergillus ficuum NRRL 3135 in canola meal. Biores. Technol., 53: 7-12 (1995) Greiner, R. and U. Konietzny. Phytase for food application. Food Technol. Biotechnol., 44(2): 125-140 (2006). Harland, B.F. and J. Harland. Fermentative reduction of phytic acid in rye, wheat and wholewheat bread. Cereal Chem., 57(3): 226-229 (1980). Heinonen, J.K. and R.J. Lahti. A new and convenient colorimetric determination of inorganicorthophosphate and its application to the assay of inorganic pyrophosphatase. Anal Biochem, 113: 313-317 (1981). Hughes, M.N. and R.K. Poole. Metals and Microorganisms. Chapman and Hall,

15.

16.

17.

18.

London.Hughes, M.N. and R.K. Poole. 1991. Metal speciation and microbial growth - the hard and softfacts. J. Gen. Microbiol., 137: 725-734 (1989). Koneman, W., E. Allen and W.C. Washington. Diagnostic Microbiology, 3rd Ed, p. 608.Lynd, L.R., P.J. Weimer, Z.W. Van and I.S. Pretorius. 2002. Microbial cellulose utilization:fundamentals and biotechnology. Microbiol. Mol. Biol. Rev., 66: 506-577 (1991). McCoy, M. Enzymes emerge as big AG feed supplements. Chem. Eng. News, 4: 2930.Onion, A.H.S., D. Allosopp and O.W. Eggins. 1986. Smith Introduction to Industrial Mycology, 7thEd, Edward Arnold Publishers, London, 187-188 (1998). Pandey, A., G. Szakacs, C.R. Soccol, J.A. Rodriguez-Leon and V.T. Soccol. Production,purification and properties of microbial phytases. Bioresour. Technol., 77(3): 203-214.Saha, C. 2003. Hemicellulose bioconversion. Ind. Microbiol. Biotechnol, 30: 279-291 (2001). Singh, B. and T. Satyanarayana. Phytase production by thermophilic mold Sporotrichumthermophile in solid-state fermentation and its application in dephytinization of sesame oilcake. Appl. Biochem. Biotechnol., 133(3): 239-250 (2006).


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