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Current World Environment

Vol. 7(2), 191-200 (2012)

Assessment of Odor Annoying Impacts on Trade and Serving Centers Close to a Vegetable Oil Manufacturing Plant MOHAMMAD REZA MONAZZAM1*, M. AVISHAN2, M.ASGHARI1 and M. BOUBEHREJH2 1

Department of Occupational Hygiene, School of Public Health and Center for Air Pollution Research (CAPR), Institute for Environmental Research (IER), Tehran University of Medical Sciences, Tehran, Iran. 2 Air Pollution Bureau, Iran Department of the Environment, Tehran, Iran. (Received: July 12, 2012; Accepted: September 17, 2012) ABSTRACT

The environmental odor pollution emitted from different sources has undesirable impacts on communities’ health and welfare in a way that caused increasing public worry and complains around the world. Pars Vegetable Oil Processing Plant (PVOPP) is located near populated residential areas in Tehran; hence, many people are exposed to the plant process annoying odor daily. In order to assess the odor annoying impacts on its nearby business centers a social survey has been applied. In the field area 200 questionnaires were intended to be filled out but 180 of them have been completed by the respondents (90%). Almost 98% of the respondents have perceived the odor from the outdoor source in their working places which is known as the industry by 78% of them. Among the respondents 42% of them have defined the odor as intolerable. Considering that industry has been recognized as the most important external parameter which affect the quality of working environments, the impact of this industrial unit on decreasing the quality level of working conditions is more obvious. The duration of presence in the working place and record of service are related to disorders in working activity and emotion and thus confirm the odor pollution impacts on the employees’ efficiency.

Key words: Odor pollution, questionnaire, annoyance, Vegetable Oil Manufacturing.

INTRODUCTION The air around us contains aromatic compounds originated from citizens’ daily activity in residential, trade and industrial areas which create the modern societies. Daily exposure to odor pollution is a part of modern life1. Odor is generally defined as the feeling caused by chemical compounds which are called odorants while being perceived by stimulating the sensory receptors of smell2. Odor is a combination of one or more volatile chemical compound that humans perceive by the sense of olfaction 3 . According to the EPA definition odorous compounds are pollutants while annoying the human or affect his health or welfare4.

Researches show that environmental irritants like noise and odor can have considerable impacts on the physical and moral condition of the people and their quality of life5-6. If this exposure is long or intensive the unpleasantness would be converted to annoyance gradually. Annoyance is described as an unpleasant feeling about a defined factor or condition which adversely affects the individuals or groups9. The human perception of odor is the result of a set of physiological and mental reactions which identify the odor quality 7 . Hence, the compatibility of odor perception is widely personal among individuals which their reaction is different due to their age and health status8. The unpleasant impacts of odor emitted from different sources have


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increased the public complaints and worry all around the world, more people are sensitive to the issue and request for more control and more effective measures to decrease the odor emission by authorities9. Odorous compounds impress the health and welfare of communities11. Since World Health Organization (WHO) defines health as “a state of complete physical, mental and social wellbeing and not merely the absence of disease or infirmity”11, in recent years health and environmental organizations have paid more attention to the odor pollution issue because of its negative impacts on the neighborhoods. Researches about odor pollution effects on human health concluded that they could be categorized to physiological and mental impacts12. The most common odor-related symptoms are reported burning eyes, soar throat, nose irritation, headache, nausea, cough, nose congestion and short breath13-18. Mental effects are depression18,20, fatigue and sleepiness21-25 mood disturbance26-30 and also decrease in the individuals working efficiency31, 32. Environmental odor can impress the evaluation of indoor and outdoor air quality and works as a warning sign. Nowadays, public awareness about the association of indoor air quality (home and office) with their health have increased which could be due to more amount of time spent indoors, aging population, decreasing air conditioning to reduce the energy consumption, increased usage of chemical compound in working and living environment and also outdoor air pollution. Millions of Americans spend two thousand hours or more per year in closed spaces and so gradually become prone to ailments related to indoor pollutant exposure such as odorous materials33. Therefore, identifying the surrounding air combination is very significant which lead to various investigations implemented about odor pollution annoyance impact assessment on nearby residents and/or the employees working in odorous industries and facilities and odor related mental and physical health effects34. On the basis of the wide reviews, no investigation about odor annoyance effects on nonindustrial workers which work in areas affected by

odor has been done yet. So, it is the first time in Iran that the nuisance impact of emitted odor from an oil processing plant on the trade and service employees around has been implemented. MATERIAL AND METHODS This study has been done in a crowded area in southern part of Tehran. The current population of Tehran as the capital of Iran is 7,975,679[34]. In spite of the measures taken to organize the industries settlement out of the city’s area, there are still some old industries working. One of these active units is Pars Vegetable Oil Processing Plant (PVOPP) which has been selected as the odor source in the area. Figure 1 illustrates the plant location and study area. It should also be mentioned that the same level of impressibility has been determined for both trade and serving centers considering their approximately equal distribution. A questionnaire method has been applied to examine the odor annoyance for workers in the study area. The questionnaires were filled out in direct interview in summer 2011. In order to implement the research, 200 workers were selected stochastically in trade and serving area and were directly interviewed by trained questioners. While designing the questionnaire German VDI Guideline (VDI3883 -Part II) published in 1993 and researches about Community Response to Odorous Emissions in other countries have been considered35. It is necessary to mention that the guideline is used in various researches to study the community response to odor annoyance in neighborhoods. So, in this study it has been tried to design an appropriate questionnaire considering the necessary parameters for odor annoyance survey in non-industrial working environment around the odor source by keeping the general structure of the guideline recommended questionnaire or in some cases adding or changing the related questions. Questions could be categorized in four sections including a) personal characteristics (age, gender, type of job, length of working time, working place conditions, record of service,… ) b) environmental issues and personal health conditions ( environmental problems,


MONAZZAM et al., Curr. World Environ., Vol. 7(2), 191-200 (2012) personal health problems,… ) c) odor nuisance variables ( type of source, intensity, frequency, quality, level of disturbance and annoyance, hedonic tone, acceptability,… ) and the final part d) which is focused on individuals’ daily activity and emotion. The related scales for the variables would be presented in the result chapter comprehensively. In order to decrease the residents’ sensitivity to the odor source and also minimizing the error percentage in results, other environmental

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aspects of the region have been also scripted in the questionnaire. Data analysis has been done using SPSS (Version 18). RESULT Part 1: Social and Statistical variables Data Among 200 questionnaires predicted for the study area, 180 have been completed by the respondents; the response rate is 90%. According to the questionnaires 174 (96.7%) of the

Table 1: Socio-statistical Data N=180

Mean

Standard Deviation

Range

Age (year) Duration of presence at work (hour) Workspace area (m) Record of service ( year)

35.8 9.8 26 9.6

13 3 23 10.3

17-75 1-17 1-120 1-48

Table 2: Workers’ common health problems Health problem

Percentage

Irritation symptoms Not getting enough sleep Headache Breathing difficulties Difficulties falling asleep Cough Waking up during the night Stomach disorders Difficulties falling asleep after Waking up

21 21 19 14 17 14 12 9 8

Table 4: Odor hedonic tone perceived by workers Hedonic tone Very pleasant Pleasant Moderately pleasant Mildly pleasant Neutral odor / No odor Mildly unpleasant Moderately unpleasant Unpleasant Offensive

Percent 3

14 5 36 42

Table 3: Odor intensity perceived by workers Odor intensity Unbearably strong Very strong Strong Distinct Weak Very weak Not perceptible

Percentage 14 9 27 23 19 6 2

respondents were male with the mean age of 35.8 (with the range of 17 to 75 years). Considering the very few number of women participated in answering the questionnaires the related data have been removed. 64% of respondents were working in trade and 36% in serving centers. The mean area of studied work places is about 26 m 2 and the average duration of presence at work is calculated to 9.8 ± 2.9 hr/day. Data related to socio-statistical variables are summarized in Table1. Data related to environmental issues


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showed that almost 87.7% of participants have chosen odor as the most considerable problem in their working environment while 42.2% have mentioned air pollution and 55.5% have implied noise pollution. Part 2: Personal Health Status Data In this part data illustrated that eye irritation (21%) and not getting enough sleep (21%) were equally more common in respondents comparing

with other health problems. Data related to this part are briefed in Table2. Generally 69% of the respondents had at least on of the problems mentioned in the above table. 69% showed no allergy symptoms. 39% of the allergic people had to take medicine. Only 19% of the participants were regular smokers. Part 3: Odor characteristics

Table 5: Relationship between odor-related variables with odor source and mutual comparison of variables Test Variable

Odor source α=.05) (α

Post Hoc (α α =.033)

Odor intensity

.010

negative impacts of activity and emotion

.001

Unpleasantness Odor disturbance

.032 >.001 *

Annoyance

.004

Vehicle < Industry P=.006 Waste water < Industry P<.001 Vehicle < Industry P=.009 Waste water < Industry P<.001 Waste water < Industry P=.001

Table 6: Relationship between odor-related variables with odor quality and Mutual comparison of variables Test Variable

Odor source α=.05) (α

Post Hoc (α α =.033)

Odor intensity negative impacts on activity and emotion

.072 .001

Unpleasantness

.017

Odor disturbance

.001 >

Annoyance

.001

Waste water < Burning P<.001 Waste water < Sulfur P=.001 Burning < Sulfur P=.006 Burning < Sulfur P<.013 Waste water < Sulfur P<.001 Waste water < Burning P=.013 Waste water < Sulfur P<.001


MONAZZAM et al., Curr. World Environ., Vol. 7(2), 191-200 (2012) Sensitivity to odor Data resulted from this item showed that 98% of the individuals have perceived the odor from the outdoor source in their working places which is known as the industry (Vegetable Oil Manufacturing plant) by 78% of them. Figures 1 and 2 illustrate the odor source and quality. Sulfuric, burning, sweet and wastewater are the options for determining odor quality.

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6 categories from 1 for once or less monthly to 6 for frequently in a day have been offered for this variable, the last item frequently in a day has been chosen by 91% of the respondents. Odor intensity 7 classes from 0 for not perceptible to 6 for unbearably strong have been chosen for determining the intensity of odor, 23% of the workers have mentioned it as distinct and totally 73% have

Odor frequency

Fig. 1: Map of Pars Vegetable Oil Processing Plant Location and Study Area

Fig. 2: Proportion of odor sources

Fig. 3: Proportion of odor quality


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chosen distinct to unbearable options. Results are shown in Table3.

This variable has been divided to 9 classes from -4 for offensive to +4 for very pleasant.

Hedonic tone

Annoyance

Fig. 4: Odor annoyance perceived by workers

Fig. 5: Odor disturbance perceived by workers

Fig. 6: Odor negative impact on workersâ&#x20AC;&#x2122; activity and emotion


MONAZZAM et al., Curr. World Environ., Vol. 7(2), 191-200 (2012) 7 scales have been offered in the questionnaire for this variable from 0 for no annoyance to 6 for maximum annoyance, 41% of the respondents have chosen the maximum annoyance item. Nearly 66.6% of the people have answered 4 to 6. The sample annoyance mean has been 4.64 ( ± 1.58). The confidence interval for odor annoyance level which has been calculated by non-parametric percentile bootstrapping was 4.6 and 4.2. Figure 3 illustrates the related results. Disturbance In order to determine the disturbance level it has been divided to 11 categories from 0 for no disturbance to 10 for maximum disturbance. 37.2% of the respondents have selected number 10 which means maximum disturbance. The mean odor disturbance degree was 7.4 ( ± 4.6). The confidence interval for odor disturbance has been calculated by non-parametric percentile bootstrapping which was 7.0 and 7.8. Figure 4 shows the related results. Odor acceptability 2 scales have been defined in this part (0 for acceptable and 1 for unacceptable). The results show that 82% of the respondents have known the odor unacceptable, 33% of which have complained to the related authorities. The statistical relationship between the respondents’ adaptability to odor and complaining to the local governors has been calculated by Fisher’s Exact 2-sided Test which was significant (p<0.002). Part 4: Odor negative impacts on workers’ activity and emotion

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disturbance and annoyance but no relationship were found with odor intensity. Spearman correlation coefficients between odor perception intensity, negative impacts on activity and emotion, hedonic tone, disturbance and annoyance show significant relationship among them (p<0.001). The coefficient values are +0.40 to +0.83. The effect of odor source on its intensity, negative impacts on activity and emotion, unpleasantness, disturbance and annoyance have been studied by Kruskal-Wallis test at first, then different sources have been compared by repeating Mann-Whitney U test and applying Bonferroni correction in order to adjust type 1 error while comparing multiple variables. According to the results, this industrial source odor and its unpleasantness are significantly more than other sources which were defined in this study. The role of odor type on the related properties including negative impacts on activity and emotion, unpleasantness, disturbance and annoyance have been also investigated by KruskalWallis test at first, then different sources have been compared by repeating Mann-Whitney U test and applying Bonferroni correction in order to adjust type 1 error while comparing multiple variables. Odor intensity is not significantly different in defined odor types but sulfur type is more unpleasant, annoying and disturbing than others. DISCUSSION

Results related to this topic showed that 10% of the respondents have always felt the odor negative effects on their activity and emotion. Figure 5 illustrates the result of this section. There is a significant relationship between the duration of time spent at work with the evidences these effects. (Spearman r=+0.26 p<0.001). The relationship between record of service and showing these impacts is significant additionally. (Spearman r= +0.34 p< 0.001). Record of service has also significant relationship with odor

The main objective of this research has been assessment of industrial source odor related parameters on non-industrial workers in the region. In many countries investigations about odor pollution have been considered and the impacts of this environmental problem on nearby residents or the employees working in the place which is known as odor source have been studied. Unfortunately there is no research about odor related effects on other workers close by. This group of people is not exposed to odor as long as near residents and also


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is not intensely in contact with odorous materials like industrial workers, but the result of this study shows that odor pollution is unbearable for 82% of the respondents. Considering that industry has been recognized as the most important external parameter which affect the quality of working environments, the impact of this plant on decreasing the quality level of working conditions is more obvious.

In this research there is an adverse relationship between age increase with annoyance, the level of which is less in older workers than younger ones. This conclusion is confirmed by the results from Konstantinidis et al (2006), Larsson et al (2009) ,Pierre M. Cavalini and RAJESH KUMAR SINGH researches38- 41.

The duration of presence in the working place and record of service are related to disorders in working activity and emotion and thus confirm the odor pollution impacts on the employees’ efficiency. The results achieved by Ludvigson et al. (1989) and Wilkinson (2002) have also mentioned this.

On the basis of results of this study, more comprehensive investigations about odor pollution management in different fields is recommended. Moreover, effective measures to decrease and control the odor related impacts and providing the citizens’ health is emphasized. It should also be mentioned that compliance with the regulations related to industrial positioning and keeping the possible maximum distance from residential area are effective ways of reducing air pollution such as odor and increasing the residents’ quality of life.

According to Winneke and Steinheider in 1993 38 and also Thuerauf et al. in 2009 39 gender affects the intensity of odor perception and females feel more level of annoyance. In this study, also average values women have given to annoyance and disturbance levels are more than men (Although due to the insufficient number of women the test is not strong enough).

Considering the lack of comprehensive management systems to decrease the odor pollution and also absence of necessary related regulations in Iran, it is expected that the results of such researches would be an effective factor in making the authorities more sensitive and a motivation to develop comprehensive studies about odor pollution management plan.

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Current World Environment

Vol. 7(2), 201-206 (2012)

Determination of Cadmium (II) Ions in Environmental Samples : A Potentiometric Sensor MOHAMMAD KARIMI, FOROUZAN ABOUFAZELI, HAMID REZA LOTFI ZADEH ZHAD, OMID SADEGHI and EZZATOLLAH NAJAFI1 Department of Chemistry, Shahr-e-Rey Branch, Islamic Azad University, P. O. Box 18735-334, Tehran, Iran. (Received: July 12, 2012; Accepted: September 17, 2012) ABSTRACT A sensor electrode was modified by multi-walled carbon nanotubes functionalized by dithizone. The electrode was used for determination of trace amounts of cadmium (II) ions. The electrode composition was 67% graphite powder, paraffin 23%, 10% modified MWCNTs (W/W). The linear range for lead (II) was 1.8×10-7 to 1.0×10-4 mol L”1 and the limit of detection was obtained 1.0×10-7 mol L”1. The lifetime of the electrode was 12 weeks and a fast response time was observed. The electrode was used for determination of trace amounts of Cd(II) ions in standard reference materials of water and soil.

Key words: Sensor, Cadmium; Modified MWCNTs, Potentiometry, dithizone.

INTRODUCTION Cadmium is a trace heavy metal of great importance in environmental protection since it is a highly toxic element. 1 Determination of cadmium in environment samples is so important as this element exist in environment samples as a contaminant originating from industrial or urban waste pollution. As a result of high toxicity even at low concentrations, and various matrix interferences in real samples, developing an accurate, precise and selective method for cadmium determination is necessary. Different instrumental methods such as flame atomic absorption spectrometry (FAAS),2 graphite furnace atomic absorption spectrometry (GFAAS), 3 inductively coupled plasma atomic emission spectrometric (ICP-AES), 4 and electrochemical methods5 have been used for cadmium determination. Among these methods, potentiometric methods using ion sensors are common due to their accuracy, high rate, low cost and also being non-destructive6. Potentiometric carbon paste electrodes, in comparison to polymeric

membrane electrodes, posses very attractive properties such as ease of preparation, renewable surface, stability of their response, low ohmic resistance and no need of internal solution7. In this technique, a chemical modifier is introduced to carbon paste electrode to increase the methods sensitivity8. In carbon paste methods, carbon nano-tubes have attract lots of attention as a modifier due to having high electrical conductivity, high mechanical and ther mal stability9. These nano-tubes can be easily modified with a ligand in order to change their selectivity toward a specific ion. In this work, multi-walled carbon nanotubes were functionalized by dithizone. The material was characterized by FT-IR, SEM and elemental analysis. A carbon paste sensor was modified by this material and used for determination cadmium content in environmental samples. The effective parameters on response of the electrode were investigated and good selectivity toward cadmium ion was observed. This electrode can be used as fast simple method for determination of


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cadmium content in environmental samples with low concentrations.

a Bruker IFS-66 FT-IR Spectrophotometer. The SEM micrograph was recorded by a Vega-TeScan scanning electron microscope.

MATERIALS AND METHODS Regents and solutions All reagents were of analytical grade and used without any further purification. Paraffin oil and Cadmium nitrate were purchased from SigmaAldrich Company. Carboxyl modified multiwalled carbon nanotube (COOH-MWCNT) was purchased from Neutrino Company (Tehran-Iran). Multiwalled carbon nanotubes were 30 µm length and 5-10 nm in diameter. The other chemicals such as Oxalyl chloride and dithizone were from Merck Company. All solutions were made using deionized water. The deionized water was provided from a Milli-Q (Millipore, Bedford, MA, USA) purification system. Preparation of dithizone functionalized multiwalled carbon nanotube For synthesis of dithizone functionalized multiwalled carbon nanotube, 1.0 g of COOHMWCNT was suspended in 50 mL of dried CH2Cl2 under nitrogen atmosphere. Then 5 mL of oxalyl chloride was slowly added to mixture from a dropping funnel. After stirring for 24 h, CH2Cl2 was removed under reduced pressure, and the residue was suspended again in 50 mL of dried methanol. Then 5 mL triethylamine and excess amount of dithizone (2 g) were added to reaction mixture. After refluxing the mixture for 24 h, methanol was removed under reduced pressure and the sorbent was dried at 80 °C under vacuum. The formation of dithizone functionalized multiwalled carbon nanotube was confirmed by IR spectroscopy, elemental analysis and SEM micrograph. A schematic diagram of this synthesis is represented in Fig. 1. Apparatus The reference electrode was a glass cell, consisted of an R684 model Analion Ag/AgCl double junction. A Corning ion analyzer 250pH/ mV meter was used for the potential measurements. The pH meter was a digital WTW Metrohm 827 Ion analyzer (Switzerland) equipped with a combined glass-calomel electrode. The pH adjustments were made at 25±1°C. The elemental analyses (CHNS) were performed on a Thermo Finnigan Flash-2000 microanalyzer (Italy). IR spectra were recorded on

Preparation of modified carbon paste electrode By thoroughly mixing an accurate of amount of graphite 67% graphite powder, paraffin 23%, 10% modified MWCNTs (W/W) the carbon paste electrode was prepared. The electrode body was fabricated from a glass tube of i.d. 5 mm and a height of 3 cm. To avoid possible air gaps, the paste was packed carefully into the tube tip, often enhancing the electrode resistance. A copper wire was inserted into the opposite end to establish electrical contact. The external electrode surface was smoothed on a soft paper. A new surface was produced by scraping out the old surface and replacing the carbon paste. Electrode conditioning and Emf measurements The electrode surfaces were conditioned in a solution of 1.0×10"4 mol L-1 Cd(NO3)2 and 1.0×10"3 mol L-1 NaNO3 for 24 hours. The electrodes were rinsed by deionized and polished before potentiometric measurements. In all solutions the potential was measured versus Ag, AgCl(s) reference electrode. The electrochemical cell can be represented as follows: Ag, AgCl (s), KCl (3 mol L-1) || analyte solution | carbon paste electrode Sample preparation The soil standard reference material was digested in an 8 mL mixture of 5% aqua regia with the assistance of a microwave digestion system. Digestion was carried out for 2 min at 250 W, 2 min at 0 W, 6 min at 250 W, 5 min at 400 W and 8 min at 550 W, and the mixture was then vented for 8 min and the residue from this digestion was then diluted with deionized water 10. RESULTS AND DISCUSSION Dithizone functionalized multiwalled carbon nanotube characterization The reaction of chlorine group in acyl chloride with amine group in dithizone group leads


KARIMI et al., Curr. World Environ., Vol. 7(2), 201-206 (2012) to formation of this composite. A schematic diagram of this synthesis is represented in Fig. 1. The formation of dithizone functionalized multiwalled carbon nanotube was confirmed by IR spectroscopy, elemental analysis and SEM micrograph. IR spectrum of this composite is as follow; IR (KBr, cm -1): 3400 (NH), 3017 (CH,

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aromatic), 2964 (CH, aliphatic), 1563 (C=C, aromatic), 1318 (C=S), 1237 (N=N) and 890 (MWCNT). In order to investigate the amount of grafted dithizone, elemental analysis was performed on this composite. According to elemental analysis results (%C=18.12, %H=1.81, %N=5.27, %S= 2.99), the dithizone concentration

Table 1: Optimization of the electrode composition Electro de No.

1 2 3 4 5 6 7 8

Graphite powder (%)

Paraffin (%)

Modified MWCNTs (%)

Slope (mV)

75 72 70 68 66 64 65 67

25 25 25 25 25 25 25 23

0 3 5 7 9 11 10 10

15.3±6.4 22.7±2.8 25.1±2.4 26.3±2.1 27.9±1.7 27.7±1.8 28.9±1.5 29.4±1.3

Table 2: Matched potential selectivity coefficient for interfering cations interfering ions (X) Na + K+ Cs+ Ca2+ Mg2+ Pb2+ Ni2+ Cu2+ Cr3+ Fe3+ Ag+ Zn2+

k MPM Hg,X 3.5×10-4 5.8×10-4 4.3×10-4 6.8×10-4 2.5×10-4 5.3×10-3 4.6×10-3 5.7×10-3 2.4×10-3 6.8×10-3 2.5×10-3 3.6×10-3

R2

Linear range (mol L-1)

5.0×10-5 7.5×10-6 1.0×10-6 5.5×10-7 6.5×10-7 2.7×10-7 1.8×10-7

to 5.0×10-2 to 1.0×10-3 to 3.5×10-4 to 1.0×10-4 to 1.0×10-4 to 1.0×10-4 to 1.0×10-4

0.932 0.941 0.952 0.961 0.966 0.973 0.983

on the surface of this composite is approximately 0.94 mmol g-1. Finally, in order to investigate the morphology and size of this composite, SEM micrograph was performed on this modified MWCNT. According to the SEM micrograph, the nano-structure of MWCNT remained unchanged after functionalization and the multiwalled carbon nanotubes have approximately 20 nm diameter (Fig. 2). Electrode composition The electrode composition is the most important factor in the responses and selectivity of the electrode. Different amounts of graphite powder, paraffin oil and modified MWCNTs were thoroughly mixed and the responses are listed in Table 1. In the first study no modifier was added to the electrode

Table 3: Recovery of determination of Cd(II) ions in certified reference materials Sample

NIST 1640 (Drinking water) SRM 2709 (San Joaquin Soil)

Unit

µg L-1 mg kg-1

Concentration

Recovery

Certified

Found

(%)

22.79 0.371

22.27 0.35

97.7 94.3


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and only graphite powder, paraffin oil were used (electrode no. 1). In the next electrodes different amounts of modified MWCNTs were added to the electrode (electrode no. 2-7). It was observed that the electrode performance can improve by adding modified MWCNTs. This should be result of two factors: 1) improving the conductivity of the electrode which is the result of high conductivity of MWCNTs; 2) complexation of cadmium ion with dithizone which increases the analyte concentration on the surface of the electrode. The response of the electrode was increased with adding modified MWCNTs up to 10% (electrode no. 7) and in higher

values the Nernstian slope was decreased (electrode no. 6). By changing the composition ratio to 67% graphite powder, paraffin 23%, 10% modified MWCNTs in electrode no. 8 the best results were ontained. A Nerstian solpe of 29.4 mV in a linear range of 1.8×10-7 to 1.0×10-4 mol L-1 was obtained. The standard deviation for ten replicates was 1.3 mV Calibration curve Quantitative determination of cadmium (II) ions was done by a calibration curve in the linear range of 1.8×10-7 to 1.0×10-4 mol L-1 versus Emf

Fig. 1: A schematic model for modification of MWCNTs by dithizone measurements. The calibration curve is shown in Fig. 3. The detection limit of the electrode was calculated by extrapolating the linear parts of the ion selective calibration curve 11,12. The limit of detection of the electrode was 1.0×10-7 mol L-1.

Fig. 2: SEM micrograph of modified MWCNTs

Influences of pH The effect of pH of the test solution on the sensor potential was investigated by following the potential variation of the sensor over the pH range of 2.0 to 9.0. The pH of a sample solution of 1×10-5 mol L -1 of cadmium (II) ion was adjusted by introducing small drops of hydrochloric acid solution (0.10 mol L-1) and/or sodium hydroxide solution (0.10 mol L-1). The result of this study is shown in Fig. 4. The results show that the potentials of the sensor remain constant from pH of 3.0 to 7.0. Under


KARIMI et al., Curr. World Environ., Vol. 7(2), 201-206 (2012) more acidic conditions, the ligand may be protonated and thereby lose its capacity to form a complex with the metal ions, whereas for the higher pH values , the hydroxyl ions in the solution react with Cd(II) to make Cd(OH)2. Study of Response time The average static response time was defined as the required time for the sensors to reach a potential of 90% of the final equilibrium values, after successive immersions in a series of solutions, each having a 10-fold concentration difference11,12. To investigate this parameter, The Cd(II) concentration was changed in the liner range and the results were studied. The results showed that the response time for the proposed electrode is 37 seconds.

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Influence of interference ions The selectivity behavior is obviously one of the important characteristics of membrane sensors in which the possibility of reliable measurement of the target sample is determined. Matched potential method (MPM) is the recommended method for studying Influence of interferences ions in ion selective electrodes by IUPAC13. The method is base on measuring the specific activity of the primary ion which is added to a reference solution. In this study the interfering ions were successively added to an identical reference solution with concentration of 1.0Ă&#x2014;10-6 mol L-1, until the measured potential matched to obtained value before adding the primary ions. Then matched potential selectivity coefficient,

k MPM Pb,X

is

calculated from the resulting primary ion to the

Fig. 3: The calibration curve for Cd (II) ion

Fig. 4: Influence of pH on electrode response to Cd(II)


KARIMI et al., Curr. World Environ., Vol. 7(2), 201-206 (2012)

206

a

Hg MPM interfering ion activity ratio, k Pb,X = Î&#x201D; a .14 The x

interference of Na+, K+, Cs+, Ca2+, Mg2+, Pb2+, Ni2+, Cu2+, Cr3+, Fe3+, Ag+ and Zn2+ was investigated and showed that they have no significant effect on the response to Cd 2+ . The

k MPM Pb,X

values for the

interferences are shown in Table 2. The electrode showed a good selectivity toward Cadmium (II) ions.

Different type of standard reference materials (water and soil) was used for validation of this method. The samples were digested by mentioned method and the Cd(II) contents were analysed by this method. As it can be seen in Table 3, the results have good compatibility with certified ones and this method can be consider as an accurate and reliable method for cadmium determination in environmental samples. CONCLUSION

Lifetime The lifetime of an electrode is the period of time that the electrode shows no changes in the efficiency of the measurements. The electrode was calibrated periodically with standard cadmium solutions. The next time the electrode was calibrated in the next week. It was observed that within 12 weeks no changes in the electrode response occur. After 12 weeks the sole was changed and linger range became more limited. Method validation

A paste electrode was developed for determination of cadmium ions. . The electrode composition was 67% graphite powder, paraffin 23%, 10% modified MWCNTs (W/W). Effects of electrode composition, and pH on the electrode response were studied. The electrode has a long lifetime and a response time. A good selectivity to cadmium ion was observed which makes the electrode a good candidate for determination of cadmium content in environmental samples. Method validation was done by analysis of standard reference materials with a matrix of water and soil.

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Bowen H. J. M., Environmental chemistry of the elements, Academic Press, London, (1979). Xiang G., Wen S., Wu X., Jiang X., He L. and Liu Y., Food Chem., 132: 532 (2012). MaranhĂŁo T. A., Martendal E., Borges D. L. G., Carasek E., Welz B. and Curtius A. J., Spectrochim. Acta B, 62: 1019 (2007). Boevski I., Daskalova N. and Havezov I., Spectrochim. Acta B, 55: 1643 (2000). Wu K., Hu S., Fei J. and Bai W., Anal. Chim. Acta, 489: 215 (2003). Khan A. A. and Paquiza L., Desalination, 272: 278 (2011). Zhang T., Chai Y., Yuan R. and Guo J., Anal. Methods, 4: 454 (2012). Mashhadizadeh M. H., Khani H., Foroumadi

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A. and Sagharichi P., Anal. Chim. Acta, 665: 208 (2010). Faridbod F., Ganjali M.R., Larijani B. and Norouzi P., Electrochim. Acta, 55: 234 (2009). Sayar O., Lotfi Zadeh Zhad H.R., Sadeghi O., Amani V., Najafi E., Tavassoli N., Biol. Trace Elem. Res. DOI: 10.1007/s12011-012-94679 Gupta V. K., Singh A. K. and Gupta B., Anal. Chim. Acta, 575: 198 (2006). Ganjali M. R., Norouzi P., Faridbod F., Yousefi M., Naji L., Salavati-Niasari M., Sensor Actuat. B-Chem., 120: 494 (2007). Buck P. R. and Lindner E., Pure Appl. Chem., 66: 2527 (1994). Umezawa Y., Umezawa K., Hamada N., Aoki H., Nakanishi J. U. N., Sato M., Ping Xiao K. and Nishimura Y., Pure Appl. Chem., 48: 127 (1976).


Current World Environment

Vol. 7(2), 207-212 (2012)

Effects of Biodiesel and Engine Load on Some Emission Characteristics of a Direct Injection Diesel Engine ALIREZA SHIRNESHAN1*, MORTEZA ALMASSI2, BARAT GHOBADIAN3, ALI MOHAMMAD BORGHEI1 and GHOLAM HASSAN NAJAFI3 1

Department of Agricultural Machinery Engineering, Science and Research Branch, Islamic Azad University, P.O.Box 14515-755, Tehran, Iran. 2 Department of Agricultural Mechanization, Science and Research Branch, Islamic Azad University, P.O.Box 14515-755, Tehran, Iran. 3 Department of Mechanics of Agricultural Machinery, Tarbiat Modares University, P.O.Box, 14115-111,Tehran, Iran. (Received: July 12, 2012; Accepted: September 17, 2012) ABSTRACT

In this research, experiments were conducted on a 4-cylinder direct-injection diesel engine using biodiesel as an alternative fuel and their blends to investigate the emission characteristics of the engine under four engine loads (25%, 40%, 65% and 80%) at an engine speed of 1800 rev/min. A test was applied in which an engine was fueled with diesel and four different blends of diesel/ biodiesel (B20, B40, B60 and B80) made from waste frying oil and the results were analyzed. The use of biodiesel resulted in lower emissions of hydrocarbon (HC) and CO and increased emissions of CO2 and NOx. This study showed that the exhaust emissions of diesel/biodiesel blends were lower than those of the diesel fuels.

Key words: Emission, Biodiesel, Waste fraying oil, Diesel.

INTRODUCTION In recent years, the demands for energy have grown very quickly due to the rapid development of certain growing economies, especially in Asia and the Middle East. Biofuels such as alcohols and biodiesel have been proposed as alternatives for diesel engines1,2,3. Especially, the environmental issues concerned with the exhaust gases emission by the usage of fossil fuels also encourage the usage of biodiesel, which has proved to be ecofriendly far more than fossil fuels. In particular, biodiesel has received wide attention as a replacement for diesel fuel because it is biodegradable, nontoxic and can significantly reduce toxic emissions and overall life cycle emission of CO2 from the engine when burned as a fuel4,5. Biodiesel is known as a carbon neutral fuel because the carbon present in the exhaust was

originally fixed from the atmosphere6-7. This supply deficit will have serious implications for many nonoil producing countries which are dependent on oil imports. Furthermore, the extensive use of fossil fuels has increased the production of greenhouse gases, especially carbon dioxide (CO 2 ), thus exacerbating the greenhouse effect. The potential to both reduce fossil fuel reliance and the release of CO2 to the atmosphere. Biodiesel from waste cooking oil is a more economical source of the fuel. Kulkarni and Dalai8 concluded that the engine performance of biodiesel obtained from waste frying oil is better than that of diesel fuel while the emissions produced by the use of biodiesel are less than those using diesel fuels except that there is an increase in NOx. Lapuerta et al., 9 tested two different biodiesel fuels obtained from waste cooking oils with different previous uses on diesel particulate


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emissions. They found no important differences in emissions between the two tested biodiesel fuels. Based on exhaustive engine tests, it can be concluded that bio-diesel can be adopted as an alternative fuel for existing conventional diesel engines without requiring any major modifications in the mechanical system of the engines. Bio-diesel emissions in a conventional diesel engine contain substantially less unburned HC, CO, sulfates, polycyclic aromatic hydrocarbons, nitrated polycyclic aromatic hydrocarbons and PM than conventional diesel emissions 10-11 . The NOx emissions from bio-diesel blends of various origins are slightly lower than those of conventional diesel, and the difference is greater for blends with higher percentages of bio-diesel12. Other researchers have observed the same behavior for all vegetable oil blends of various origins13-15. Various studies have shown that biodiesel made from waste cooking oil can be used in different types of diesel engines with no loss of efficiency16 and significant reductions in PM emissions17-21, Co emissions17,20 and total hydrocarbon (THC) emissions20-22 when compared with emissions from conventional fossil diesel fuel. The performance and smoke results obtained from an engine used for generating electricity, when fueled with biodiesels of waste cooking oil origin, showed that the smoke reduction was about 60% for B100 and approximately 25% for B20 12. Dorado et al.,23 used waste olive oil in a four-stroke, threecylinder, and 2.5 L direct injection engine with a power rating of 34 kW through an eight mode test. They achieved 58.9% reduction in CO, 8.6% reduction in CO 2 and 57.7% reduction in SO 2 emissions. On the other hand, increases of 32 and 8.5% in the NOx emissions and specific fuel consumption were observed in the B100 and B20 mixtures, respectively. Murillo et al., (2007)24 tested a four-stroke diesel outboard engine running on conventional diesel, conventional diesel blended with certain amounts of waste cooking oil biodiesel (10, 30 and 50%), and pure bio-diesel and proved that the bio-diesel blends are environmentally friendly alternatives to conventional diesel. They found some reduction in power of approximately 5% with B10 and B30, and 8% with B50 and B100 with respect to the power obtained from conventional diesel.

The biodiesel from waste cooking oil was tested by Meng et al.,24-25 on an unmodified diesel engine, and the results showed that under all conditions, the dynamical performance remained normal. Moreover, B20 and B50 blend fuels created unsatisfactory emissions, while the B20 blend fuel reduced PM, HC and CO emissions significantly. In another study, wasted cooking oil from restaurants was used to produce neat biodiesel through transesterification, and this converted biodiesel was then used to prepare biodiesel/diesel blends. The authors of the study concluded that B20 and B50 are the optimum fuel blends in terms of emissions26. In this research, the performance of waste frying oil methyl ester blended with diesel fuel in ratios of 20% (B20), 40% (B40), 60% (B60) and 80% (B80) was investigated and compared with that of regular diesel in terms of emissions in diesel engine under four engine loads at an engine speed of 1800 rev/min. MATERIAL AND METHODS The experiments were conducted on a four cylinders, four-stroke, turbocharged direct injection diesel engine. The engine specifications are given in Table 1. The test engine was coupled to a hydraulic dynamometer providing a maximum engine power of 110 KW with a Âą0.1 KW of uncertainty to control engine speed and load. The test engine was operated at different torques when different fuels were tested. The load on the dynamometer was measured by using a strain gauge load sensor that was calibrated by using standard weights just before the experiments. An inductive pickup speed sensor was used to measure the speed of the engine, and it was also calibrated by an optical tachometer. An AVL DICOM4000 gas analyzer was used to measure CO, CO2, NOx and HC emissions. In the experiments, diesel fuel no. 2 and four diesel fuel/biodiesel blends were tested. Waste frying oil methyl ester was blended with diesel fuel in 0%, 20%, 40%, 60% and 80% proportions by volume. The blends were prepared just before the experiments. In the tests, wasted frying oil was supplied from Modares university biodiesel institute.


SHIRNESHAN et al., Curr. World Environ., Vol. 7(2), 207-212 (2012) The specifications of the waste frying oil methyl ester are shown in Table 2. All fuels were tested at 1800 rpm and four engine partial loads (25%, 40%, 65% and 80%). The general testing procedure can be summarized as follows. The engine was run with the diesel fuel. After completion of standard warm-up duration, the engine speed was increased to 3000 rpm. The tests and data collection were performed at four different engine loads. The engine was kept running to flush out the diesel/biodiesel blend from the fuel lines, injection pump and the injectors for a while before shutting down. RESULTS Experiments were performed at the rated torque speed of 1800 rev/min, and at 25%, 40%, 65% and 80% engine loads. At each engine load, experiments were carried out for diesel and each blended fuel. In this paper, the effects of engine load and biodiesel on emissions included HC, CO, CO2 and NOx were investigated. As shown in Fig. 1, for Diesel, the HC emission decreases with increase of engine load, due to the increase in combustion temperature associated with higher engine load. For biodiesel blended fuel, the HC emission is lower than that of diesel and decreases with increase of biodiesel in the fuel. However, for the biodiesel blended fuel, the HC emission, instead of decreasing straightly with engine load, has a peak value at the 40% engine load. The reduced HC emission with

biodiesel blended diesel can be accounted for by several reasons as stated in Lapuerta et al. (2008)[8]. However, the lower volatility of biodiesel compared with diesel contributes to the larger difference in HC emission at low engine loads. The maximum concentrations of HC are 35 ppm, 29 ppm, 27 ppm, 26 ppm and 25 ppm, respectively, for diesel, B20, B40, B60, B80, indicating that the maximum HC emission declines with the addition of biodiesel. The characteristics of CO emission are shown in Fig. 2. For each fuel, there is a decrease of Co emission on increase of the engine load. The peak concentrations at the 25% engine load are 0.04%, 0.037%, 0.036%, 0.035% and 0.035%, respectively, for diesel, B20, B40, B60, B80. The higher combustion temperature at higher engine load contributes to the general decreasing trend. With the addition of biodiesel, CO emission also decreases. It is possible that the oxygen contained in the fuel enhances complete combustion in the cylinder and reduces CO emission 27-29 . Fig.3 compares the CO2 emissions of various fuels used in the diesel engine. The CO2 emission increases with increases in load, as expected. The lower percentage of biodiesel blends emits very low Table 1: Specifications of the test engine Cylinder number Displacement(Lit) Compression ratio Power (kW/rpm) Torque (Nm/rpm) Cooling system

4 3.9 17:1 85:2800 340:1800 Water cooled

Table 2: Specifications of diesel and biodiesel fuels Property

Method

Biodiesel

Property

Flash point, closed cup Pour point Kinematical viscosity Sulfated ash Total Sulfur Copper strip corrosion Cloud point

D D D D D D D

64 ° C 0°C 4.03 mm²/s 0.05 wt.% 1a 2°C

182 ° C -3 ° C 4.15 mm²/s 0 wt.% 0.0018 wt.% 1a 0°C

93 97 445 874 5453 130 2500

209


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SHIRNESHAN et al., Curr. World Environ., Vol. 7(2), 207-212 (2012)

amount of CO2 in comparison with diesel. B20 emits very low level of CO2 emissions. Using higher concentration biodiesel blends as the fuel, CO2 emission is found to increase. But, its emission level

is lower than that of the diesel mode. more amount of CO2, as compared biodiesel blends. More amount of CO2 emission is an indication of the

Fig. 1: Effect of biodiesel and engine load on hydrocarbon emission

Fig. 2: Effect of biodiesel and engine load on CO emission

Fig. 3: Effect of biodiesel and engine load on CO2 emission

B80 emits to that of in exhaust complete


SHIRNESHAN et al., Curr. World Environ., Vol. 7(2), 207-212 (2012) combustion of fuel. This supports the higher value of exhaust gas temperature. Fig.4 shows the variation of NOx emission with engine load. The NOx concentration increases with increase of engine load for all the fuels. Compared with diesel, NO x emission of the

211

biodiesel blended fuel increases slightly at all tested engine loads and the increase is more obvious at higher engine loads. From diesel to B80, the NOx emission increases. The peak concentrations at the 80% engine load are 670 ppm, 640 ppm, 640 ppm, 620 ppm and 600 ppm respectively, for diesel, B20, B40, B60, B80.

Fig. 4: Effect of biodiesel and engine load on NOx emission CONCLUSION Experiments have been conducted on a diesel engine using diesel, diesel-biodiesel blended fuels. Biodiesel used in the present study was manufactured from waste frying oil. Blended fuels containing 20%, 40%, 60% and 80% by volume of biodiesel, were used in the tests. The effect of engine load and fuel mix on emissions was investigated. The use of diesel blended with biodiesel, compared with diesel on the emissions; in general, HC and CO emissions are higher at

low engine loads and lower at high engine loads while NOx increase with engine loads. Also the CO2 emission increases with increases in load, as expected. The lower percentage of biodiesel blends emits very low amount of CO 2 in comparison with diesel. After the addition of biodiesel in the blended fuel, HC and CO emissions decrease due to improved combustion with oxygen enrichment of the fuel. However, NOx emissions increase due to the higher combustion temperature and the increased oxygen level in the combustible mixtures.

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Agarwal AK., Biofuels (alcohols and biodiesel) applications as fuels for internal combustion engines. Prog Energy Combust Sci 33: 233-71 (2007). Demirbas A., Biodiesel impacts on compression ignition engine (CIE): Analysis of air pollution issues relating to exhaust emissions. Energy Sources, 27(6): 549-558 (2005). Ribeiro NM, Pinto AC, Quintella CM, Rocha GOD, Teixeira LSG, Guarieiro LLN, et al., The role of additives for diesel and diesel blended (ethanol or biodiesel) fuels: a review. Energ

4.

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Fuel, 21: 2433-45 (2007). CvengroĹĄ J, Povaâ&#x20AC;˘anec F., Production and treatment of rapeseed oil methyl esters as alternative fuels for diesel engines. Bioresour Technol 55: 145-52 (1996). USEPA., A comprehensive analysis of biodiesel impacts on exhaust emissions; EPA. 420-P-02-001 (2002). Srivathsan VR, Srinivasan LN, Karuppan M., An overview of enzymatic production of biodiesel. Bioresour Technol, 99(10): 397581 (2008). Manish Kumar Mishra and D.P. Pandey,


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Orient J. Chem., 27(1): 305-311 (2011). Kulkarni MG, Dalai AK., Waste cooking oilan economical source for biodiesel: a review. Ind Eng Chem Res; 45: 2901-13 (2006). Lapuerta M, Rodriguez-Fernandez J, Agudelo JR., Diesel particulate emissions from used cooking oil biodiesel. Bioresour Technol 99: 731-740 (2008). Cherng-Yuan L, Lin H-A., Engine performance and emission characteristics of a three-phase emulsion of biodiesel produced by peroxidation. Fuel Processing Technol. 88(1): 35-41 (2007). Demirbas A., Progress and recent trends in biofuels. Prog Energy Combust Sci, 33: 1-18 (2007). Rakopoulos CD, Antonopoulos KA, Rakopoulos DC., Comparative performance and emissions study of a direct injection diesel engine using blends of diesel fuel with vegetable oils or biodiesels of various origins. Energy Conver. Manage. 47(18-19): 3272-3287 (2006). Ulusoy Y, Tekin Y, Çetinkaya M, Karaosmano_lu F., The engine tests of biodiesel from used frying oil. Energy Sources, 26: 27-932 (2004). Kaplan C, Arslan R, Sürmen A, Performance Charecteristics of Sunflower Methyl esters as Biodiesel. Energy Sources, 28: 751-755 (2006). Çetinkaya M, Karaosmano_lu F., A new application area for used cooking oil originated biodiesel: Generators. Energy Fuels, 19(2): 645-652 (2005). Hamasaki K, Kinoshita E, Tajima H, Takasaki K, Morita D., Combustion characteristics of diesel engines with waste vegetable oil methyl ster. The fifth International Symposium on Diagnostics and Modeling of Combustion in Internal Combustion Engines (COMODIA 2001). Nagoya, Japan (2001). Lapuerta M, Armas O, Jose RF., Effect of biodiesel fuels on diesel engine emissions. Prog Energ Combust, 34:198-223 (2008). Tat ME., Investigation of oxides of nitrogen emissions from biodiesel-fueled engines. PhD thesis. Iowa State University. http:// www3.me.iastate.edu/biodiesel/Technical

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Papers/Dissertati on_link.htm (2003). Çanakçi M, VanGerpen JH., Comparison of engine performance and emissions for petroleum diesel fuel, yellow grease biodiesel, and soybean oil biodiesel. Trans. ASAE, 46(4): 937-944 (2003). Mittelbach M, Tritthart P., Diesel fuel derived from vegetable oils, III. Emission tests using methyl esters of used frying oil. J American Oil Chemists’ Soc. 65(7): 1185-1187 (1988). Payri F, Macián V, Arregle J, Tormos B, Martínez JL, Heavy-duty diesel engine performance and emission measurements for biodiesel (from cooking oil) blends used in the ECOBUS project. SAE paper. 200501-2205 (2005). Aakko P, Nylund NO, Westerholm M, Marjamäki M, Moisio M, Hillamo R., Emissions from heavy-duty engine with and without after treatment using selected biodiesels. FISITA 2002 World Automotive Congress Proceedings; F02E195 (2002). Dorado M, Ballesteros E., Arnal J, Gomez J, Lopez F., Exhaust Emissions from a Diesel Engine Fueled with Transesterified Waste Olive Oil. Fuel, 82: 1311-1315 (2003). Murillo S, Mý´guez JL, Porteiro J, Granada E, Mora´n JC., Performance and exhaust emissions in the use of biodiesel in outboard diesel engines. Fuel, 86: 1765-1771 (2007). Meng X, Chen G, Wang Y., Biodiesel production from waste cooking oil via alkali catalyst and its engine test. Fuel Processing Technol. 89: 851-857 (2008). Preeti Jain and Sucheta Khowal, Orient J. Chem., 26(2): 509-516 (2010). Lin Y, Wu YG, Chang CT., Combustion characteristics of waste oil produced biodiesel/diesel fuel blends. Fuel, 86: 17721780 (2007). Ullman, T.L., Spreen, K.B., Mason, R.L., Effects of cetane number, cetane improver, aromatics and oxygenates on 1994 heavyduty diesel engine emissions. SAE Tec Pap Ser; No. 941020 (1994). Ramadhas AS, Muraleedharan C, Jayaraj S., Performance and emission evaluation of a diesel engine fueled with methyl esters of rubber seed oil. Renew Energy; 30: 1789800 (2005).


Current World Environment

Vol. 7(2), 213-220 (2012)

Assessment of Heavy Metals in Water, Fish and Sediments from UKE Stream, Nasarawa State, Nigeria O.D. OPALUWA1*, M. O. AREMU1, L. O. OGBO2, J. I. MAGAJI2, I.E. ODIBA3 and E.R. EKPO1 1

Department of Chemistry, Nasarawa State University, Keffi, Nigeria. Department of Geography, Nasarawa State University, keffi, Nigeria. 3 Department of Geology and Mining, Nasarawa State University, Keffi, Nigeria. 2

(Received: July 12, 2012; Accepted: September 17, 2012) ABSTRACT The levels of lead, zinc, copper, iron, manganese, cadmium and mercury were determined in various body parts of two species of catfish; Clarias gariepinus and Synodontis schall, water and sediment samples from Uke stream using atomic absorption spectrophotometer (AAS) method. The results obtained showed that iron (Fe) had the highest concentration with average of 8.78 mg/g and 7.51 mg/l in sediment and water respectively followed by Zn with 4.79 mg/g (sediment) and 3.19 mg/l (water) while Cd had the lowest concentration of 0.035 mg/g and 0.023 mg/l in the sediment and water respectively. In the two fish species, zinc (0.17 – 3.25 mg/g) was the most highly concentrated in the various matrices while lead (0.011 – 0.031mg/g) was the lowest. Metal levels in the various body parts of the two species of fish studied were found to be more concentrated in either, the head, gills or the intestine. In both species zinc had the widest variability while lead was the least. The metal levels determined in water and sediment are all above the tolerable limits recommended by regulatory bodies which is an indication that this ecosystem is contaminated with heavy metals which would eventually end up in the food chain. The metals determined in various body parts of two species of catfish were below deleterious level; however there is the need for regular monitoring of the heavy metal load in this water body and the aquatic organisms in there because of the long term effects.

Key words: Clarias gariepinu, Synodontis schall, water, sediments, heavy metals, AAS.

INTRODUCTION Over the last few decades, there has been growing interest in determining heavy metal levels in the marine environment and attention was drawn to the measurement of contamination levels in public food supplied, particularly fish1-3. Although heavy metal is a loosely defined term4, it is widely recognized and usually applied to the wide spread contaminants of terrestrial and fresh water ecosystems. Some examples of heavy metal include lead, zinc, cadmium, copper and manganese. Many of these heavy metals are toxic to organisms at low concentration5-6.

The concentration of metals in bioavailable form is not necessarily proportional to the total concentration of the metal. The concentration of various elements in the air, water and land may be increased beyond their natural level due to the agricultural, domestic and industrial effluents. These substances are described as “contaminants” when discharged to the environment7. In water, insoluble heavy metals may be bound to small silt particles. Metals and other fluvial contaminants in suspension or solution, do simply flow down the stream, they form complexes with other compounds settle to the bottom and ingested by plants and animals or adsorbed to sediments 8. Consequently, aquatic organisms may acquire heavy metals in body


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directly from the water via gills or food chain mechanisms9.

of this ecosystem for the benefits of the residents of Uke and its environs.

Work has been presented on heavy metal concentrations in water, sediments and fishes from Nasarawa and Antau streams in Nasarawa State to ascertain the extent of heavy metal pollution in these aquatic ecosystems and their eventual uptake by aquatic organisms. Different parts of fish (head, gills, intestine and flesh) were used and by drying these parts of fish and the sediment samples and employing the method of wet digestion and AAS, the level of metals in these parts of fish and the sediment were determined. The level of metals in water was also determined using AAS after pretreatment. The results showed the presence of metals determined in all the samples but were below the deleterious level5,10.

MATERIALS AND METHODS

Water and sediments are commonly used as indicators for the state of pollution of aquatic ecosystem11. Uke stream runs through the centre of the town and the water from this stream serves domestic purposes as well as irrigation farming and aquatic organisms (fish) from this water body is one the major sources of protein for the populace of this location. However, the stream also serves as points of discharge for domestic wastes in some areas along the length of the stream and runoffs from agricultural lands always flow into the stream at different points. Aquatic animals (including fish) bioaccumulate heavy metals in considerable amount in tissues over a long time and the dependence of the populace in this area on this water body for domestic water supply and its aquatic organisms (fish) as source of protein makes it imperative to assess the level of heavy metals in this aquatic ecosystem in view of the health implications that cut across the food strata. This research reports the level of Pb, Zn, Fe, Cd, Cu and Mn in parts of fish caught from Uke stream as well as the stream water and sediments in order to ascertain the relationship between bioaccumulation of these metals in the aquatic organisms (fish) with the distribution and concentrations of these metals in the stream water and sediments. This is aimed at ensuring the safety

Collection of samples Water samples were collected using plastic containers to fetch water below the surface at designated points, mixed properly and stored in a plastic container rinsed with 0.01N nitric acid and kept in deep freezer prior to the time of analysis11. The sediment samples were collected by scooping with a plastic spoon from the points where the water samples were taken, air dried and kept awaiting analysis. The samples of available fish species (Clarias gariepinus and Synodontis schall) in the stream were purchased from fishermen at the stream site. They were properly and carefully washed and stored at 40C pending analysis. These samples were all collected at7.00 local time while the temperature (28ÂşC) of the water was taken at the point of collection. Sample treatment Five (5.0) cm3 of concentrated hydrochloric acid were added to 250.0 cm3 of water sample and evaporated to 25.0 cm 3. The concentrate was transferred to a 50.0 cm3 standard flask and diluted to the mark with de-ionized water11. 5.0 g of prepared sediment sample was digested with 15.0 cm3 nitric acid, 20.0 cm 3 perchloric acid and 15.0 cm 3 hydrofluoric acid and placed on a hot plate for 3h. On cooling, the digest was filtered into a 100.0 cm3 volumetric flask and made up to the mark with distilled water12. Different body parts of the fish (Head, gills, intestine and flesh) were dried in the oven at 1050C until constant weight is obtained and blended. 2.0 g of the blended fish parts were weighed and digested using the approved method14. Mineral analysis Lead, zinc, copper, iron, manganese, cadmium and mercury were determined in samples of fish body parts of Clarias gariepinus and Synodontis schall , water and sediment using computer controlled Atomic Absorption Spectrophotometer (AAS VGB 210 System). The instrument setting and operational conditions were done in accordance with the manufacturersâ&#x20AC;&#x2122;


OPALUWA et al., Curr. World Environ., Vol. 7(2), 213-220 (2012) specifications. All determinations were in triplicates. Statistical analysis The results obtained were subjected to statistical evaluation. Parameters evaluated were grand mean, standard deviation (SD) and coefficient of variation (CV %). RESULTS AND DISCUSSION Table 1 shows the mean metal concentrations, grand mean, standard deviation and coefficient of variation percent of water and sediments. The mean concentration of metals determined in the water samples ranged from 0.023 – 7.51 mg/L and for sediments the range was 0.095 – 8.78 mg/g. The metals determined were Pb, Zn, Fe, Cd, Cu, Mn and Hg with mean concentrations of 0.040, 3.19, 7.51, 0.023, 0.95, 0.51 (mg/l) in water and 0.095, 4.79, 8.78, 0.035, 1.34, 0.24, and (mg/ g) in sediment respectively with Hg not detected in both water and sediment samples. The concentrations of Fe, Zn, in both samples and Cu in sediment were high (> 1.0 mg/L). The concentration of Fe being highest in sediment

215

agrees with the result of the report of heavy metals in sediments of Rafin Mallam stream10 but its value in water, also highest is high than the value recorded in the report of heavy metals in water and fish from River Antau5. However, the concentration of Fe in sediments and water to an extent is determined by the nature of soil along the stream banks15 from where it is leached into the water body and sediments. The values of Zn recorded are lower than the ones obtained from the results of the report of heavy metals in water, sediments and fish from River Nasarawa and for Cu, its concentration is the same for water and higher for sediment than that obtained for River Nasarawa10. Zinc is widely used for making paints, dyes, rubber, wood preservatives and through wares and tears; zinc from this sources is discharged into the environment. Although zinc is required by plants and animals for normal growth, higher concentration of it is toxic16. The concentrations of Cd and Pb obtained are lower for water and higher for sediments from the work on a water body used for irrigation in Keffi10. The concentration of Mn in sediment is lower and higher in water than those obtained from the work

Table 1: Mean metal concentrations in water (mg/L) and sediment (mg/g) Parameter

Pb

Zn

Fe

Cd

Cu

Mn

Hg

Water Sediment Grand mean SD CV%

0.040 0.095 0.068 0.039 57.35

3.19 4.79 3.99 1.13 28.35

7.51 8.78 8.15 0.90 11.04

0.023 0.035 0.029 0.008 2.76

0.95 1.34 1.15 0.28 24.35

0.51 0.24 0.38 0.19 50.00

ND ND -

standard deviation, SD; coefficient of variation percent, CV%.

Table 2:National and International Standards Metals

Pb Zn Cu Fe Mn Cd

Water (mg/L)

Fish (mg/g)

FDA

WHO

EPA

WHO

0.005 1.0 0.005

0.01 3.0 1-2 0.3 0.1-0.5 0.003

0.05 5.0 1.0 0.1 0.05 -

1.5 150 2.5 0.2

carried out on River Tammah12. Cu, Pb and Mn are some of the metals that get into aquatic ecosystem from runoffs from agricultural lands as a result of the use of agrochemicals containing heavy metals such as Cu, Mg, Mn, Pb and Zn17. The probable sources of Cd in surface water includes leaching from Ni – Cd batteries, run off from agricultural soils where phosphate fertilizers are used and other wastes18-19.


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All the metals determined were above the World Health Organization (WHO) safety standards, Food and Drugs Administration (FDA) Table-2, and the United States Environment Protection Agency (USEPA) maxima20 except for copper in water which is within the range recommended by W.H.O higher than the ranges recommended by other regulatory bodies. The level of zinc in sediment is however within the range recommended by EPA20. Iron though high above WHO safety standard, it is still safe because it has benefits to organism though in very high concentration leads to conjunctivitis, chroiditis and retinitis if it is in contact and remains in the tissue but Cd is a toxic metal and has no metabolic benefits to human and aquatic biota21. Its presence in any compartment of the aquatic ecosystem indicates contamination. The high level of these metals in both the water and sediment samples are as a result of the runoffs during the rainy season from agricultural

fields and the dumping of domestic wastes in the water body at different points along the length of the stream as they are known to contain heavy metals such as As, Cd, Co, Cu, Fe, Hg, Mn, Pb, Ni and Zn which will eventually end up in this aquatic ecosystem23. Among all these metals determined iron has the highest concentration with average of 8.78 mg/g and 7.51 mg/l in sediment and water, respectively followed by Zn with 4.79 mg/g (Sediment) and 3.19 mg/l (Water) while Cd has the lowest concentration of 0.035 mg/g and 0.023 mg/ l in the sediment and water respectively. These results are in agreement with the result of in which Cd was found to have the lowest concentration in both sediment and water. Going by the calculated coefficient of variation percent (CV %) when the levels of metals in water and sediment were compared the variability was highest in lead while cadmium was the least varied.

Table 3: Mean metal concentrations in the body parts of African catfish (Clarias garipienus), mg/g Parameter

Pb

Zn

Fe

Cd

Cu

Mn

Hg

Head Gills Intestine Flesh Grand mean S.D CV (%)

0.031 0.022 0.012 0.013 0.020 0.009 45.00

0.17 2.35 0.26 0.18 0.73 1.08 147.94

0.13 1.63 0.26 0.13 0.54 0.73 135.18

0.005 0.016 0.025 0.001 0.012 0.011 91.67

0.05 1.31 0.31 0.15 0.46 0.58 126.08

0.22 0.12 0.21 0.11 0.37 0.27 72.97

ND ND ND ND -

SD standard deviation; CV% coefficient of variation percent; ND not detected

Table 4: Mean metal concentrations (mg/g) in the body parts of African catfish (Synodontis schall) Parameter

Pb

Zn

Fe

Cd

Cu

Mn

Hg

Head Gills Intestine Flesh Grand mean S.D CV (%)

0.021 0.014 0.011 0.012 0.015 0.005 33.33

0.19 3.25 0.21 0.17 0.96 1.53 159.38

0.12 1.52 0.31 0.16 0.53 0.67 126.41

0.005 0.015 0.026 0.001 0.118 0.111 94.06

0.06 1.35 0.25 0.15 0.45 0.60 133.33

0.24 0.11 0.18 0.11 0.39 0.26 66.67

ND ND ND ND -

SD standard deviation; CV% coefficient of variation percent; ND not detected


OPALUWA et al., Curr. World Environ., Vol. 7(2), 213-220 (2012) Table-3 and Table-4 show mean metal concentrations in the body parts (head, gills, intestine and the flesh) of African catfish, Clarias garipienus and Synodontis schall respectively. The presence of these metals analysed in the body parts of fish serves as an indicator for the extent of heavy metal pollution of the water body from where these aquatic organisms (fish) are obtained10. Also the presence of most of the metals determined in the fish parts agrees with the results of the report of the level of heavy metals in aquatic organism from different water bodies24-25 which showed that aquatic animals, fish, inclusive bio-accumulate heavy metals in considerably amount, and because these metals are not bio-degradable, the metal tend to stay in the fish tissues for a very long time which upon consumption of these fish, the heavy metals get transferred to man, leading to heavy metal poisoning in man especially if present in higher concentrations. In both species of the fish zinc presented the highest concentrations followed by

217

iron in the various parts studied and this is relative to the concentrations of these metals observed in both water and sediment samples. Copper was the next metal after zinc and iron with concentration range of 0.05 â&#x20AC;&#x201C; 1.35 mg/g in the various parts of both species of the fish studied. Lead, cadmium and manganese showed different distribution among the various parts of fish. Mercury was not detected in any part of both species just as it was neither detected in water nor sediment samples. Zinc showed the highest variability of 147.94 and 159.38 % in Clarias garipienus and Synodontis schall respectively with lead having the least in both cases. This results agrees with that obtained for the analysis of the levels of metals in organs of Clarias lazera from river Nasarawa10. Most of the metals had highest concentrations either in the head part (lead and manganese) or the gills part (zinc, iron and copper).

Table 5: Bioconcetration factors of the various metals in the body parts of Clarias garipienus Parameter

Pb

Zn

Fe

Cd

Cu

Mn

Hg

Head Gills Intestine Flesh Grand mean S.D CV (%)

0.78 0.55 0.30 0.33 0.49 0.22 44.90

0.05 0.74 0.08 0.06 0.23 0.34 147.82

0.02 0.28 0.04 0.02 0.09 0.13 144.44

0.22 0.70 1.09 0.04 0.51 0.48 94.12

0.05 1.38 0.33 0.16 0.48 0.61 127.08

0.43 0.24 0.41 0.22 0.33 0.11 33.33

-

SD standard deviation; CV% coefficient of variation percent

Table 6: Bioconcentration factors of the various metals in the body parts of Synodontis schall Parameter

Pb

Zn

Fe

Cd

Cu

Mn

Hg

Head Gills Intestine Flesh Grand mean S.D CV (%)

0.53 0.35 0.28 0.30 0.37 0.12 32.43

0.06 1.01 0.07 0.05 0.30 0.47 156.67

0.02 0.20 0.04 0.02 0.07 0.08 114.29

0.22 0.65 1.13 0.04 0.51 0.49 96.08

0.06 1.42 0.26 0.16 0.48 0.64 133.33

0.47 0.22 0.35 0.22 0.32 0.12 37.50

-

SD standard deviation; CV% coefficient of variation percent


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OPALUWA et al., Curr. World Environ., Vol. 7(2), 213-220 (2012)

This is as result of the fact that the gills helps in respiration and filtration of water24. Relatively high concentrations of some of the metals were found in the intestine since the intestine is part of the visceral muscles which concentrates toxic metals25. Zinc and copper are mineral elements which are essential metals and play vital role in enzyme activity and iron is very important in heamoglobin formation. Lead and cadmium are toxic at very low concentration and have no known functions in biochemical processes. Sources of cadmium include wastes from cadmium- based batteries, incinerators and runoff from agricultural soils where phosphate fertilizers are used since cadmium is a common impurity in phosphate fertilizers18. Lead is mainly from storage batteries, type metal and antiknock compound in petrol27. The levels of all the metals determined were however below the concentrations recommended by regulatory bodies21. Table-5 and Tables-6 show the bioconcentration factors for Clarias garipienus and Synodontis schall, respectively. Most of the values obtained for the various fish parts were relatively low (< 1) which showed there was no biological magnification of metal concentration in fish samples except for cadmium (in the intestine) and copper (in gills) for Clarias garipienus and zinc (in gills), cadmium (in the intestine) and copper (in gills) for Synodontis schall. Order of bioconcentration in the various body parts of Clarias garipienus is Zn > Fe

> Cu > Cd > Pb > Mn while that of Synodontis schall is Zn > Cu > Fe > Cd > Mn > Pb. Zn showed the widest variation in both species of fish while the least variations were recorded in Mn and Pb for Clarias garipienus and Synodontis schall, respectively. The levels of metals in the body parts of the two species of catfish were lower than that of the water or sediment. However the presence of metals in the two fishes biochemically showed that fish is relatively dependent on the levels of metals available in aquatic ecosystem. CONCLUSION This research has presented data on the levels of heavy metals in sediments, water and various body parts of two species of catfish from Uke stream in Uke town, Nasarawa State. Although the results obtained does not show any form of danger posed to consumers of sea foods and water from this stream but the possibility of deleterious effects after long period cannot be ruled out. This is as a result of the fact that this water body serves as the receptor for domestic wastes as well as runoff from agricultural lands where phosphate fertilizers and other agrochemicals are frequently used. There is therefore the need for continual assessment of the level of pollution of this stream with metals from the mentioned sources with a view to reducing the level of pollution via education and public enlightenment.

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Kalay, M; Aly,O. and Canil,M., Heavy metal concentrations in fish tissue from the Northeast Mediterranean Sea, Bullentin of Environ. Contamination and Toxicity, 63: 673671 (1999). Rose, J., Hutcheson, M.S., West, C.R .and Pancorbo, O., “Fish Mercury Distribution in Massachusetts, USA Lakes”, Environ. Toxicology and Chem., 18(7): 1370-1379 (1999). Tariq, J., Jaffa, M. and Ashraf, M., “Heavy Metal concentrations in fish, shrimp, seaweed, sediment and water from Arabian

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Sea, Pakistan”, Marine Pollution Bulletin, 26(11): 644-647 (1993). Duffus, J. H., “Heavy Metal” - A meaningless term. Pure and Applied chemistry, 74: 793807 (2002). Galloway, J.N., Thornton, J.D., Norton, S.A., Volchok, H.L and MCclean H.L., Trace Metals in Atmospheric depositions, A review and assessment. Atmospheric Environment, 16: 1677-1700 (1982). P. Sannasi and S. Salmijah, Orient J. Chem., 27(2): 461-467 (2011). Madu, P.C., Tagwoi, J.T. and Babalola, F., A


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study of heavy metal pollution of River Antau, Keffi, Nasarawa State, Nigeria, India J. of Multi. Res., 4(1): 8-18 (2008). Odiete, W.O., Environmental Physiology of Animals and Pollution, 1st ed. Diversified Resources Limited, Lagos.1-end (1999). Collison, C. and Shrimp, N.F., Trace elements in bottom sediments from Upper Peria Lake. Middle Illinois River. Illinois Geo. Survey and Environ. Geology Note, 56: 21 (1972). Huckabee, J.W and Blaylock, B.G., Transfer of mercury and cadmium from terrestrial to aquatic ecosystem. Environmental sciences Division, Oak Ridge National Laboratory Oak Ridge, Tennesse, 55 (1972). Aremu, M.O., Atolaiye, B.O., Shagye, D., and Moumouni, A., Determination of trace metals in Tilapia zilli and Clarias lazera fishes associated with water and soil sediment from River Nasarawa in Nasarawa State, Nigeria, India J. Multi. Res., 3(1): 159-168 (2007). Opaluwa, O.D. and Umar, M.A., Level of heavy metals in vegetables grown on irrigated farmland, Bull. of Pure and Applied Sci., 29C (1): 39-55 (2010). Atolaye, B. O, Aremu, M.O., Shagye, D. and Pennap, G.R. I., Distribution and concentration of some mineral elements in soil sediment, ambient water and body parts of Claria gariepinus and Tilapia queneensis fishes in stream Tammah, Nasarawa State Nigeria, Curr World Environ., 1(2): 95-100 (2006). Adekenya B., Variation of metal pollutants with depths, Techforum, An Interdisci., J. 2(3): 82-97 (1998). Ibok, U.J; Udosen, E.D and Udoidiong, O.M., Heavy Metals in Fishes from Streams in Ikot Ekpene Area of Nigeria, Nigeria J. Tech. Res., 1: 61-68 (1989). Osakwe, S. A. and Peretiemo-Clarke, B.O., Evaluation of heavy metals in sediments from River Ethiope, Delta State, Nigeria. 31st CSN Conference paper, 611-613 (2008). Umar, M.A. and Opaluwa, O.D., Evaluation of heavy metals in sediments of Rafin Mallam stream in Keffi, Nasarawa State, Intl. J. Chem., 20(2): 99-103 (2010).

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Pate, K.P., Pandy, R.M. and George, L., Heavy metal content of different effluents water around major industrial cities of Guryurat, J. of Indian Society of Soil Sci., 59(1): 89-94 (2001). Hutton, M. and Symon, C., The quantities of cadmium, lead, mercury and arsenic entering the U.K environment from human activities, Science of the total environment, 59: 129-150 (1986). Stoeppler, M., Cadmium. In: Merian E (ed) Metals and their compounds in the environment: Occurrence, analysis and biological relevance. VCH. New York, 803851 (1999). United States environmental protection Agency (USEPA), Quality Criteria for Water. United States Environment Protection Agency Office of Water Regulations and Standards, Washington DC, 20460, 1986a. Environmental Protection Agency EPA, (1976): â&#x20AC;&#x153;Quality Criteria for Waterâ&#x20AC;?. Washington, 440 (9): 76-123 (1986a). Woodworth, J.C and Pascoe, V., Cadmium toxicity to rainbow trout, salmon gairdneri Richardson, A Study of Eggs and Alevins, J. Fish. Biol., 21: 47-57 (1982). Oluyemi, E.A.; Fenyuit, G.J; Oyekunle, J.A.O. and Ogunfowokan, A.O., Seasonal variations in heavy metal concentrations in soil and some selected crops at a landfill in Nigeria, African J. of Sci. and Tech., 2(5): 8996 (2008). Kemdrin, E.C., Trace metal contents of microbenthos of two city reservoirs in Jos, Plateau in relation to their feeding functional groups, N.J.T.E., 14(1): 42-44 (1979). Etuk, E.U.I and Mbonu, C.O., Comparison of trace and toxic metal contaminants in Perionkle from Qua-Iboe River (Ibeno) and Cross River (Oron), Proceeding of the 23rd Annual Conference of the Nigeria Institute of Food Science and technology held at Abuja Oct. 25-27th, (1999). Ayejuyo, O.O., Olowu, R.A., Megwa, K.C., Denloye, A.A.B. and Owodehinde, F. G., Trace metals in Clarias lazera, water and sediments from Majidun River, Ikorodu,


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nilotica). Food Chem. 58: 1-4 (1997). Crossby, N.T. Determination of metals in Food. A Review. Analyst , 102: 225-268 (1997).


Current World Environment

Vol. 7(2), 221-226 (2012)

Structural Properties, Natural Bond Orbital, Theory Functional Calculations (DFT), and Energies for the Îą Halorganic Compounds NAJLA SEIDY and SHAHRIAR GHAMMAMY Department of Chemistry, Faculty of Science, Imam Khomeini International University, Qazvin, Iran. (Received: July 12, 2012; Accepted: September 17, 2012) ABSTRACT In this paper, the optimized geometries and frequencies of the stationary point and the minimum-energy paths of C3H2F4Br2 are calculated by using the DFT (B3LYP) methods with LANL2DZ basis sets. B3LYP/ LANL2DZ calculation results indicated that some selected bond length and bond angles values for the C3H2F4Br2.

Key words: Halo fluoroalkane, C3H2F4Br2, Electronic structure, Calculations, Vibrational analysis, B3LYP level.

INTRODUCTION Organic halogen alkane compounds or halocarbon compounds are chemicals in which one or more carbon atoms are linked by covalent bonds with one or more halogen atoms (fluorine, chlorine, bromine or iodine - group 17) resulting in the formation of organofluorine compounds, organochlorine compounds, organobromine compounds, and organoiodine compounds. Chlorine halocarbons are the most common and are called organochlorides. Many synthetic organic compounds such as plastic polymers, and a few natural ones, contain halogen atoms; they are known as halogenated compounds or organohalogens. Organochlorides are the most common industrially used organohalides, although the other organohalides are used commonly in organic synthesis. Except for extremely rare cases, organohalides are not produced biologically, but many pharmaceuticals are organohalides. Organic halogen compounds have many uses in theoretical and industrial1-5. Common uses for halocarbons have been as solvents, pesticides, refrigerants, fireresistant oils, ingredients of elastomers, adhesives

and sealants, electrically insulating coatings, plasticizers, and plastics. Many halocarbons have specialized uses in industry. One halocarbon, sucralose, is a sweetener. Many different data have been found about the structural properties of halo compounds, but they are insufficient and opposing in somewhere. The investigation of the structures and properties of the compound and similarities are interested. The structure has been confirmed by neutron diffraction studies and is justified by VSEPR theory5-8. During this study we report the optimized geometries, assignments and electronic structure calculations for the compound. The structure of the compound has been optimized by using the DFT (B3LYP) method with the LANL2DZ basis sets, using the Gaussian 09 program [9]. The comparison between theory and experiment is made. Density functional theory methods were employed to determine the optimized structures of C3H2F4Br2 and Initial calculations were performed at the DFT level and split- valence plus polarization LANL2DZ basis sets were used. Local minima were obtained by full geometrical optimization have all positive frequencies10.


222

SEIDY & GHAMMAMY, Curr. World Environ., Vol. 7(2), 221-226 (2012) METHODS

All computational are carried out using Gaussian 09 program [11]. The optimized structural parameters were used in the vibrational frequency calculations at the HF and DFT levels to characterize all stationary points as minima. Harmonic vibrational frequencies (í) in cm-1 and infrared intensities (int) in Kilometer per mole of all compounds were performed at the same level on the respective fully optimized geometries. Energy minimum molecular geometries were located by minimizing energy, with respect to all geometrical coordinates without imposing any symmetrical constraints.

in bond lengths and bond angle values with the experimental data. Because the crystal structure of the title compound is not available till now. B3LYP/ LANL2DZ calculation results showed that the (C1F6) bond length values for the C3H2F4Br2 and in compounds 1-2 are 1.3909 Å and 1.3765 Å respectively. And (C-Br-) bond length values for the C 3 H 2 F 4 Br 2 compounds 1-2 are 1.8031Å and 1.7727Å respectively. Alkyl halide compounds are mostly dense liquids and solids that are insoluble in water. The halogens are all more electronegative than carbon and this makes the carbon-halogen bond a polar bond with a slight positive charge (d +) residing on the carbon end of the bond and a slight negative charge (d-) on the halogen end.

RESULTS AND DISCUSSION Molecular properties The structures of compounds are shown in Figure 1. All calculations were carried out using the computer program GAUSSIAN 09. Theoretical calculation of bond and angle for the compound was determined by optimizing the geometry (Table 1).

The carbon-halogen bond strength decreases in the order C-F > C-Cl > C-Br > C-I

NBO Analysis in Table1 and The NBO Calculated Hybridizations are reported in Table2. We could not compare the calculation results given

Alkyl fluorides tend to be less reactive than other alkyl halides, mainly due to the higher strength of the C-F bond.

Table 1: Geometrical parameters optimized for C3H2F4Br2 some selected bond lengths (Å) and angles (°C) B3LYP/6-311 C3H2F4Br2 Bond lengths (Å) C1-C3 C3-F6 C1-F7 C3-F5 C1-Br8 Bond angles (°) C1-C3-F4 C1-C3-F5 C1-C3-F4

Method C3H2F4Br2

angles (°)

Bond lengths (Å)

angles (°C)

2.41 1.86 1.56 1.97 3.86

C1-C2 C3-F4 C2-H9 C-2Br11 C2-H10 Bond angles (°) C2-C1-F4 C2-C1-F5 F4-C1-F5

3.15 0.75 0.53 0.80 0.53

123.258 123.258 113.483

123.255 123.253 113.491


SEIDY & GHAMMAMY, Curr. World Environ., Vol. 7(2), 221-226 (2012) NBO study on structures Natural Bond Orbital’s (NBOs) are localized few-center orbital’s that describe the Lewis-like molecular bonding pattern of electron pairs in optimally compact form. More precisely, NBOs are an orthonormal set of localized “maximum occupancy” orbital’s whose leading N/2 members (or N members in the open-shell case) give the most accurate possible Lewis-like description of the total N-electron density. This analysis is carried out by examining all possible interactions between

223

“filled” (donor) Lewis-type NBOs and “empty” (acceptor) non-Lewis NBOs, and estimating their energetic importance by 2nd-order perturbation theory. Since these interactions lead to donation of occupancy from the localized NBOs of the idealized Lewis structure into the empty non-Lewis orbitals (and thus, to departures from the idealized Lewis structure description), they are referred to as “delocalization” corrections to the zeroth-order natural Lewis structure. Natural charges have been computed using natural bond orbital (NBO) module

Table 2: The NBO Calculated Hybridizations for (C3H2F4Br2, B3LYP/LANL2DZ) (1)C3H2F4Br2

(2)C3H2F4Br2

Bond

Atom

B3LYP

Bond

Atom

B3LYP

C-C C-F C-C C-H C-Br C-F C C F F Br

C1-C2 C1-F7 C1-C2 C2-H9 C2-Br11 C3-F5 C1 C3 F5 F7 Br11

S1P2.56, S1P2.91 S1P4.22, S1P2.57 S1P2.56, S1P2.91 S1P2.51, S1P0 S1P4.44, S1P7.37 S1P3.84, S1P2.62 S1P0.00 S1P0.00 S1P0.00 S1P0.00 S1

C-C C-Br C-C C-H C-F C-F C F F Br

C1-C3 C1-Br8 C1-C3 C1-H10 C3-F4 C3-F6 C2 F4 F6 Br8

S1P2.00, S1P1.61 S1P4.16, S1P7.90 S1P2.00, S1P1.61 S1P2.63, S1 S1P3.92, S1P2.64 S1P3.85, S1P2.52 S1P0.00 S1P0.00 S1P0.00 S1

Table 3: Second order perturbation theory analysis of Fock matrix in NBO basis for (1) C3H2F4Br2 (2))a means energy of hyper conjugative interaction (stabilization energy); b Energy difference between donor and acceptor i and j NBO orbital’s; c F(i, j) is the Fock matrix element between i and j NBO Donor (i)

C3F4H2Br2 C1F4 C1F5 Br(2) F (4) F (5) C3H2F4Br2 C1F4 C1F5 Br (2) F (4) F (5)

Type

ED/e

Acceptor (j)

Type

ED/e

E(2) (KJ/mol)

E(j) E(i) b (a.u)

F(i,j)c (a.u)

a

σ σ n n n

1.98934 1.98934 1.97731 1.97731 1.97731

C1F5 C1F4 C1F4 C1F4 C1F4

σ* σ* σ* σ* σ*

1.98934 1.98934 1.98934 1.98934 1.98934

0.92 0.92 2.75 2.75 2.75

1.00 1.00 0.58 0.58 0.58

0.027 0.027 0.036 0.036 0.036

σ σ n n n

1.97477 1.97477 1.95128 1.95128 1.95128

C1F5 C1F4 C1F4 C1F4 C1F4

σ* σ* σ* σ* σ*

1.97477 1.97477 1.97477 1.97477 1.97477

2.39 2.39 1.94 1.94 1.94

0.64 0.64 0.40 0.40 0.40

0.036 0.036 0.025 0.025 0.025


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Fig. 1: The schematic structure of the C3H2F4Br2

E LUMO = -0.08718 a.u Î&#x201D;E=0.21634

E HOMO = -0.30352 a.u

Fig. 2: The atomic orbital of the frontier molecular orbital for C3H2F4Br2 B3LYP/6-311 level of theory


SEIDY & GHAMMAMY, Curr. World Environ., Vol. 7(2), 221-226 (2012) implemented in Gaussian09. The NBO Calculated Hybridizations are significant parameters for our investigation. These quantities are derived from the NBO population analysis. The former provides an orbital picture that is closer to the classical Lewis structure. The NBO analysis involving hybridizations of selected bonds are calculated at B3LYP methods and LANL2DZ level of theory (Table 2). These data shows the hyper conjugation of electrons between ligand atoms with central metal atom. These conjugations stand on the base of p-d σ-bonding. The NBO calculated hybridization for C3H2F4Br2 shows that all of complexes have SPX hybridization and non planar configurations. The total hybridization of these molecules are SPX that confirmed by structural. The amount of bond hybridization showed the in equality between central atoms angles (Table 2) Shown distortion from octahedral and VSEPR structural and confirmed deviation from VSEPR structures. In C3H2F4Br2 the lone pair located on bromin atoms and significantly delocalized hybrid orbital’s of C-F bonds. Indeed, in the interaction energy from the charge transfers C 3 H 2 F 4 Br 2 complex confirms the above point and in the average for C3H2F4Br2 the maximum interaction energy is predicted (Table 3).

225

acceptor represents the ability to obtain an electron. The HOMO and LUMO energy were calculated by B3LYP/ LANL2DZ method 12 . This electronic absorption corresponds to the transition from the ground to the first excited state and is mainly described by one electron excitation from the highest occupied molecular or orbital (LUMO). Therefore, while the energy of the HOMO is directly related to the ionization potential, LUMO energy is directly related to the electron affinity. Energy difference between HOMO and LUMO orbital is called as energy gap that is an important stability for structures. In addition, 3D plots of highest occupied molecular orbitals (HOMOs) and lowest unoccupied molecular orbitals (LUMOs) are shown in Figure 2. The HOMO–LUMO energies were also calculated at the LANL2DZ and the values are listed in Figure 2, respectively. CONCLUSION In this research we are interested in studying on two Halo Organic Compounds was chosen to theoretical studies. In this paper, the optimized geometries and frequencies of the stationary point and the minimum-energy paths are calculated by using the DFT (B3LYP) methods with LANL2DZ basis sets. B3LYP/ LANL2DZ calculation results indicated that some selected bond length and bond angles values for the C3H2F4Br2. ACKNOWLEDGMENTS

Frontier molecular orbital Both the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) are the main orbital take part in chemical stability. The HOMO represents the ability to donate an electron, LUMO as an electron

We gratefully acknowledge the financial support from the Research Council of Imam Khoemieni International University by Grant No, 751387-91.

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Ghammamy, Sh., Z. Anvarnia, M. Jafari, K. Mehrani, H. Tavakol, Z. Javanshir, and G. Rezaeibehbahani, Synthesis and characterization of two new halo complexes of Iodine (C4H9)4N[I2Br]- and (C4H9)4N[I2Br]and theoretical calculations of their structures. Main Group Chemistry, 8: 299-306 (2009).

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Becke, A. D., Density-Functional Thermochemistry. III. The Role of Exact Exchange. J. Chem. Phys., 98: 5648-5652 (1993). Sundaraganesan, N. and S. Ilakiamani, Dominic Joshua B Vibrational spectroscopy investigation using ab initio and density functional theory analysis on the structure of


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SEIDY & GHAMMAMY, Curr. World Environ., Vol. 7(2), 221-226 (2012) 3, 4-dimethylbenzaldehyde. Spectrochimica Acta Part A., 68: 680-687 (2007). Lewis, D. F. V., C. Ioannides, and D. V. Parke, Interaction of a series of nitriles with the alcohol-inducible isoform of P450: computer analysis of structure-activity relationships. Xenobiotica, 24: 401-408 (1994). R. Soleymani, R.D. Dijvejin, A.G.A. Hesar and E. Sobhanie, Orient J. Chem., 28(3): 12911304 (2012). Ralph, G., Chemical hardness and the electronic chemical potential Inorganic, chimica Acta, 198: 781-786 (1992). Fleming, I., Frontier Orbitals and Organic Chemical Reactions, Wiley, London, pp. 125 (1976). Zhang, W., D.P. Curran, Synthetic Application of Fluorous. Tetrahedron 62: 11837-11865 (2006). Smith, M. C., Y. Ciao, H. Wang and S. J. George, Coucouvanis D, Koutmos M,

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Sturhahn W, Alp EA, Zhao J, Kramer SP Normal-Mode Analysis of FeCl4- and Fe2S2Cl42- via Vibrational Mossbauer, Resonance Raman, and FT-IR Spectroscopies. Inorg. Chem., 44: 55625570 (2005). Vrajmasu, V. V., E. Mu¨nck, and E. L. Bominaar, Theoretical Analysis of the Jahnâ&#x20AC;?Teller Distor tions in Tetrathiolato Iron(II) Complexes. Inorg. Chem., 43: 4862-4866 (2004). Ghammamy, Sh., K. Mehrani, S. Rostamzadehmansor, and H. Sahebalzamani, Density functional theory studies on the structure, vibrational spectra of three new tetrahalogenoferrate (III) complexes. Natural Science, 3: 683-688 (2011). Frisch, M. J. Trucks, G. W., GASSIAN 98 (Revision A. 3) Gaussian Inc., (1998).


Current World Environment

Vol. 7(2), 227-232 (2012)

Pyridine-Functionalized TiO2 Nanoparticles as a Sorbent for Preconcentration and Determination of Ultra-Trace Palladium Ions MOHAMMAD KARIMI1, MONA FEIZ BAKHSH BAZARGANI2, FOROUZAN ABOUFAZELI1, HAMID REZA LOTFI ZADEH ZHAD1, OMID SADEGHI1 and EZZATOLLAH NAJAFI1 1

Department of Chemistry, Shahr-e-Rey Branch, Islamic Azad University, Tehran, Iran. 2 Department of Chemistry, Islamic Azad University, Karaj Branch, Tehran, Iran. (Received: July 12, 2012; Accepted: September 17, 2012) ABSTRACT

In this work, TiO2 nano-particles were modified by pyridine group and characterized by scanning electron microscopy (SEM), X-Ray diffraction (XRD), FT-IR and elemental analysis (CHN). This sorbent was applied for pre-concentration of ultra-trace amount of palladium prior to its determination by flame atomic adsorption spectroscopy (FAAS). Through this study, different factors such as sample pH, sample flow rate, eluent parameters (type, concentration and volume), and elunet flow rate were optimized. Also effects of the selectivity of sorbent toward Pd(II) was investigated by palladium determination in presence of various interfering ions. The limit of detection was 3.8 ng mLâ&#x20AC;?1 and recovery was 99.1 % with a relative standard deviation of 2.5%. Finally the method was validated using standard reference material which their paladium concentrations are certified.

Key words: Palladium determination; Pyridine-functionalized TiO2 nanoparticles; solid phase extraction; Flame atomic absorption spectrometry.

INTRODUCTION Increasing demand for noble metals, particularly platinum group metals (PGM), such as palladium(II), platinum(IV), ruthenium(III), rhodium(III) has been recently observed because of their wide range of industrial applications, e.g. as catalysts in organic processes, value added components in metal alloys and vehicle catalytic converter systems, in chemical, pharmaceutical, petroleum and electronic industries and also in jewellery making. These applications of PGMs have increased the demand for these metals, whereas the natural resources are limited1-3. Flame atomic absorption spectrometry (FAAS) is one of the most popular techniques for determination of metal ions because of its high

specificity and low cost. However its sensitivity is usually insufficient for determination of trace metal ions in environmental samples. In order to overcome this problem and prevent interference effects, those who use this method usually include an efficient preconcentration step4-5. Solid-phase extraction (SPE) is one of the most common methods for preconcentration of noble metals. It has the advantages of flexibility, economical and environmental-friendly, simplicity, and being fast and safe. 5 Since the key point in SPE is choosing adsorbent, several SPE methods based on sorbents such as different polymers7, silica8 and Fe3O4 9 have been developed. Compared to the other sorbents TiO2 has attracted more attention due to its high surface area10-12. In this work, a novel sorbent based on functionalization of TiO2 nano-particles by pyridine


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group is constructed. This sorbent was applied for preconcentration of Pd(II) ions in aqueous samples after characterization by FT-IR, XRD pattern, elemental analysis and SEM micrograph. EXPERIMENTAL Reagents and Materials The standard solution of Pd(II), 1000 mg L -1 , was purchased from Aldrich Company (Milwaukee, Wi, USA). TiO2 nano-particles with 1015 nm in diameter were purchased from Neunano Company (Tehran, Iran). All reagents includes solvents, acids, 3-aminopropyltriethoxysilane, triethylamine, dichloromethane, oxalyl chloride and 4-pyridine carboxylic acid were of analytical grade and purchased from Merck Company (Darmstadt, Germany). The standard reference material (NIST SRM 2557) was purchased from National Institute of Standards. Apparatus The atomic absorption spectrometer (AAS) used in this experiment was a Shimadzu AA-680 equipped with a single element hollow cathode lamp (6.0 mA for palladium). Burner head was 50 mm and air acetylene burner head was used during the experiment. Resonance line for palladium is 244.8 nm, so the wavelength was set at this value. The spectral band width was set at 0.5 nm and the ratio of air-acetylene was set at 4.7. The pH was measured at 25 ±1 ºC with a digital WTW Metrohm 827 Ion analyzer (Herisau, Switzerland) equipped with a combined glass-calomel electrode. The Fourier Transform Infrared (FT-IR) spectrum was recorded on a BOMEM MB-Series FT-IR spectrometer in the form of KBr pellets. The elemental analyses (CHNS) were performed on a Thermo Finnigan Flash-2000 microanalyzer (Italy). The SEM micrograph was recorded by a VegaTeScan scanning electron microscope. Preparation of Pyridine functionalizing agent Pyridine functionalizing agent was synthesized according to earlier report 12 and characterized by 1H NMR. Briefly, 1.0 g of 4-pyridine carboxylic acid was suspended in 100 mL of dried CH2Cl2 under nitrogen atmosphere and 10 mL of oxalyl chloride was slowly added to the mixture and was stirred for 12 h. Then CH2Cl2 was removed

under reduced pressure, and the residue was suspended again in 100 mL of dried CH2Cl2. After addition of 17 mL triethylamine to reaction mixture, 4.0 g 3-aminopropyltrimethoxysilane was slowly added. The reaction mixture was stirred at room temperature for further 4 h. Then the solvent was removed under reduced pressure to obtain brownish viscose oil. Preparation of pyridine functionalized TiO2 nanoparticles In a typical reaction, 1.0 g TiO2 nanoparticles were suspended in 50 mL toluene, and 2 mL pyridine functionalization agent was added and the mixture was refluxed for 24 h under nitrogen atmosphere. Then the solid was collected by filtration and washed with methanol and acetone and then dried at room temperature. Formation of pyridine functionalized TiO2 nano-particles (Py-TiO2 NPs) was confirmed by FT-IR spectroscopy, XRD pattern, elemental analyses and SEM micrograph. Column preparation A glass column, 120 mm in length and 20 mm in diameter, was blocked by polypropylene filters at the ends, filled with 200 mg of the Py-TiO2 nano-particles, and then used for the experiments. Before extraction, the column was treated with 5 mL hydrochloric acid (1 M), 5 mL nitric acid (1 M), 5 mL toluene, 5 mL ethanol and 20 mL distilled water to remove organic and inorganic contaminants. Preconcentration procedure A solution containing 1 µg mL -1 of palladium with pH=7.0 was prepared. The pH was adjusted with Na2HPO4/ NaH2PO4 buffer solution and then 50 mL of solution was passed through the column at a flow rate of 8 mL min-1. The column was eluted by 12 mL of 1 mol L-1 thiourea in 0.1 mol L-1 HCl solution, then the eluent was analyzed by FAAS. Standard reference materials pretreatment Auto-catalyst NIST SRM 2557 of 0.1000 g were mixed with about 5.0 mL aqua regia and 1.0 mL HF (48–51%, v/v) in a Teflon vessel, and heated until the sample was completely decomposed. Then the solutions were evaporated in a water bath. The residues were dissolved with 0.05 mol l-1 HCl and diluted to the appropriate volume with distilled water13.


KARIMI et al., Curr. World Environ., Vol. 7(2), 227-232 (2012) RESULTS AND DISCUSSION Sorbent Characterization Modification of TiO2 nano-particles have been performed according to previous report14. Reaction of pyridine functionalizing agent with active hydroxyl group on the surface of TiO2 leads to formation of this sorbent (Fig. 1). Formation of this sorbent was confirmed by FT-IR spectroscopy, XRD pattern, elemental analyses and SEM micrograph. The presence of peaks at 3027 (CH, aromatic), 2953 (CH, aliphatic), 1561&1470 (C=C, aromatic) and 1402 (C=N) in IR spectrum confirm presence of pyridine in this sorbent. Also the amount of grafted pyridine was calculated by elemental analysis. According to the elemental analysis results (%C= 6.74, %H= 0.69, %N= 1.73), approximately 0.61 mmol pyridine is grafted on each gram of TiO2 nano-particles. In order to confirm remaining TiO2 nano-particles unchanged after functionalization (no decomposition or converting to the other oxides), XRD pattern of final product was recorded. Comparing to reference pattern (JCPDS file, No. 86â&#x20AC;&#x201C;0147), the results show the TiO2 nanoparticles structure has not been changed after functionalization (Fig. 2). Finally in order to

229

investigate the size and morphology of this sorbent, SEM micrograph of Py-TiO2 nano-particles was recorded. As it can be seen in Fig. 3, spherical nanoparticles with approximately 15-20 nm in diameter were obtained. Optimization studies Influence of pH In order to study the effect of pH on the Pd(II) extraction, the pH of 50 mL of different sample solutions containing 1 mg L -1 palladium were adjusted in the range of 2-9. The samples were passed through the column at a flow rate of 8 mL min-1. Then the column was eluted by 12 mL of 1 mol L-1 thiourea in 0.1 mol L-1 HCl solution and the Pd(II) content in eluent was analyzed by FAAS. As the results in Fig. 4 show, the highest palladium recovery is at pH=7.0. The best recovery at neutral pH may be attributed to the presence of free lone pair of electrons on the nitrogen atoms which are suitable donors for coordination to the palladium ions. Effect of type, concentration and volume of eluent Different eluent solutions including different HCl solutions and their mixture with

Table 1: The effect of diverse ions on recovery of palladium(II) on Py-TiO2 nano-particles Interfering ion

Concentration(Âľg mL-1)

Recovery(%)

1000 1000 1000 1000 1000 250 100 250 100 250

98.3 98.9 98.6 98.1 98.3 96.4 91.8 95.7 92.3 96.1

Na+ K+ Cs+ Ca2+ Mg2+ Fe2+ Pb2+ Mn2+ Cd2+ Cr3+

Table 2: The analysis of standard reference materials (NIST SRM 2557) Sample Name NIST SRM 2557

Certified value (ng g-1)

Obtained value (ng g-1)

Recovery (%)

RSD (%) (n=10)

239.8

235.9

98.3

3.2


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KARIMI et al., Curr. World Environ., Vol. 7(2), 227-232 (2012)

Fig. 1: A schematic diagram for synthesis of pyridine functionalized TiO2 nanoparticles

Fig. 2: The XRD pattern of pyridine functionalized TiO2 nanoparticles

Fig. 3: SEM micrograph of pyridine functionalized TiO2 nanoparticles

thiourea with different concentrations were used for desorption of palladium from Py-TiO2 nanoparticles. In this approach, a solution containing 1 Âľg mL -1 of palladium with pH=7.0 was passed through the column at a flow rate of 8 mL min-1. Then the adsorbed ions were desorbed by 20 mL of each eluent. Then the palladium content in each eluent was analyzed by FAAS. According to these results the best eluent is a solution of 1 mol L-1 thiourea in 0.1 mol L-1 HCl. Moreover in order to study the effect of elunet volume, different volume of 1 mol L-1 thiourea in 0.1 mol L-1 HCl solution (2 , 4, 6, 8, 10, 12, 14, 16 and 18 mL) was used for palladium desorption. The results show that at least 12 mL of this eluent is needed for complete palladium desorption from the column.


KARIMI et al., Curr. World Environ., Vol. 7(2), 227-232 (2012) Sample and eluent flow rates In order to study sample and eluent flow rates, the pH of 100 mL of 1 Âľg mL-1 palladium (II) solution was adjusted to 7 and the solution was passed through the column with different flow rates in the range of 1-10 mL min-1 using a peristaltic pump. As Fig. 5 show, the maximum flow rate for complete adsorption is 8 mL min -1. Also same experiments were performed by different eluent

231

flow rates. As it is shown in Fig. 5, at the flow rates more than 2 mL min-1, the Pd(II) desorption will be decrease. So in the further experiments, 8 and 2 mL min-1 were choosed as optimum sample and eluent flow rates, respectively. Influence of interference ions To investigate the selectivity of the sorbent, the effect of different cations such as Na+, K+, Cs+,

Fig. 4: The effect of pH on adsorbtion of palladium on pyridine functionalized TiO2 nanoparticles

Fig. 5: Investigation of adsorption and desorption time of palladium on pyridine functionalized TiO2 nanoparticles


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Mg2+, Ca2+, Fe2+, Pb2+, Mn2+, Cd2+ and Cr3+ in the Pd(II) determination was studied. The cations of as their chloride salts with various concentrations were added to a 100 mL of single solution containing 1 µg mL-1 palladium (II) and the extraction procedure was followed. As can be seen from Table 1, a good selectivity for palladium extraction was observed in pH=7.0 and this sorbent could be used as a selective Pd(II) extractor in natural samples with diverse interfere ions. Maximum adsorption capacity In order to determine the maximum adsorption capacity of this sorbent, 500 mL of a solution containing 100 mg palladium was treated with the extraction procedure and the maximum capacity was calculated by analyzing the adsorbed palladium in eluent. The maximum adsorption capacity for three replicates was found to be 61 mg g-1 (0.57 mmol g-1). Analytical performance In order to determine the detection limit (DL) of the presented method, 500 mL of ten blank solutions were passed through the column under the optimal conditions. The LOD values of 3.8 ng

mL”1 was obtained for palladium with Py-TiO2 nanoparticles from CLOD= KbSb/m using a numerical factor of kb=3.The analytical values of the proposed method were calculated from the data obtained under the optimum conditions. The recovery of the extraction of palladium ion on Py-TiO 2 was determined to be 99.1 % with a relative standard deviation of 2.5 % for ten replicated analysis. Method validation The method validation was done by analyzing a standard reference material. NIST SRM 2557 was analyzed by this method and the results of this study are presented in Table 2. The obtained results were in a good agreement with the certified value of the standard reference material. CONCLUSION The proposed solid phase extraction procedure based on TiO 2 functionalized with pyridine group shows a good selectivity for preconcentration and determination of palladium ions in trace levels. The low detection limit, palladium at trace level can be determined by this rapid and selective proposed method.

REFERENCES

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Matthey J., Platinum 2008: 1 (2008). C. Hagelüken, Metall. 1-2: 31 (2006). Mehran Raizian, Naser Montazeri and Esmaeil Biazar, Orient J. Chem., 27(3): 203219 (2012). Spivakov B. Y., Malofeeva G. I. and Petrukhin O. M., Anal. Sci., 22: 503 (2006). Bulut V. N., Gundogdu A., Duran C., Senturk H. B., and Soylak M., J. Hazard. Mater., 146: 155 (2007). Thurman E.M., and Mills M.S. Solid-Phase Extraction: Principles and Practice, Wiley, New York (1998). Kiyoyama S., Yonemura S., Yoshida M., Shiomori K., Yoshizawa H., Kawano Y. and Hatate Y., React. Funct. Polym., 67: 522 (2007). Ghaedi M., Rezakhani M., Khodadoust S., Niknam K. and Soylak M., Scientific World

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Journal. doi:10.1100/2012/764195 (2012). Lotfi Zadeh Zhad H. R., Aboufazeli F., Sadeghi O., Amani V., Najafi E. and Tavassoli N., http://dx.doi.org/10.1155/2013/482793, (2013). Zhaoa X. N., Shia Q. Z., Xieb G. H., Zhoua Q. X., Chin. Chem. Lett., 19: 865 (2008). Ali Moghini and Mohamad Javad Poursharifi, Orient J. Chem., 28(1): 203-219 (2012). Hoogboom J., Garcia P. M. L., Otten M. B., Elemans J. A. A. W., Sly J., Lazarenko S. V., Rasing T., Rowan A. E., Nolte R. J. M., J. Am. Chem. Soc. 127: 11047 (2005). Fan Z., Jiang Z., Yang F., Hu B., Anal. Chim. Acta 510: 45 (2004). Tasviri M., Rafiee-Pour H. A., Ghourchian H., Gholami M. R., functionalized A., Appl. Nanoscience 1: 189 (2011).


Current World Environment

Vol. 7(2), 233-241 (2012)

Assessment of Arsenic, Nitrate and Phosphorus Pollutions in Shallow Groundwater of the Rural Area in Kurdistan Province (Iran) ZAHED SHARIFI* and ALI AKBAR SAFARI SINEGANI Department of Soil Science, College of Agriculture, Bu-Ali Sina University, Postal Code - 6517833131, Hamedan, Iran. (Received: July 12, 2012; Accepted: September 17, 2012) ABSTRACT Quality of water resources in the rural area of Qorveh Plain (Kurdistan Iran) is facing a serious challenge due to arsenic (As) pollution and agricultural development. Therefore, 25 shallow groundwater samples (from 14 households and 11 farms) were collected from this area with aim of evaluating their quality as drinking purposes. The water samples were analyzed for pH, water electrical conductivity (Ecw), As, Mn, Fe, Ca, Mg, Na, K, NO3, P, Cl, HCO3, SO4, Si, total hardness (TH), and total dissolved solids (TDS) by using standard methods. Results showed that the toxicity of arsenic (on average, 51.8 ppb), nitrate (on average, 116.7 ppm) and phosphorus (on average, 0.32 ppm) are in an alarming state in this area. Furthermore, all of the wells under test in this study fail to meet at least one safe drinking water standards, particularly with regard to arsenic, nitrate, TDS and pH. Among the appeared pollutions arsenic has a geologic origin and nitrate and phosphorus can affect by human activities such as agriculture, household chemicals, run-off and failing septic systems in this area. Based on the results of this assessment, the quality of the groundwaters is not suitable for drinking purpose without appropriate remediation.

Key words: Water quality, Arsenic, Nitrate, Phosphorus, Pollution, Iran.

INTRODUCTION The rule of water quality on human health is well known and recently attracted a great deal of interest. Many water quality problems have been identified and addressed in the past from several parts of the world1. According to Nature (2010) about 80% of the worldâ&#x20AC;&#x2122;s population (4.8 billion in 2000) lives in areas with threats to water security2. Most cases of waterborne diseases and related deaths occur in developing nations are directly due to unsafe water, unsanitary conditions and insufficient hygiene3, 4. Shallow groundwater provides drinking water for human in most parts of the world including Iran. But, the water table of shallow groundwater is often quite near the surface. Therefore, there are a lot of risks for this groundwater both on its quantity

and quality. In some areas groundwater resources are at risk from the results of point and non-point source pollutants such as agricultural fertilizer application, irrigation return flows, industrial and wastewater discharges, animal waste and household chemicals run-off, failing septic systems, etc5-7. Kurdistan, a western province of Iran, is facing the problem of As con-tamination with geologic origin. The discover y of As in the groundwater of Kurdistan is a major concern to peopleâ&#x20AC;&#x2122;s livelihood in the province. Exposure to high doses of As can cause organ cancers, organ damage, weakness, neural disorders and decreased appetite1, 8. Qorveh Plain is one of the most important agriculture areas in the Kurdistan province. However, the water and fertilizers in this area are not used effectively and economically.


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Thus, arsenic pollution along with agricultural drain waters from the heavy fertilizer lands is a great challenge to water recourses in this area. No sci-entific and systematic studies have been conducted in the region. However, several studies have documented that contamination (e.g. nitrate) of household and farm wells can occur from agricultural activities around the wells7, 9-11. In order to improvement in water supplies and sanitation, the monitor and assessment of water quality on regular basis is very important. Hence, the present work is undertaken with the objective to assess shallow groundwater quality for drinking purpose in the rural area of Kurdistan province (Iran). MATERIALS AND METHODS Study area Seven villages of Qorveh plain located around the Sari Gunay Gold Mine were selected for this study. These villages confined between longitudes 47° 57× 40' and 48° 8× 34' E and latitudes 35° 7× 2' and 35' 12× 47° N (Figures, 1a, 1b and 1c) in the northern-east region of Qorveh city in Kurdistan province, western Iran. The climate in this area is semi-arid and the average annual rainfall and temperature is 339 mm and 11.4 o C, respectively. Twenty-five shallow groundwater samples were collected from the area during September 2009. Of all these samples, 14 were collected from household wells (depth on average, 11 m) including Babashydolah (B1), Dashkasan (D1 to D6), Dosar (S), Jodaqye (G1 to G3), Narenjak (N) and Nayband (A1 to A3), the other 11 (depth on average, 26 m) were collected nearly from all shallow farm wells in this area including Babashydolah (B2 and B3), Dashkasan (D7 to D9) and Zang Abad (Z1 to Z5) (Table 1).

points used by local residents. The samples were collected after at least 10 min of pumps and taps operation. To keep the cations as solution and prevent adsorption or deposition on the walls of the sample containers, pH of the smaller containers was reduced to below 2 using ultra pure HNO3 immediately after filtering. After the sampling, the samples were immediately transferred to laboratory and refrigerated (at 4 °C) until their analysis. Sample analysis Samples were analyzed in the laboratory for the major physio-chemical properties according to the Standard Methods for the Examination of Water and Wastewater (volume 1) described in Andrew et al. (2005) [12]. The pH and water electrical conductivity (EC w) were measured on pH and electrical conductivity meters, respectively. Calcium (Ca2+) and magnesium (Mg2+) were determined by complexometric method. Chloride (Cl – ) was measured by AgNO3 titration method. Bicarbonate (HCO3–) was determined by titration with H2SO4. Sodium (Na+) and potassium (K+) were measured by flame emission photometric method. Sulphate (SO42–) was determined by turbidimetic method. Silicon (Si) was measured by the spectrophotometric molybdosilicate method. Nitrate (NO3–) and phosphorus (P) were measured by spectrophotometric method. Total arsenic (Astotal) was determined by the graphite furnace atomic absorption spectrophotometry (GF-AAS) (Varian 220, Mulgrave, Victoria, Australia) and the total iron (Fetotal) and total manganese (Mntotal) were also determined using atomic absorption spectrophotometry (AAS). Total hardness (TH) was calculated as CaCO3. Total dissolved solids (TDS) were calculated by using the following equation: TDS (ppm) = 640 × ECw (dSm–1).

Sampling method To collect the water samples, 300 ml (for assessment of cations) and 1000 ml (for assessment of anions plus pH and electrical conductivity (EC) clean polyethylene containers were washed by detergent, rinsed first with hot water, then once with 0.1 N HCl and twice with distilled water. Then containers were left to dry, and then they were capped. The containers were then ready to be used to collect the water samples from the wells. Water samples were collected from wells, taps or other

RESULTS AND DISCUSSION The physicochemical analyses of the household and farm wells were statistically analyzed and the results are presented in Tables 2 and 3 respectively. In this study, assessment of the suitability of collected samples for human consumption was evaluated by comparing the physicochemical parameters with standard set of the World Health Organization (WHO 2011a) [4].


SHARIFI & SINEGANI, Curr. World Environ., Vol. 7(2), 233-241 (2012) The results have been discussed by the following basic criteria (Tables 2 and 3): pH The pH values of the water samples ranged between 6.0 to 7.7 at household and 5.9 to 7.4 at farm wells. On average, water sampled from household wells (7.2, weakly alkaline) had comparatively higher pH contents than those sampled from farm wells (6.5, acidic). Lower pH values in the farm wells may be attributed by larger quantities of dissolved minerals15 and acidic ions such as SO42– due to the cropping activity (use of fertilizers, pesticides, etc) 14. It confirm by the higher amounts of SO42– and TDS at the farm wells than the household wells (Tables 2 and 3). In the current study because of acidic pH values of farm wells 54% of the samples go beyond the normal permissible range of pH (6.5-8.5) for drinking usage.

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However, 14% of household wells did not fall in this desirable range. Waters with a low pH are corrosive, which can damage to metal pipes and other fixture of the plumbing system. The problem is more acute when the waters contact toxic metal piping systems where these metals such as copper, lead, zinc, etc, can dissolve into the human’s drinking water. Arsenic The deleterious effect of heavy metals in the environment is well known 15 . Total As concentrations ranged from 15.6 to 60.5 ppb in household wells, 47.4 to 102.4 ppb in farm wells. It is a major concerning that all water samples from household and farm wells showed As concentrations of above the WHO guideline value in potable water (10 ppb) 4, while 91% of farm wells and 21% of household wells exceeded the

Table 1: Identification of sampling wells No

Code

Village and type of water

Depth (m)

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

B1 B2 B3 D1 D2 D3 D4 D5 D6 D7 D8 D9 S G1 G2 G3 N A1 A2 A3 Z1 Z2 Z3 Z4 Z5

Babashydolah, source of drinking water of village Babashydolah, farm well Babashydolah, farm well Dashkasan, source of drinking water of village Dashkasan, household well Dashkasan, household well Dashkasan, household Well Dashkasan, household well Dashkasan, household well Dashkasan, farm well Dashkasan, farm well Dashkasan, farm well Dosar, farm well Jodaqye, household well Jodaqye, household well Jodaqye, household well Narenjak, source of drinking water of village Nayband, household well Nayband, household well Nayband, household well Zang Abad, farm well Zang Abad, farm well Zang Abad, farm well Zang Abad, farm well Zang Abad, farm well

8 6 15 6 12 10 15 10 12 14 6 12 40 12 12 25 7 7 12 7 22 40 50 50 30


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maximum acceptable level in potable water in Iran (50 ppb) [16]. High concentration of As in the drinking water can have detrimental effects on health. It is worth to note that some multi-chronic arsenical poisoning symptoms, such as skin lesions (including, keratosis and pigmentation), and even amputation due to gangrene, have been reported among residents in west of Iran1, 8. In this area, as in many part of the world, naturally-occur-ring As is responsible for groundwater contamination. It is well known that natural enrichment of groundwater by As is governed by the geophysical, chemical and biological processes, such as oxidation–reduction, dissolution–precipitation and sorption– desorption177An important observation in this study is that As contamination was increased with depth of wells (r = 0.71; P<0.01) and its concentration in farm wells (on average, 70.8 ppb) was nearly 2 times higher than household wells (on average, 36.8 ppb). In fact, in household wells, As concentrations in 79% of water samples stay below

50 ppb because As in the oxic shallow groundwater, and in recharging water, is sorbed to aquifer sediments18. Iron and manganese Total iron and Mntotal concentration varied from 0 to 0.23 and 0 to 0.33 ppm in household wells, and 0.03 to 1.86 and 0 to 0.12 ppm in farm wells, respectively. Out of all wells sampled, D7 and D9 (from farm wells) contain Fetotal higher than allowable limit (0.3 ppm) for drinking purpose [4]. Eight percent of water samples i.e. D5 (from household wells) and D9 (from farm wells) showed Mntotal concentrations above the allowable limit (0.1 ppm) for drinking usage4. Nitrate and phosphorus The concentrations of NO3– varied from 23.2 to 916.9 ppm at household wells, 1.8 to 79.0 at farm wells with a mean of 178.3 and 38.2 ppm, respectively. In compared to the WHO’s drinking

Table 2: Summary statistics of physicochemical analysis and wise suitability categorization of them for drinking in household wells collected in the rural area of Qorveh plain (unit as ppm except As (ppb) and Ecw (dSm-1) Parameter

Min

Mean

Max

Std. dev.

MPL1 (WHO, 2011a)

SEMPL2

pH AsTotal NO3-

6.0 15.6 23.2

7.2 36.8 178.3

7.7 60.5 916.9

0.5 14.2 234.4

6.5-8.5 10 50

Cl HCO3SO42P Na + K+ Ca2+ Mg2+ FeTotal MnTotal SiO2 Ecw5 T.D.S6 TH7

34.5 201.0 37.8 0.02 41.0 1.0 52.75 7.3 N.D N.D 16.2 0.44 279.2 162.0

139.9 333.5 133.0 0.09 91.4 5.9 152.0 38.1 0.09 0.03 23.8 1.30 826.5 536.5

469.0 461.5 309.7 0.19 169.6 30.4 468.9 125.4 0.23 0.33 37.5 3.50 2217.3 1687.1

122.4 86.1 95.1 0.05 32.2 7.9 108.3 33.1 0.07 0.08 6.6 0.78 501.7 401.8

250 N.G 250 N.G 200 N.G 200 150 0.3 0.1 N.G N.G 1000 1000

14% (D3&D5) 100% 71% (N,D1,D3-D6, G1,G3,A1&A3) 14% (A13&D3) – 14% (D4&G3) – 0 – 14% (D3&D4) 0 0 7% (D5) – – 28% (A1,G1,D3&D4) 0

1 5

Maximum Permissible Limits, 2Samples Exceeding the Maximum 3Not Detected Permissible Limits, 4No Guideline, Water Electrical Conductivity, 6Total Dissolved Solid, 7Total Hardness


SHARIFI & SINEGANI, Curr. World Environ., Vol. 7(2), 233-241 (2012) water guideline of 50 ppm for NO 3" , 71% of household wells and 45% of farm wells showed higher concentrations4. The high concentration of nitrate in the surveyed groundwaters is toxic and can cause methemoglobimia or blue-baby syndrome in infant and also can increase the risk of gastric cancer19. In compared to farms wells, concentrations of nitrate at household wells were unusually high (on average 178.3 ppm). It can be as a result of closeness of septic tank to the wells20, 21, lower depth and higher pH of the wells15 and abandoned livestock yards in the rural area. In addition to all the aforementioned, most of the household wells often left open that exposes the wells to contamination by runoff during heavy precipitation. The concentration of phosphorus was between 0.02 to 0.19 ppm at household wells, 0.05 to 0.17 ppm at farm wells. There is no guide line for phosphorous in drinking water, but phosphorus concentrations in all of the water samples were considerably higher than the

237

normal limit of phosphorus (0.02 ppm) in shallow groundwater24. It is possible that the high concentration of nitrate and phosphorous in these groundwaters result from excessive application of manure and inorganic fertilizer at a rate greater than agronomic rate in this area. Farmer inquiries indicate that in addition to chemical fertilizer – used often up to 2– 3 times the recommended rate – the use of organic manure, especially poultry manure, the type most frequently used (for potato fields about 10 ton ha1 year-1 is used). Nitrate and phosphorus from such sources coupled with widespread irrigation can be increased groundwater contamination via runoff and infiltration in this area as previously shown by Jeyaruba and Thushyanthy (2009) [23] and Jalali (2005 and 2009) 10, 11. Chloride The concentrations of Cl – ion lie in between the ranges of 34.5 to 469.0 and 51.5 to 202.7 with a mean of 139.9 and 112.0 ppm, at

Table 3: Summary statistics of physicochemical analysis and wise suitability categorization of them for drinking in farm wells collected in the rural area of Qorveh plain (unit as ppm except As (ppb) and Ecw (dSm-1) Parameter Min

Mean

Max

Std. dev.

pH AsTotal NO3Cl HCO3SO42P Na + K+ Ca2+ Mg2+ FeTotal MnTotal SiO2 Ecw5 T.D.S6 TH7

6.5 70.8 38.2 112.0 600.0 187.6 0.1 122.2 11.7 185.0 33.0 0.3 0.02 26.0 1.47 944.4 597.8

7.4 102.4 79.0 202.7 958.3 331.1 0.17 151.8 28.2 253.2 64.2 1.9 0.12 35.4 1.91 1223.4 756.2

0.6 19.0 27.3 38.7 187.7 65.9 0.04 19.8 5.7 50.3 14.4 0.04 0.04 4.8 0.28 179.1 102.7

1 5

5.9 47.4 1.8 51.5 397.4 85.3 0.05 91.2 7.7 117.2 7.3 0.03 N.D 19.2 1.02 652.2 448.8

MPL1 (WHO, 2011a) 6.5-8.5 10 50 250 N.G 250 N.G 200 N.G 200 150 0.3 0.1 N.G N.G 1000 1000

SEMPL2 54% (D9&Z1-Z5) 100% 45% (B2,S&Z2-Z4) 0 – 9% (S) – 0 – 45% (S,Z1&Z3-Z5) 0 18% (D7&D9) 9% (D9) – – 45% (S,Z1&Z3-Z5) 9% (D9)

Maximum Permissible Limits, 2Samples Exceeding the Maximum 3Not Detected Permissible Limits, 4No Guideline, Water Electrical Conductivity, 6Total Dissolved Solid, 7Total Hardness


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household and farm wells, respectively. The concentration of Cl– at all of farm wells were well within the acceptable drinking limit values for Cl– (250 ppm) [4], however, 14% of household wells i.e. A1 and D3 exceeded the recommended level. Bicarbonate and sulphate The concentrations of HCO3– and SO42– varied from 201.0 to 461.5 and 37.8 to 309.7 ppm at household, 397.4 to 958.3 and 85.3 to 331.1 ppm at farm wells, respectively. Fourteen percent of household wells and 9% of farm wells were beyond the permissible limit (250 ppm) for SO42– [4]. Although the amount of this ion at Z2 (176.7 ppm), Z3 (192.3 ppm) and Z4 (213.8 ppm) was considerable.

Sodium, Calcium and magnesium The concentrations of the Na+, Ca2+ and 2+ Mg ranged from 41.0 to 169.6, 52.7 to 468.9 and 7.3 to 125.4 ppm, with the respective average values 91.4, 152.0 and 38.1 ppm at household wells, 91.2 to 151.8, 117.2 to 253.2 and 7.3 to 64.2 ppm with the respective average values 122.2, 185.0 and 33.0 ppm, at farm wells. As shown in Tables 2 and 3 all of water samples under test are well within the acceptable drinking limit values for Na+ (200 ppm) and Mg2+ (150 ppm) [4]. However, 14% of household wells i.e. D3 and D4 and 45% of farm wells i.e. S, Z1 and Z3 to Z5 are exciding the maximum permissible level for Ca2+ (200 ppm) in drinking water4.

Fig. 1: The Sanandaj-Sirjan zone in Iran (a), Kurdistan province map and location of study area (b), Location of farm wells sampled (c)


SHARIFI & SINEGANI, Curr. World Environ., Vol. 7(2), 233-241 (2012) Silica and potassium The Si and K+ concentrations varied from 16.2 to 37.5 and 1.0 to 30.4 ppm, with the respective mean values of 23.8 and 5.9 ppm at household wells, 19.2 to 35.4 and 7.7 to 28.2 ppm, with the respective mean values 26.0 and 11.7 ppm at farm wells. Permissible limit for silica in drinking water have not been prescribed not only by the WHO but also by similar agencies. However, in view of the high concentration of Si in the Earth’s crust (28% by weight); life would have been real precarious if excessive ingestion of Si is really harmful. Further research is required in this direction. In the case of potassium, although potassium may cause some health effects in susceptible individuals, potassium intake from drinking-water is well below the level at which adverse health effects may occur24. Thus, there is no guideline for potassium.

239

consumers, owing to excessive scaling in water pipes, heaters, boilers and household appliances4. Total Hardness (TH) Water hardness is primarily due to the amount of calcium and magnesium and, to a lesser extent, iron. The TH value ranged from 162.0 to 1687.1 and 448.8 to 756.2 with an average of 536.5 and 597.8 ppm as-CaCO3, in household and farm wells, respectively. According to the grading standards of TH, all of farm wells and 71% of household wells fall in the very hard waters category (TH>300 ppm as-CaCO3). The recommended value of TH for potable water is 1000 mg as CaCO3. The TH of all water samples except one sample (D9) was well within the permissible limit. But previous studies have shown that consumption of waters with high TH cause numerous human diseases such as heart disease and kidney stone27.

Salinity Salinity is the total amount of inorganic solid material dissolved in any natural water, and water salinization refers to an increase in total dissolved solids (TDS) and the overall chemical content of the water25. Salinity of groundwater is a useful indicator of the land area and drinking water at risk from salinity. Electrical conductivity and TDS are used as tools for salinity assessment; their amounts ranged from 0.4 to 3.5 dSm–1 and 279.2 to 2217.3 ppm at household wells, 1.0 to 1.9 dSm–1 and 652.2 to 1223.4 ppm at farm wells, respectively. As shown in Tables 2 and 3, on average, the TDS at farms wells (944.4 ppm) was higher than household wells (826.5 ppm), it can be attributed to the grater effects of human activities such as application of fertilizers and irrigation practice on salinity of farm wells than the household wells in this area. Previous studies have shown that salinity is usually affected mainly by topography, lithology of aquifer, recharge, runoff and discharge conditions of groundwater 26. The palatability of water with a TDS level of less than about 600 ppm is generally considered to be good; all of farm wells and 71% of household wells were exceeded this desirable limit. However, Drinkingwater becomes significantly and increasingly unpalatable at TDS levels greater than about 1000 ppm; 28% of household wells and 45% of farm wells exhibit TDS values outside the maximum permissible limit. The presence of high levels of TDS in these groundwaters can have an objectionable to

CONCLUSIONS The shallow groundwater sources in the rural area of Kurdistan province have been evaluated for their physicochemical composition and suitability for drinking purpose. Results showed that As, NO3– and P pollution are in an alarming state in this area. The observed As in these groundwaters has a geologic origin and the high NO3– and P could occur from human activities such as agriculture, household chemicals run-off and failing septic systems. All wells under test failed at least one safe drinking water standard. So that, based on Astotal, NO3–, TDS, pH, Ca2+, SO42– and Mntotal, 100%, 71%, 28%, 14%, 14%, 14%, and 7% of analyzed samples at household wells and 100%, 45%, 45%, 54%, 45%, 9%, and 9% of analyzed samples at farm wells were unsuitable for human consumption, respectively. Other parameters that exceeded WHO guideline values in this assessment were Fetotal (18% of farm wells) and Cl – (14% of household wells). In conclusion, in order to improve public health, the users of the groundwaters must be awareness on the dangers of consumption of the waters. ACKNOWLEDGMENTS We acknowledge our gratefulness to the residents of all the villages we visited for their contribution to the research.


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a semi-arid basin southern Malayer western Iran, Environ. Geol., 57: 1011-1020 (2009). G.S. Kalwania and R. Shyam, Orient J. Chem, 28(1): 547-552 (2012). B.Y. Kamaruzzaman, M.S. Zahir, B.A. John, K.C.A. Iqbal and J.S. Goddard, Orient J. Chem, 27(2): 505-510 (2011). Andrew D. Lenore S. Eugene W. and Arnolr E., Standard Methods for the Examination of Water and Wastewater, 21th edition, American Public Health Association/ American Water Works Association/Water Environment Federation Washington DC (2005). Napacho Z.A. and S.V. Manyele., Quality assessment of drinking water in Temeke District (part II): Characterization of chemical parameters, Afr. J. Environ. Sci. Technol., 4(11): 775-789 (2010). Liu A. Ming J. and Ankumah R. O., Nitrate contamination in private wells in rural Alabama United States, Sci. Total. Environ., 346(1-3): 112-120 (2005). Sharma R. K. and Agarwal M., Biological effects of heavy metals. J. Environ. Biol., 26: 301-313 (2005). Iranian Industrial Research and Standard Association Natinal standard of drinking water, Repor t of the Iranian Industrial Research, No, 1053 (1999). Wang S. and Mulligan C. N., Natural attenuation processes for remediation of arsenic contaminated soils and groundwater, J. Hazard. Mater., 138: 459-470 (2006). Nickson R. T. McArthur J. M. Shrestha B. KyawMyint T. O. and Lowry D., Arsenic and other drinking water quality issues Muzaffargarh District Pakistan, Appl. Geochem., 20(1): 55-68 (2005). Fewtrell L., Drinking-Water Nitrate Methemoglobinemia and global burden of disease: a discussion, Environmental Health Perspective, 112: 1-5 (2004). Abdel-Lah A. K. and Shamrukh M., Impact of septic system on ground water quality in a nile valley village Egypt, Sixth International Water Technology Conference IWTC, Alexandria Egypt, (2001).


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Current World Environment

Vol. 7(2), 243-250 (2012)

Insect Diversity and Water Quality Parameters of Two Ponds of Chatla Wetland, Barak Valley, Assam PINKI PURKAYASTHA and SUSMITA GUPTA* Department of Ecology and Environmental Science, Assam University, Silchar - 788 011, India. (Received: July 12, 2012; Accepted: September 17, 2012) ABSTRACT An investigation was carried out on two ponds of Chatla floodplain, Barak valley, Assam with special reference to aquatic insects. Pond 1 is purely a fish pond where as pond 2 is a community pond too. Present study revealed the status of water quality and in turn diversity, density, dominance and abundance of aquatic insects in both the ponds. Almost all the physico chemical parameters of both the ponds were found within permissible range for aquatic life .However in pond 2 level of phosphate was found little higher than pond 1 due to release of soaps and detergents by human influence. In both the ponds order Hemiptera showed maximum relative abundance ( 98% in pond 1 and 94% in pond 2). The study revealed lower diversity of aquatic insects in pond 2 than that in pond 1.

Key words: Chatla floodplain, Pond, Human interference, Water quality, Aquatic insects.

INTRODUCTION Among different ecosystems, wetlands constitute one of the most important ecosystems for man offering numerous regulating services. Water quality assessment of small water bodies of the wetlands are of immense importance in the management of fisheries, water supply, and irrigation. Pollution status of water bodies are usually expressed as biological and physico-chemical parameters1. Several authors have extensively documented the responses of macro-invertebrates to organic and inorganic pollution 2,3 . Chatla floodplain (24042/697// N and 92046/264//E) situated in the south of Silchar town, Barak Valley, Assam has 1500 fishery ponds and 12 seasonal lakes. (Fig.1). Although the wetland is resourceful with variety of macrophytes, trees and fishes it is in a derelict or near derelict state due to high rates of siltation, infestation of weeds, unscientific fishing activities, and use of pesticides in the surrounding tea gardens and agricultural fields 4 which led to a loss of 73% wetland area of Chatla floodplain 5. All these factors can affect the communities of aquatic organisms leading to loss of diversity and species

extinction 6. Since, fluctuations in aquatic insect community can give quick information of their surrounding water quality and are commonly used as tools for marking an integrated assessment of water quality, investigation on water quality of two fishery ponds of Chatla wetland with special reference to aquatic insects was carried out. MATERIALS AND METHODS The topography of the Chatla floodplain is fenland type with small hillocks strewn among large stretches of lowland. Pond 1 is a fish pond and is relatively undisturbed. Pond 2 is a fishery cum community pond. Water and insect samples were collected in replicates from both the sites during 2009-2010. Physico-chemical parameters such as Air temperature (AT), Water temperature (WT), Transparency, pH, Electrical Conductivity (EC), Dissolved oxygen (DO), Free CO2 , Total alkalinity (TA), Nitrate (NO3-) and Phosphate (PO4 3), Nitrite (NO2- ), and Ammonium (NH4 +) content of water were analyzed by standard methods 7,10. The aquatic insects were collected by kick method whereby the vegetation was disturbed and the


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circular net (mesh size 60µm) was dragged around the vegetation for one minute 11-12. They were immediately sorted, preserved in 70% ethyl alcohol and were later identified using Dewinter advanced stereo zoom microscope with the help of standard keys 13-19. A number of identified insects were confirmed in the entomological laboratory of Zoological Survey of India. Statistical analyses were done by MS EXCEL 2007; SPSS 15.0 for Windows, Shannon Wiener Index of Diversity (H/ ), Evenness Index (J/) and Berger–Parker Index of Dominance (d) were calculated by Biodiversity professional version 2 for windows. RESULTS AND DISCUSSION Different physico-chemical parameters (AT, WT, Transparency, pH, EC, DO, Free CO2,TA, PO4 3-, NO3 -, NO2 -, NH4 +) in pond 1 and 2 during Post monsoon 2009 to Monsoon 2010 and their mean concentrations are shown in Table 1. Table 2 showed the distribution of aquatic insects in pond 1 and 2. The significant correlations that exist among environmental variables, diversity and density of insect are shown in Table 3. Fig.2 showed the relative abundance of aquatic insect orders recorded from pond 1 and pond 2 during the study period. Relative abundance of aquatic insect families and aquatic insect species in pond 1 and 2

are shown in the Fig.3 and Fig.4 respectively. Pattern of variation in the levels of Shannon – Weiner Diversity index (H’) and Evenness index (J’) and Berger-Parker index of Dominance (d) are shown in the Fig.5.The study revealed that in pond 1 and 2 both air and water temperature did not show much variation. In pond 1 DO, EC, NH4 and NO3 - concentration were slightly higher than that of pond 2 while other parameters such as Transparency, Free CO 2 , TA, pH, and PO 4 3concentration were recorded to be higher in pond 2. The solubility and availability of nutrients is affected by oxygen content of water and therefore the productivity of aquatic ecosystems 18. The range of DO recorded in the present study is similar to the DO concentration reported in a previous study in the same area21. In pond 1 correlation coefficient analyses revealed a significant negative relationship of WT with pH and DO. Classical negative relationship of WT with DO was also recorded in a previous study on Chatla floodplain 22 which is attributed to the fact that in lower temperature oxygen carrying capacity of water increases 23. Negative relationship of DO with Rainfall might be an indication that surface runoff transported sewage, fertilizer etc. into the pond which have lowered DO value by bacterial respiration 22. EC was found to be higher in pond 1 (4.59ms/ppt ± 2.93) compared to pond 2 ( 3.24ms/

Table 1: Physico-chemical properties of water of Pond 1 and Pond 2 Study Sites Pond 1

Pond 2

Parameters

Range

Mean±Std dev.

Range

Mean±Std dev.

AT(0C) WT(0C) Rainfall(cm) pH EC (ms/ppt) Transparency (cm) DO ( mg l-1 ) Free CO2( mg l-1 ) TA( mg l-1 ) PO4 3- ( mg l-1 ) NO3- ( mg l-1 ) NO2-( mg l-1 ) NH4 +

22.6-29.83 23.37-31.5 0-1484.7 5.24-6.88 0.10-3.57 0-33.67 5.91-10.43 2.31-11.65 11-30.53 0.32-1.88 0.14-1.01 0.007-0.02 0.08-0.48

25.93±0.75 26.13±1.40 551.98±590.2 6.27 ± 0.31 4.59 ± 2.93 14.79 ± 1.60 8.84 ± 0.86 8.28 ± 0.57 19.93 ± 2.26 0.86 ± 0.27 0.53 ± 0.23 0.01 ± 0.01 0.30 ± 0.13

22.6-29.3 23-30.5 0-1484.7 6.38 – 7.8 0.09-7.82 13.08-24.83 6.77-9.18 8.42-35.60 10.43-52.37 0.40-2.16 0.13-0.66 0.01-0.08 0.07-0.33

25.09 ± 0.88 26.83 ± 0.75 551.98±590.2 7.15 ± 0.52 3.24 ± 0.20 17.19 ± 2.77 7.83 ± 0.72 16.15 ± 1.60 26.89 ± 3.49 1.25± 0.72 0.46 ± 0.19 0.03± 0.03 0.17 ± 0.09


PURKAYASTHA & GUPTA, Curr. World Environ., Vol. 7(2), 243-250 (2012) ppt Âą 0.20) where it showed significant positive correlation with TA and NO3-. The range of NO3-. between 0.1 - 3.0 mgl-1 is considered favorable for fish productivity 25 . In both the ponds, NO 3 -. concentration was found within the said range indicating their suitability for fish production. In pond 2 EC showed significant positive correlation with

TA, Free CO 2, and DO. Higher free CO 2 accompanied by higher TA and higher pH in pond 2 could be due to external application of lime. It is known that addition of lime increases fish production in soft (low total hardness) waters by stabilizing the pH of bottom mud and increasing the availability of Phosphorus and Carbon dioxide for

Table 2: Distribution of aquatic insect species in Ponds 1 and 2 of Chatla floodplain during study period Order

Family

Sp. Name

Pond 1

Pond 2

Hemiptera

Gerridae

Gerris lepcha Distant Limnogonus nitidus Mayr Neogerris parvula StĂĽl Mesovelia vittigera Horvath Enithares fusca Brooks Anisops barbata Brooks Enallagma sp. Culex sp.

+ + + + + + + -

+ + + + + + +

Mesoveliidae Notonectidae Odonata Diptera

Coenagrionidae Culicidae

245

Table 3: Significant Correlations among environmental variables, diversity and density of aquatic insects for pond 1 and pond 2 Parameters

Pond 1

Pond 2

WT Vs pH WT Vs DO pH Vs DO pH Vs Rainfall EC Vs DO EC Vs Free CO2 EC Vs TA EC Vs NO3DO Vs Rainfall DO Vs TA Free CO2 Vs Insect Density TA Vs NO3NO3- Vs Rainfall NO2- Vs NH4+ NO2- Vs Rainfall PO43- Vs NO2PO43- Vs Insect density NO2- Vs Insect density Transparency Vs Diversity of insects

-.956(*) -.989(*) .989(*) -.987(*) .970(*) .983(*) -.961(*) .997(**) .955(*) -.984(*) -.963(*) -

.995(**) .954(*) .973(*) .977(*) .993(**) -.993(**) .967(*) .960(*) .977(*)

* Correlation is significant at the 0.05 level (2-tailed). ** Correlation is significant at the 0.01 level (2-tailed).


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Fig. 1: Location of the two Ponds , 1 and 2 in the floodplain of Chatla Wetland

Fig. 2: Relative abundance of insect orders in Pond 1 and Pond 2

Fig. 3: Relative abundance of aquatic insect families in Pond 1 and Pond 2


PURKAYASTHA & GUPTA, Curr. World Environ., Vol. 7(2), 243-250 (2012) photosynthesis. The overall effect of liming is to increase phytoplankton production which results in increased fish production26. Another reason might be that in heavily stocked fish ponds, Carbon dioxide (CO2) concentration can become high as a result of respiration. High CO2 concentrations are almost always accompanied by low DO concentrations (high respiration). Acidity of rain water has impact on the pH of natural water bodies. As rain falls to the earth, each droplet becomes saturated with CO 2 and pH is lowered 27 . This

247

explained the negative relationship of Rainfall with pH in pond 1. However in pond 2 no such relationship could be found due to application of lime. In pond 1 DO has shown significant positive correlation with pH , such type of positive correlation in between DO and pH have been recorded from the study of Asa lake llorin , Nigeria28 where DO distribution followed a similar annual cycle with the pH. In pond 2 DO has shown a positive significant correlation with TA. These alkalinity relationships are extremely important in water

Fig. 4: Relative abundance of aquatic insect species in Pond 1 and Pond 2

Fig. 5: Pattern of variation in the levels of Shannon diversity index, Evenness index and Berger-Parker dominance of different insect species in both the Ponds


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chemistr y, since the most prominent water problems are deposits and corrosion, and these are closely related to the instability of each specific water caused by the tendency of CaCO 3 to dissolve in or precipitate from it 29. Range of PO 43- ( 0.86 ± 0.27 in pond 1 and 1.25 ± 0.72 in pond 2) recorded in the present study is supported by the previous study in a marsh of the same floodplain 30. Relatively high concentration of PO 4 3- in pond 2 might be due to its use as community pond where PO 43- is contributed by household activities such as washing, bathing etc. In pond 1 PO 4 3- has shown significant positive correlation with NO 3 . Actually large concentration of PO 43- and NO 3 reported together from a water body indicate that water is eutrophic in nature 31 but as the water of this pond showed low concentration of both ,it indicates the water is not eutrophicated. Rainfall showed significant negative relationship with NO 3 - and positive correlation with NO 2 - in pond 2. A previous study conducted in the same study area also reported relatively high concentration of NO 3 during dry months 32. A positive correlation between NO 2- and NH 4+ is supported by the fact that the most possible way of Nitrate entry in an aquatic system is through oxidation of Ammonia form of Nitrogen to NO 2- and to NO 3 consequently 31. Aquatic insect community of pond 1 was represented by two orders- Hemiptera, Odonata; four families- Gerridae, Notonectidae, Mesoveliidae (Hemiptera), Coenagrionidae (Odonata) and seven species. Pond 2 was represented by three orders Hemiptera, Odonata, Diptera; five families- Notonectidae, Gerridae, Mesoveliidae (Hemiptera), Coenagrionidae (Odonata); Culicidae (Diptera) and seven species (Table 2). In both the ponds order Hemiptera was the most prominent order, having 98% relative abundance in pond 1 and 94% in pond 2. The most abundant family in Pond 1 is Notonectidae (64%), followed by Gerridae (32%), Mesoveliidae (2%), and Coenagrionidae (2%). In Pond 2 the relative

abundance of Gerridae was highest (76%) followed by Notonectidae (16%), Coenagrionidae (5%), Mesoveliidae (2%) and Culicidae (1%) (Fig.2 and 3). The aquatic insect species found common in both the ponds were Gerris lepcha Distant, Limnogonus nitidus Mayr, Enithares fusca Brooks, Mesovelia vittigera Horvath , Enallagma sp . and Anisops barbata Brooks. In addition to these species Neogerris parvula Stål was recorded in pond 1 and Culex sp. in pond 2 (Fig.4). Values of Shannon –Weiner Diversity index (H’) and Evenness index (J’) were found higher in pond 1 than that of Pond 2 while Berger-Parker index of Dominance (d) value was found higher in pond 2 (Fig. 5). However the H’ values were found to be less than 1 in both the ponds indicating polluted nature of water35. In pond 1 insect density has shown negative correlations with PO43- and NO2. This might be due to the reason that increased pollution level with high concentration of PO 43and NO2-.might have disturbed the colonization as many species of aquatic insects are very susceptible to pollution or alteration of their habitat 33. In pond 2 density of aquatic insects showed positive correlation with Free CO 2 which might be due to increased respiration by more number of insects. Rainfall 34 has shown no significant relationship with diversity or density of aquatic insects in both the ponds. The diversity of aquatic insects showed positive correlation with Transparency. Such kind of positive correlation was reported from lake Victoria 37. From the study, it can be said that different physico chemical parameters of water quality are inter related and these factors influence diversity, density and distribution of aquatic insects in a particular water body. ACKNOWLEDGEMENTS The authors are thankful to University Grants Commission, New Delhi, India for financial support. Authors are also thankful to the Head, Department of Ecology and Environmental Science, Assam University, Silchar, Assam for providing laboratory facilities.


PURKAYASTHA & GUPTA, Curr. World Environ., Vol. 7(2), 243-250 (2012)

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Current World Environment

Vol. 7(2), 251-258 (2012)

The Occurrence of TDS and Conductivity of Domestic Water in Lumding Town of Nowgong District of Assam, N.E. India M.K. PAUL1 and SUJATA SEN2 1

Department of Chemistry, Lumding College, Lumding - 782 447, India. 2 Department of Geology, Lumding College, Lumding - 782 447, India. (Received: July 12, 2012; Accepted: September 17, 2012) ABSTRACT

Total dissolved solid (TDS) and Conductivity are important parameters to determine the quality of water. The seasonal variations in TDS are mainly due to the ionic composition of water. In the present study the seasonal variations in TDS and Conductivity of Lumding Town were studied from May, 2001 to April, 2004. It was found that the TDS of Dug well, Ring well and Ponds were maximum high, but the TDS of River water and Supply water were appreciable.

Key words: TDS, Conductivity, Domestic Water

INTRODUCTION Water- the elixir of the life system and without it life cannot exist. The diverse uses of water for drinking, cooking, washing, bathing a lot of other purposes. The presence of safe and reliable drinking water is an essential prerequisite for a stable community. So quality of water is to be determined for a locality of various purposes. Water covers about 71 percent of the earth’s surface and it is abundant natural resource on the earth. It includes various resources such as rivers, seas, lakes, oceans, glaciers, groundwater, surface water, streams etc. Without water, life of any kind is not possible. Drinking water quality is a matter of concern as it is related to human health and many hazardous problems may arise due to various pollutants in it. Drinking water sources have been poisoned by directly or indirectly by sewage, pesticides, fertilizers, excess salt, agricultural run off and drainage water from households and also from industrial run off or due to natural geological factors. It is difficult to get pure potable water for public health and water scarcity has led to take unsafe, unconventional water sources. The water

balance is also causing change due to human activities like industrialization, deforestation and population explosion. Water is a “ Cradle of life” on which all organism play. As water balances human body in a positive way, it has a negative role in transmitting variety diseases and other pathogenic germs. Many physico-chemical parameters in water is not in a proper way, they have harmful factor. In developing and underdeveloped countries to get pure potable water is a difficult term and contamination of drinking water by domestic and industrial water as well as human and animal excreta is a common feature. If the amount of certain chemicals crosses the permissible limit causes harmful to public health. Many studies have carried out on the quality of drinking water in various parts of the country but for Lumding Town no attempt has been taken so far. Study area The district of Nowgong is situated on the South bank of Brahmaputra occupies a central geographical position in the state of Assam. The district lies between 25 045" and 26 045" North latitudes and 91050" and 93020" East longitudes.


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Lumding Town is 90 Kilometer far South East direction of the Nowgong from the district. The Lumding town is surrounded by Mikir hills (Now N.C. hills/Dima Hasao District) on its three sides (east, west and south) and in the west it is covered by deep forest, which is named as Lanka Forest. The area of Greater Lumding is 411.8 Sq.km as per 1971 census (Assam District Gazetters, 1978). Lumding Town is a valley like place surrounded by hills and the place is important as it connects the Barak Valley, Upper Assam and Lower Assam by various trains. Its projected population is 2 lakhs. The railway people are dependent on its own supply water, which is irregular, insufficient and limited to only railway areas. The other people depend on dug wells, ring wells, ponds, rivers etc. The place is highly dry area, i.e., during March to May. Weather is pleasant due to high humidity. During the month July â&#x20AC;&#x201C; August the temperature becomes very high 350C to 390C. The southwest monsoon continues during June to September and during this period 85 - 90% rainfall occurs. There is no major industrial establishment in this town. There are a few factories like soaps, biscuits, potteries, plywood, and brick industries. The brick industries contribute to the soil and the land becomes unfertile and polluted. The big railway industry distributes effluent like burning diesel etc. to the soil and water. There are a few big drain of the railway and its attached area to release polluted waters from the town but there is no proper outlet for them. In civil areas many new drain construction are going on by municipality and PWD. The commercial wastes of the market and household wastes are dumped hither and thither inside the town. Sometimes these wastes are burnt without incinerators. Sometimes proper sanitary systems are not observed. They produce odor pollution and contamination and sewerage goes to the drinking water. Increase of vehicles with leaded petrol contaminates to the nearby drinking water adjacent to the roads. Sometimes pitching makes water and soil pollution and the people are affected by carcinogen. Village people are dependent on rabi and kharif crops and for them they use various fertilizers and pesticides and ultimately affect their land use pattern and these washed away by surface

run off. Overall the modern society uses various non-biodegradable polymeric products they accumulates in water bodies and also penetrates to the soil â&#x20AC;&#x201C; thus pollutes the ground and surface water. During the summer and rainy seasons various people of the locality are affected by water borne diseases like typhoid, dysentery, diarrhea, jaundice etc. and many lives have gone due to these diseases. Aquatic biotas are also affected by consuming polluted water. Common people are not concerned with the chemistry of water because polluted waters occur 80% of diseases. So it is important to determine the chemical quality of water for human welfare. Aims and objectives Water and its quality is deteriorated day by day by modern civilization, population explosion, household byproducts and sewage materials. The geochemical position of an area are also determines the presence of various chemicals present in drinking and other types of water in a locality. Due to direct relationship of water with human health and so very limited supply of freshwater for domestic purposes, the problems of them were considered. The following objectives was aim of this study:1. To determine the quality of water from various drinking water sources with respect to the total dissolved solid (TDS) and Conductivity. 2. To determine the conclusion regarding the drinking water quality in Lumding Town of Nowgong District of Assam, India. MATERIALS AND METHODS To study the water quality parameters from different sources of Lumding Town of Nowgong District, the samples were collected season wise depending on climatic and geographical conditions of the town. The samples were collected in different seasons throughout the whole year from to May, 2001 to April, 2004. Water samples were collected in pre- cleaned polythene containers of 2 litres capacity from Dug well (DW), Ring well (RW), Pond


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Table 1: The name of the sampling stations, serial no. and nature of the sources are given below S. No.

Sampling stations

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.

Nadirpar Halflong Road Subash Palley Patupather Khanger basti Santipara Subash Palley Ananda Palley Lanka Road Upper Babupatty Nadirpar (East Lumding) Bazar Area (Main Bazar) Jarangdisha New Coloney Samajbari Area Buddhamandir Murabasti Kamakhya Colony Loco Coloney Nadirpar (Sitlabari Area) Ananda Palley Halflong Road Santipara Jarangdisha Jhulanpool Lanka Road Near DRM Office Balunala Railway Coloney ASEB Area

Nature of source DW DW DW DW DW RW RW RW RW RW RW RW RW RW RW RW RW RW P P P P P P R R R R RSW PHE

Abb : DW – Dugwell, P = Pond, RSW – Railway supply water, RW – Ring Well, R – River, PHE – Public Health Engineering supply water.

(P), River water (R), Public Health Engineering (PHE) and Railway supply water (RSW). Total Dissolved Solids(TDS) TDS is determined as according to the APHA procedure. TDS is determined as the residue left after evaporation of the filtered sample

TDS, mg/l =

( A − B) ×1000 V

Where A = Mass of dried residue and beaker in g, (after evaporation), B = Initial weight of the beaker in g, V = Vol. of water taken. The process is as above of the total solids determined, but here the water samples are filtered by Whatman 40 and having 50 ml. sample and then evaporated to dryness and then the beaker dried


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Fig. 1: Relative variation of Conductivity with respect to TDS for Dugwells, RSW and PHE water samples

Fig. 2: Relative variation of Conductivity with respect to TDS for Ringwell water samples

Fig. 3: Relative variation of Conductivity with respect to TDS for Pond and River water samples


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Fig. 4: Relative variation of TDS, Conductance and Chloride (All Season Mean) for dugwells, RSW and PHE water samples

Fig. 5: Relative variation of TDS, Conductance and Chloride (All Season Mean) for ringwell water samples

Fig. 6: Relative variation of TDS, Conductance and Chloride (All Season Mean) for Pond and River water samples


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in an oven at 103 â&#x20AC;&#x201C; 1050C and weighed. Initial weight of the beaker was also taken. TDS affects water quality in different ways. Excessive TDS in water imparts a bad taste in water due to mineralization of various salts. A dissolve solid over 2000 mg/l produces a laxative effect (Kumaraswamy, 1991, Dembere 1998) This is due to Magnesium sulphate along with some sodium sulphate. Sodium parts affect the cardiac part and women with toxemia associated with pregnancy (Train, 1979). The maximum permissible limit of TDS in drinking water is 1000 mg/l (WHO). For irrigation it is 500 mg/l and above this limit crops have detrimental effect (Dieborg 1991). Total dissolved solids can be determined by two methods. In the first method the EC values are multiplied with factor, which is usually, varies from 0.55 mg/l to 0.75 mg/l depending upon the nature of ions present. Because electrical conductance and total dissolved solids are independent it is generally agreed that, if the TDS are less than 3000 mg/l, the factor 0.64 (Kumar and king, 2004) can be used to multiply the EC values to obtain the TDS values. In other method, the TDS values can be determined by evaporation technique in which the total solid material will be collected and determined gravimetrically. Conductivity Conductance of water is measured by a digital Conductivitymeter (systronic Model, 304, India) and first calibrated with standard 0.01 M KCl solution (of conductivity 1287 ms/cm at 298 K). The conductivity is not a direct pollution parameter. It helps to give idea about the mineralization of water. The mineralization of ground water is due to perfect entrapment as well as recharge of solubilisation of minerals from soils. Higher mineralization may impart bad taste as potable water (Jain, 1998). Freshly distilled water has a conductivity value of 0.5 to 2 ms/cm which changes to ~ 4 ms/cm on standing due to absorption of atmospheric CO 2 . Drinking water has a conductivity in the range of 1500 mmho/cm (WHO, 1993).

RESULTS AND DISCUSSION Total Dissolved Solids (TDS) The TDS contents of water samples are given in the ranges below â&#x20AC;&#x201C; 15 mg/l to 530 mg/l (Dug well water), 10 mg/l to 300.6 mg/l (Ring well water), 5.8 mg/l to 350 mg/l (Pond water), 45 mg/l to 253 mg/l (River water), 80.1 mg/l to 251 mg/l (Railway supply water) and 65 mg/l to 188 mg/l (PHE supply water). In this investigation, the highest TDS content (530 mg/l) was recorded in the dugwell of Nadirpar (DW1) in the premonsoon season and the lowest value 5.8 mg/l was recorded in the pond water of Loco colony (P1) during monsoon season. Maximum TDS was observed in the dug wells and ring wells during the pre monsoon was due to the addition of lime and bleaching powder in the wells as well as in the monsoon season for the treatment of water. The maximum permissible limit of TDS in drinking water is 500 mg/l by USEPA (1996) and 1000 mg/l (WHO, 1993). In drinking water, the dissolved solids may be due to inorganic salts, organic matter and dissolved gas. A concentration of dissolved solids over 2000 mg/l produces laxative effect (Dhembare et al, 1998). The TDS contents of dug well water in Cuddaph town (Andhra Pradesh) were found to be extended over a range of 800-13,464 mg/l, with an average value of 2528 mg/l, which was very much higher than the permissible limit (Kumarswamy, 1991). A high TDS (8704 mg/l) was observed in the east coast of South India (Guru Prasad and Satya Narayan, 2004). Normally ground water has a higher TDS load compared to surface water (Veera Bhadram et al., 2004). Murugesan et al., (2004) showed high TDS (1000 to 1800 mg/l) in the ground water quality of seashore, due to seawater enter into the aquifers of the Chennai city of Tamilnadu. High values of TDS are due to salt-water contamination and industrial pollution (Kumar et al., 2005). The TDS content at deeper levels (> 40 m depth) is comparatively low in all the samples and lies well within desirable limit of 500 mg/l. It


PAUL & SEN, Curr. World Environ., Vol. 7(2), 251-258 (2012) may conclude that there is more mineralization of ground water at depth upto 40 meters (Jain, 2004). Conductance The values of conductance of water samples are given in Table 4.3 (a, b and c). The measurement were found in the ranges of 99 mmhocm-1 to 1483 mmhocm-1 (Dugwell water), 97 mmhocm-1 to 1378 mmhocm-1 (Ringwell water), 89 mmhocm-1 to 1410 mmhocm-1 (Pond water), 99 mmhocm-1 to 1040 mmhocm-1 (River water), 130 mmhocm-1 to 300 mmhocm-1 (Railway supply water), 179 mmhocm-1 to 400 mmhocm-1 (PHE supply water). Figs 1 to 6 represent ranges and seasonal averages of the conductance of various sources. The highest value of conductance was observed for the water samples of ring well of Patupather (DW4) in monsoon season. Again, the lowest value was observed in the pond water (P5). The conductivity qualitatively measures the extent of mineralization. The mineralization may

257

be caused of entrapment, ground water recharge and solubisation of minerals from soils. Higher mineralization may impact a bad taste to the potable water (Jain 1998). Drinking water can have a conductivity range of 1500 mmho/cm (WHO). The conductance values changed from season to season but no clear trend was observed. Viswanath and Anantha Murthy (2004) showed that high electrical conductivity (1580 mmho/cm) due to septic leakage from households. Prasad et al (2004) showed high conductivity (13390 mmho/cm) in different sources of ground water Machilipatnam town of Andhra Pradesh, Electrical conductivity of the ground water samples in both Mandya and Maddur towns (Andra Pradesh) ranged from 1524 to 2409 ms/cm which indicates the presence of high dissolved solids in ground water samples. (Shivashankara and Sharmila, 2004). A maximum conductivity value of 2210 ms/ cm and 1914 ms/cm was observed at Shasradhara (Dehradun, Uttranchal) was observed during pre and postmonsoon season (Jain, 2004) respectively.

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parameters at Machlipatnam Town. Nat. Env. Poll. Techn. 3(1): P. 47-50 (2004). ISI, Indian Standards for drinking water. IS: 10500:1991 (1991). Jain, C. K., Groundwater quality of District Dehradun, Uttranchal. Ind, J. Env. & Ecoplan. 8(2): P 475-484 (2004). Kakati, G.N., Study of surface water pollution in Greater Guwahati. A Ph. D.Thesis submitted to G.U (1990). Kumar, Dinesh; Jatin Mukta; Dhindsa, S.S.: Devanda, H.S. and Singh, R.V., Physicochemical characteristics of Amanishah nallah and neighbouring groundwater sources in Sanganeur, Jaipur. Ind. J. Env. Sc., 9(1): P. 71-74 (2005). Kumarswami, N., An approach towards assessment of dug well water quality by physico-chemical characteristics-a case


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reference to Mangaldoi sub â&#x20AC;&#x201C; division. A Ph. D. Thesis submitted to G.U (1997). USEPA, United State Environmental Protection Agency, Washington D.C. Source: Quality Criteria for water by Russel E. Train.1979, USEPA, Washington D.C (1979). Veerabhadram, K.; Ravichandra, M. and Prasanthi, M., Evolution of water quality index at Vishakapatnam city, Andhra Pradesh. Nat. Env. Poll. Tech. 3(1): P. 65-68 (2004). WHO, Guidelines for drinking water quality (2nd edn.), WHO, Geneva (1993).


Current World Environment

Vol. 7(2), 259-265 (2012)

Distribution Pattern of Enteropathogens in Greater Imphal Area of Imphal River, Manipur TH. ALEXANDER SINGH1, L. BIJEN MEITEI2 and N. SANAMACHA MEETEI3 1

Research Scholar, CMJ University, Laitumkhrah Shillong, Meghalaya - 793 003, India. Junior Research Officer, Directorate of Environment, Porompat, Imphal East - 795 005, Manipur. 3 Directorate of Environment, Imphal East - 795 010, Manipur, India.

2

(Received: July 12, 2012; Accepted: September 17, 2012) ABSTRACT An investigation on enteropathogens in the water of Imphal river at five different sites within greater Imphal area of Manipur was carried out as a part of water quality documentation at monthly intervals for one year. Densities of enteropathogens were found to be high during rainy season and low during summer and winter seasons. The degrees of survival for the different bacteria were influenced by various environmental factors as well as anthropogenic activities.

Key words: Enteropathogens, anthropogenic, allochthonous, indicator organism, pollution.

INTRODUCTION The increasing anthropogenic activities in and around the aquatic ecosystems and their catchments areas in recent years, have contributed to large scale mineral enrichment and incidence of many pathogenic micro-organisms in different water bodies. Besides, many major water bodies are being degraded due to continuous heavy discharge of untreated waste and surface run-off, causing deleterious effects in flora and fauna and other aquatic organisms (Sah et al., 2000). The distribution pattern and periodicity of different organisms in water solely depends upon the imprint of preceeding environmental factors (Badge and Verma, 1982). As such the significance of those factors as potent ecological parameters can be appreciated by considering the structure, physico-chemical characteristics, flora and fauna, primary and secondary productivities of the water bodies. Out of the many bacteria found in water, some are indicator of pollution and a small number of them are pathogenic. The coliform groups of bacteria are of great importance and include a number of organisms (Mc Kinney, 1962), causing

different water borne diseases. Coliform bacterial contamination in urban and rural surface water has been a major public health concern for decades (Bur ton et al, 1987). The sources for the contamination of different water bodies (Weibel et al, 1964, Crane et al., 1983, Tunnicliff and Brinkler, 1984) and relationship between land use and coliform level (Faust, 1982) had already been established. Water qualities especially those of rivers have been deteriorating due to disposal of garbage, religious offerings, sewage, recreational and constructional activities in the catchments areas. While many pollution problems affecting water quality are the direct result of human activity, some are less easily isolated (Cooper and Night, 1989). Contaminated water provides shelter to a variety of diverse micro-organisms (Khulbe et al., 1989), which many cause various water borne diseases. Therefore, the present investigation has been carried out with the objectives to assess the degree of persistence and distribution patterns of enteropathogenic groups of bacteria in greater Imphal area of Imphal river.


420.00 510.00 626.67 733.33 660.00 350.00 462.67 530.00 517.33 420.00 310.00 380.00 456.67 359.33 318.67 298.67 347.33 437.33 381.33 312.00 238.67 257.33 346.67 297.33 240.00 290.00 273.33 376.67 384.00 296.67 347.33 379.33 420.00 426.67 360.00 450.00 512.67 820.00 671.33 607.33 410.00 524.67 610.00 458.67 470.00 342.67 389.33 482.00 756.67 680.00

400.00 482.67 520.00 561.33 458.00

Apr. ‘12 Mar. ‘12 Feb. ‘12 Jan ‘12 Dec. ‘11 Nov ‘11 Oct. ‘11 Sep. ‘11

1 2 3 4 5

This trend of fluctuating density of total coliform population depend upon many factors such as physical chemical and environmental factors, including rainfall temperature, oxygen profile etc (Akpata, et al., 1993). The rainfall pattern influences the environmental condition of the water body

Aug. ‘11

Coliform bacterial density at the dilution level of 101 in the course of the river was found to be gradually increased from January onwards exhibiting peak value of 820.00 CFU 100-1 ml during rainy season of October and lowest value of 240.00 CFU 100-1 ml during winter season of January (Table-1). Similar observations was reflected in the findings of Sharma and Bharadwaj (2000) and Sharma and Rajput (1996) that coliform bacterial density was found to be correlated with rainfall due to fecal runoff from the disturbed as well as undisturbed catchment areas. Similar observations were also reported by Geldreich (1976), Das and Pande (1986), Baxter-potter and Gilliand (1988), Cooper and Knight (1989) and Rajender and Khulbe (1998).

Jul. ‘11

RESULT AND DISCUSSIONS

Table 1: Monthly variations in the microbial populations of Imphal river (July, 2011 to June, 2012) (Total Coliform Count x10 100-1 ml)

Samples for the enumeration of bacteria were collected at monthly intervals from five (5) experimental sites within greater Imphal area of Imphal City, Manipur (1-Koirengei, 2-Lamlong, 3Sanjenthong,4-Ningom Thongjao, and 5-Lilong) during July, 2011 to June, 2012. Water samples from different sites were collected by means of shallow water sampler in a wide-mouthed bottle which is pre-sterilized. Samples were chilled and returned to the laboratory on the same day for analysis. Total coliform and fecal coliform were quantitatively estimated by using standard membrane filter technique with appropriate dilutions (APHA, 1989). Triplicate analysis was done for each parameter. Further qualitative characterization and verification, selective medium for subsequent biochemical test were carried out (Buchanan and Gibbons, 1984; APHA, 1989). For the calculation of ANOVAR (Analysis of variance) in different seasons, the methods of parker (1973) and Trivedi, Goel and Trisal (1987) were used in computing the analysis.

May. ‘12 Jun ‘12

MATERIAL AND METHODS

480.00 536.67 682.67 730.00 658.67

SINGH et al., Curr. World Environ., Vol. 7(2), 259-265 (2012)

Sites

260


246.67 310.00 360.00 349.33 326.67 220.00 287.33 340.00 370.00 314.67 156.67 169.33 280.00 216.67 169.33 120.00 130.00 168.67 139.33 126.67 126.67 159.33 186.67 133.33 126.67 237.33 259.33 346.67 297.33 240.00 106.67 119.33 126.67 189.33 160.00 120.00 143.33 149.33 246.67 219.33 226.67 247.33 376.67 349.33 310.00 206.67 310.00 420.00 347.33 236.67 210.00 289.33 326.67 330.00 401.33 1 2 3 4 5

273.33 316.67 328.67 270.00 263.33

Apr. ‘12 Mar. ‘12 Feb. ‘12 Jan ‘12 Dec. ‘11 Nov ‘11 Oct. ‘11 Sep. ‘11 Aug. ‘11 Jul. ‘11

It is difficult to monitor the actual contamination sources in mixed cover watersheds since total coliform enumeration is general in nature and several streptococci are ubiquitous in soil and aquatic environment (Kebbey et al., 1978; Faust, 1982). The best data application for separating humans sources of contamination from other warm

Sites

The high count in fecal coliform population in the river might be resulted from fecal material of both human beings and animals. The same was reported by Sharma and Rajput (1996), Fatma et al. (1997), Shidhu and Khulbe (1998) and Khalil (2000) that they are mainly resulted from the continuous contamination of human and animal excreta. But, according to Faust et al. (1975), survival of fecal coliform was affected by many factors like interaction with metal, algal toxins, temperature, dissolved nutrients, ions, organic matters, protozoa, etc. Ranges of fecal coliform population of 106.67 to 420.00 CFU 100-1 ml (Table-2) at the dilution level of 10 1 was also found in close association with Sharma and Rajput (1996) and Sharma and Bhardwaj (2000). In the present finding, high population of fecal coliform during rainy seasons and low population during winter season (Table-2) were in consistent with the observation of Geldreich (1991), Joshi and Rajput (1992) and Islam et al. (1993). According to Thomas and Levin (1978) and Watnabe et al. (1981), fecal streptococci are mainly originated from the animal excreta because they are the normal habitat in the gastrointestinal tracts of warm blooded animals.

Table 2: Monthly variations in the microbial populations of Imphal river (July, 2011 to June, 2012) (Faecal Coliform Count × 10 100-1 ml)

during which many biodegradable materials are washed and carried down, thus explaining increasing in high bacterial population (Hill and Webb, 1958).The survival of bacteria in water is directly correlated with the presence of some organic materials and there is fluctuation in the population with the increasing and decreasing loads of biodegradable waste input in the water system (Flint, 1989). On the other hand, Knox (1986) suggested those bacteria and algae as food sources for primary consumer such as zooplankton, benthic invertebrates and some fishes resulting in the decrease of bacterial density. Therefore, the results of the present findings were also closely related with the observations of Nwachukwu et al. (1989), Jama et al. (1986) and McSwain and Swank (1997).

May. ‘12 Jun ‘12

SINGH et al., Curr. World Environ., Vol. 7(2), 259-265 (2012)

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47.33 63.33 87.33 82.00 73.33 52.00 61.33 82.00 87.33 62.00 31.33 35.00 56.67 48.00 42.00 27.33 30.00 36.67 29.33 22.00 31.33 37.33 46.00 42.67 39.33 27.33 32.00 40.00 47.33 45.33 37.33 40.00 42.67 50.00 47.33 42.00 45.33 62.00 66.67 57.33 59.33 62.00 76.00 64.00 60.00 57.33 62.00 89.33 66.07 62.00 47.33 56.67 79.33 86.67 110.00 1 2 3 4 5

63.33 72.00 86.67 70.00 56.00

Apr. ‘12 Mar. ‘12 Feb. ‘12 Jan ‘12 Dec. ‘11 Nov ‘11 Oct. ‘11 Sep. ‘11 Aug. ‘11

In the rainy season coliform bacterial population were found to be significantly fluctuating. This might be due to input of allochthonous material by influx of rainwater and soil, which impart significant variation of bacterial population. In the present study, analysis of variance of the critical value of ‘F’ at 5% level during rainy season revealed significant effect on the density of total coliform (P<0.05) and fecal coliform (P<0.05), while fecal streptococci revealed insignificant effect (P<0.05). However, significant differences were observed in summer and winter at the level of p<0.05 to P<0.01 for all the bacteria except faecal coliform which shown insignificant differences during winter (P>0.05). Their significance differences indicated

Jul. ‘11

According to Cooper and Knight (1989) coliform count could not be linked statistically with physical parameters because variability of indicator bacteria masked relationships as shown by large site-to-site fluctuations in bacterial count. He also stated that coliform counts did not vary with incremental changes in stage (± 0.1m) or with instream suspended sediment concentrations, which were excellent indicators of rainfall and runoff. In the present study, it was observed that during summer there were insignificant variations of coliform count, which might be due to low rainfall activity. This is in agreement with the findings of Robbins et al., (1972) that all coliform indicator groups were significantly higher in rainy season than the preceding summer or following winter. Robbins et al., (1972) also indicated that coliform concentrations were overshadowed by large-scale hydrologic events but most water quality parameters did not produce statistically significant equation for predicting bacterial pollution.

Sites

blooded sources of contamination may be fecal coliform (FC): fecal streptococci (FS) ratio over time (Cooper and Knight, 1989). According to Geldreich (1976), Baxter-potter and Gilliland (1988), the ratio less than 1.0 indicated warm blooded animal pollution while ratio of 4.0 or more suggested domestic waste pollution. During the study period 66 percent of all the samples had a ratio greater than 4.0 while 50 percent had a ratio greater and 1.0 (Table-4). These ratio indicated that domestic waste pollution is common than the warm blooded animal pollution.

May. ‘12 Jun ‘12

SINGH et al., Curr. World Environ., Vol. 7(2), 259-265 (2012)

Table 3: Monthly variations in the microbial populations of Imphal river (July, 2011 to June, 2012) (Faecal Streptococci Count × 10 100-1 ml)

262


SINGH et al., Curr. World Environ., Vol. 7(2), 259-265 (2012) continuous contamination of domestic and animal wastes along with run-off during rainy season. This is also in agreement with the finding of Sharma and Bharadwaj (2000). They also stated that correlation between total coliform and rainfall was found to be positively significant and it appears that human inhabitation and other activities based on land usage around the water body were responsible for the input of indicator organisms. Cooper and Knight (1989) also showed marked significant seasonal and monthly differences (P<0.05) of fecal coliform and fecal streptococci at two different locations of Agarian hill land streams due to rainfall pattern over the area. Hill and Webb (1958) also reported that the variability of bacterial count at different sites was found correlated with the sources of pollution. They found that bacteria formed an important link between primary producers and consumers, so it would appear that pollution affects the aquatic food chain. Flint (1989) reported that

263

survival of E. coli in filtered water was due to the presence of some organic materials. It is therefore, possible that specific bacterium survives with specific form of organic matter and this impart in the variability of species composition. So, the results in the present study were closely associated with the above observations. Thus, from the above results it is clear that the bacterial population had varied densities in different seasons which was influenced by the different environmental factors and their persistence at different densities in the river water throughout the study period offer an excellent opportunity to characterize the microbial quality of the water system and it is suggested that the river water is not suitable even for domestic purposes and need to be treated before use from hygienic point of view.

Table 4: Fecal Coliform : Fecal Streptococci ratio of Imphal River from July, 2011 to June, 2012 Months

July ‘11 Aug. ‘11 Sep. ‘11 Oct. ‘11 Nov. ‘11 Dec. ‘11 Jan. ‘12 Feb. ‘12 Mar. ‘12 Apr. ‘12 May ‘12 Jun. ‘12

Sites 1

2

3

4

5

4.43 4.31 3.60 3.82 2.86 2.86 8.67 4.04 4.44 5.00 4.23 5.21

5.11 4.40 5.00 3.99 3.16 4.98 8.10 4.27 4.33 4.84 4.68 4.89

4.12 3.79 4.70 4.96 2.41 2.97 8.67 4.06 4.60 4.94 4.15 4.12

3.81 3.86 5.25 5.46 3.70 3.79 6.28 3.12 4.75 4.51 4.24 4.26

3.65 4.70 3.81 5.16 3.83 3.38 5.29 3.22 5.75 4.03 3.84 4.45

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Akpata, T.V.I., Oyenekan, J.A. and Nwanko, D.I., Impact of organic pollution on the bacterial, plankton and benthic population of Lagos lagoon, Nigeria. Intl. J. Eco. and Env. Sci. 19: 73 - 82 (1993). APHA. Standard Methods for the Examination of Water and Waste Water

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Royal Society of London 214(B): 319-333 (1958). Islam, M.S., Hussain, M.K. and Khan, S.I., Growth and survival of Shigella in common Bangladeshi food under various conditions of time and temperature. Appl. & Env. Microbiol. 59(2): 652-654 (1993). Jama, B.B., Patel, G.N., Roy, S.K. and De, V.K., Growth characteristics of heterotropic bacterial population of water and bottom sediments in the tanks under different trophic conditions. Hydrobiologia 75: 231-239 (1986). Joshi, A and Rajput, S. Distribution of some human pathogenic bacteria in two freshwater lakes at Jabalpur. Ind. J. Env. Protection 12 (5): 321-323 (1992). Kebbey, H., Hagedorn, C. and McCoy, F., Use of fecal streptococci as indicators of pollution in soil. Appl. Environ. 35(4): 711-717 (1978). Khalil, M.T., Impact of pollution on productivity and fisheries of lake Mariut, Egypt. Intl. J. of Ecol. and Envn. Sci. 26: 8997 (2000). Khulbe, R.D., Sati, M.C. and Dhyani, A.P. Water pollution in Nainital lake; A survey. IN: perspectives in aquatic biology (Khulbe, R.D. Ed.), Papyrusi Publishing House, New Delhi (1989). Knox, G.A., Estuarine Ecosystem: A system Approach. Vol. X. CRC Press Inc. Boca Roton, Florida (1986). McKinney, R.E., Microbiology for Sanitary Engineers. McGrow-Hill, New York (1962). McSwain, M.R. and Swank, W.J., Fluctuation in naturally occuring population of bacteria in oligotrophic water of Waster North Carolina. USDA Forest Service Res. Pap. SL: 158 (1997). Nwachukwu, S.U., Akpata, T.V.I. and Essien, M.E., Microbiological assessment of industrial and domestic sewage at Agbara Industrial Estate (AIE) in Ogon state (Nigeria). Intl. J. Ecol. Environ. Sci. 15: 109-11 (1989). Parker, R.E., Introductory Statistics for Biology. Edward Arnold (publisher) Ltd. 25Hill Street, London (1973). P.J. Parmar, Orient J. Chem., 28(2): 927-931 (2012). Rajender, K.S. and Khulbe, R.D., A survey of


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impact and evaluation of water pollution on reservoir fisheries in Kumaun Himalayas, India with special reference to microorganisms. Curr. Sci. 75 (12): 13031308 (1998). Robbins, J.C., Howells, D.H. and Kriz, G.J. Stream pollution from animal production. J. Water Pollution Control. Fed. 44: 1536-1544 (1972). Sah, J.P., Sah, S.K., Acharya, P., Pant, D. and Lance, V.A., Assessment of water pollution in the Narayani river, Nepal. Intl. J. Ecol. & Environ. Sci. 26: 235-252 (2000). Sharma, V.K. and Bharadwaj, R., Bacteriological investigation of the water of Kolayatzi village pond of Bikaner (Rajasthan). Uttar Pradesh J. Zool. 20(1): 79-82 (2000). Sharma, A. and Rajput, S., Microbial quality and persistence of enteropathogenics in freshwater environment. Ecol. Env. & Cons. 2: 29-36 (1996). Shidhu, R.K. and Khulbe, R.D., A survey of impact and evaluation of water pollution on reservoir fishereis in Kumaun Himalayas,

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India, with special reference to microrganisms. Current Science 75(12): 1303-1308 (1998). M.R. Ansari, J. Ghomi and M. Riazian, Orient J. Chem., 27(4): 1523-1530 (2011). Thomas, C.D. and Levin, M.A., Quantitative analysis of group D-streptococci. Abs. Annual Meeting. American Soc. Microbiology. p. 210 (1978). Trivedy, R.K. , Goel, P.K. and Trisal, C.L., Practical Methods in Ecology and Environmental Science. Environmental publication, Karad , 340 (1987). Tunnicliff, B. and Brinkler, S.K., Recreational water quality analysis of the Colorado River Carrider in Grand Canyon, USA. Appl. Environ. Microbiol. 48: 909-917 (1984). Watanabe, T., Shimchashi, H., Kawai, Y. and Mutal, M., Studies on streptococci. I. Distribution of fecal streptococci in man. Microbiol. Immunol. 25: 275 (1981) Weibel, S.R., Dixon, F.R., Weider, R.B. and McCabe, L.J., Water borne disease outbreak (1946-1960). J. Amm. Waterworks Assoc. 56(2): 947-958 (1964).


Current World Environment

Vol. 7(2), 267-273 (2012)

Wind Field Modifications in Habitable Urban Areas SEEMI AHMED and ALKA BHARAT Department of Architecture and Planning, M.A.Natonal Institute of Technology, Bhopal, India. (Received: July 12, 2012; Accepted: September 17, 2012) ABSTRACT This paper discusses different criteria for the assessment of wind field environments in urban areas and how they relate to field observations. The importance of the inclusion of wind environment studies in the planning process is also discussed. The increasing influence of the built environment on wind speed and direction makes any forecast for heights below 50 meter very hazardous1. This increase in the areas with more built form where the roughness is extremely high. It is not always possible to make a quantitative forecast of wind speed and direction in urban environment. Examples are provided to illustrate how development controls can be designed to ensure that pedestrian amenity is not compromised by new development while at the same time not become a burden to innovative design approaches or good design practice due to wind modification. The paper concludes with a number of case studies that provide examples of how innovative techniques for mitigation of adverse wind environments can achieve the desired level of pedestrian amenity without having to compromise with the architectural design intent.

Key words: Wind engineering, pedestrian environment comfort, Urban Heat Island (UHI) effect

INTRODUCTION Urban areas and inhabitants of cities tend to increase. Nowadays, about half of the world total population live in urban settlements. This large number of dwellers produce variety of activities and modify urban air quality and pattern. Urban wind flow is driven by a deep, stratified urban boundary layer with significant wind fluctuations. Solar heating effects include shadows from buildings and trees, aerodynamic drag, heat exchange affected by the surface property variations and turbulent heat transport. Causes of wind field modifications in urban areas In urban areas, main air flows from prevailing winds are strongly modified, depending on constructions’ morphology and urban microclimate effects.3 Wind field modifications have become particularly significant because of the increasing number of high-rise buildings, industrial and vehicular activities etc. Significant differences can be found in wind speed frequency distributions

at vertical levels in urban areas due to following elements and phenomenon. ´ Buildings, Vegetation ( Physical and thermal Obstacles/ Roughness) ´ Air conditioners (thermal) ´ Natural Topography (moisture properties of the surface, undulations etc) ´ Street canal effects due to Vehicular movements. (thermal) ´ Tall buildings - Turbulence, Roughness ´ Local Climatic conditions/ Seasonal Variations ´ Shelter from nearby buildings, ´ Urban Heat Island Effect (UHI) Wind field modifications due to UHI effect Urban surfaces act as a giant reservoir of heat energy. Concrete can hold roughly 2,000 times as much heat as an equivalent volume of air. The large daytime surface temperature within the UHI is easily seen via thermal remote sensing. At night time an inversion layer is formed


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This traps urban air near the surface, and keeping surface air warm from the still-warm urban surfaces, forming the nighttime warmer air temperatures within the UHI. Lose of heat at night is blocked by the buildings in an urban area. Difficulties and peculiarities of an urban wind regime Urban Roughness Prediction of the wind speed in the built environment is difficult. One of the reasons is “surface roughness”. The many obstacles and different heights of buildings give the built environment a high roughness coefficient 2 , compared to open, rural locations. The roughness coefficient is generally used to extrapolate wind Table 1(a): Roughness coefficients for different surfaces 2 Roughness length m

Landscape Type

0.0002 0.0024

Water surface Complete open terrain with a smooth surface eg. Concrete walkways, airports, mowed grass etc. Open agricultural area without fences and hedgesrows and very scattered buildings, only smoothly rounded hills Agricultural land with some houses and 8 mtrs tall sheltering hedgerows with a distance of approximately 1250mtrs. Agricultural land with some houses and 8 mtrs tall sheltering hedgerows with a distance of approximately 500mtrs. Agricultural land with some houses and 8 mtrs tall sheltering hedgerows with a distance of approximately 250mtrs. Villages small towns with many or tall hedgerows, forests or very uneven and rough terrain Large cities with tall buildings Very large cities with tall buildings and skyscrapers

0.03

0.055

0.1

0.2

0.4

0.8 1.6

Table 1(b): Urban Building Roughness – Flow Regime Low Density –isolated flow Buildings and trees are small and widely spaced, eg. Modern single family housing with large lots and wide roads, light industrial area or shopping mall with large paved or open space. Medium Density- wake interference flow Two to four storey buildings and mature trees elements of various heights occupy more than 30% surface area and create semi enclosed spaces (street canyons and courtyards), closely spaced and large and semi detached hoses, block of apartments in open surroundings. Mixed houses with shops, light industry, churches, and schools High Density- Skimming flow Buildings and trees closely packed and of similar height, narrow street canyons eg. Old town centres dense row and semidetached housing, dense factory sites. High rise- chaotic or mixed flow Scattered or clustered tall towers of different heights jutting up from dense urban surroundings, eg. Modern city core, tall apartment, major institutions

speed at different heights from measurement at only one or two heights and locations. A high roughness coefficient means slower acceleration of speed as height increases and therefore lower energy yields. Table 1a gives the roughness coefficient (or length) generally used for a type of surface. It is worth noting the difference between open agricultural area (even with some houses and

Fig. 1: The wind speeds at Ground and higher levels (Grimmond et al., 2007)


AHMED & BHARAT, Curr. World Environ., Vol. 7(2), 267-273 (2012) hedgerows) at 0.055 to 0.1 roughness, compared to 0.8 for larger cities with tall buildings – which are typical of the locations now being considered for small wind installations. Due to the high roughness in the built environment, the wind speed close to the ground becomes a local parameter (dependent on local conditions near the ground). It is then not possible to measure a local parameter (wind speed) on the basis of some average characteristics of the roughness of the broader area of the built environment. Turbulence The roughness of the earth’s surface, which causes drag on the wind, converts some of the wind’s energy into mechanical turbulence. Since the turbulence is generated at the surface, the surface wind speed is much less than the wind speeds at higher levels fig.1. Turbulence includes vertical as well as horizontal air movement and hence the effect of the surface frictional drag is propagated upwards. The mechanical turbulence and the effect of frictional drag gradually decrease with height and at the “gradient” level (around 1000 to 2000 feet) the frictional effect is negligible. The pressure gradient at this level is balanced by the Coriolis force (and possibly the centrifugal force), and the wind blows almost parallel to the isobars Wind Assessment and Planning Controls The development of appropriate planning guidelines is an important step in avoiding adverse

Fig. 2(a): Wind movements in and around an exposed building

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wind environments in urban areas. Currently there are a diverse range of wind assessment criteria like placing and spacing of buildings on site. Most of these are effective in general agreement with each other and with field observations. Other criteria tend to be either unnecessarily stringent or slightly lenient. In the case of former, this is also undesirable as it will present unnecessary restrictions to the form and appearance of a building. The use of wind tunnel testing remains the most reliable technique to model the wind environment effects around buildings in urban and suburban environments.. The use of Computation Fluid Dynamics (CFD) or wind tunnel visualisation techniques such as the scouring technique may be useful only as form of initial qualitative assessment and should not be solely relied upon. Planning Controls Care should be taken in the formulation of planning controls such that the requirements are not overly restrict innovative design. Features such as aerodynamic tower forms, adequate podiums, provision of awnings, strategic planting should be encouraged but not mandatory. At the same time, controls should be provided with regards to adequate modelling of the wind effects. The most critical areas around an exposed building are usually the areas near the corners at the base of the building (side-stream effects), at the base of a wide face of the exposed building (downwash effect, which is applicable for buildings more than 12 levels in height) and though arcades or openings at the base of the building that are

Fig. 2(b): Flow patterns around tall, slab-like building. areas of increased wind speeds at pedestrian level


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open to opposite aspects of the base of the tall building (gap effect). The extent of each will depend on the level of exposure, the strength and directionality of the wind climate and the shielding or funneling effects from the surrounding buildings. Other aspects that need to be investigated are the wind conditions like turbulent wind, funneling effect of wind in any planned outdoor areas within or adjacent to the proposed development. Urban Wind Environment Criteria If a low building is located in the wind shadow of a tall building fig. 3b., the increase in height of a obstructing block will increase the air flow through the low building in a direction opposite to that of the wind. The lower wing of a large vortex would pass through the building. It is has been established experimentally that wind comfort is more closely related to the gust wind speeds rather than the mean wind speeds.1 This is particularly so in the case of extreme winds which can lead to people losing balance in the wind. Rofail (2005) proposed a set of criteria that converts the mean comfort criteria into a set of criteria for maximum gusts, or peak wind speeds. However, this set of criteria is based on an assumption of 15% turbulence intensity, which in the vast majority of cases is very conservative. An alternative set of peak wind speed criteria has been proposed by Rofail (2007). The average airflow, the dynamic fluctuations, and the building scale turbulence are all closely coupled to the complicated geometry of the building. An equally valid approach would be to compare the mean wind speed criteria such as those by Davenport5 against a Gust-Equivalent Mean (the maximum of either the mean or the gust wind speed divided by a gust factor). In addition to comfort criteria there is a safety limit that is applicable to all accessible outdoor areas regardless of type or frequency of use. The safety limit suggested by Melbourne (1978) of 23m/s for annual maximum1 gust has been adopted by most consultants and forms part of most sets of criteria. Requirements for Reliable Wind Tunnel Tests The key factors that ensure a reliable set of wind speed measurements in the wind tunnel are: ´ The scale model of the building and surrounds, ´ The modelling of the behaviour of the

´

approach wind and The sampling parameters and type of instruments that are used to measure the wind speeds.

Main Factors for wind modelling These three factors are Comparison of Various Mean and Gust Wind Environment Criteria, assuming 15% turbulence and a Gust Factor of 1.5. Wind tunnel model scales should not be less than 1:500m in scale. 1) The model must include the effect of the surrounds, including the local land topography. The study building(s) as well as the buildings in the immediate vicinity need to be modelled to a greater accuracy. The proximity model should extend to a radius of at least 400m. Care should be taken in modelling of porous elements such as trees, louvres or porous screens to ensure the same aerodynamic properties such as Reynold’s Number similarity. To achieve this, it may be necessary to distortion of the model’s geometry. The modelling of features such as balustrades in balconies may over-constrict the flow through these areas in the model scale and require special treatment. Similarly the modelling of gaps through a building may need to be distorted to achieve similarity in the flow regime between model-scale and full-scale.4 2) The key parameter in modelling the behaviour of the approach wind is to ensure that the flow correctly matches with the fullscale in terms of the variation of the mean wind speed as well as the turbulence intensity with height to within 10 percent. The other parameter is the modelling of the integral length scale of turbulence to within a factor of 3 (AWES, 2002). The reference wind speeds need to be based on an analysis of the wind climate data obtained from an observation station located within a reasonable distance from the study site. It is recommended that the climate data used of wind speeds for a period of at least 10years7. The wind climate data should be properly corrected for the effect of upstream terrain, shielding effects and the effect of the local land topography.7


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Measurements should be made of the peak and mean wind speeds. Filtering of the velocity signal needs to be applied for the maximum gust to represent a 3-second peak. Measurements should be taken from at least 8 wind directions, although 16 wind directions is currently the standard practice and is recommended. There are two types of instruments that can be used, hot-wire anemometry and pressure-based sensors such as the Irwin probe7. Note that some types of pressure based sensors are very sensitive to wind direction and should be avoided. Pressure based sensors should be properly calibrated to ensure that they provide a reliable wind speed estimate for the range of wind speeds within which they operate in the wind tunnel. The results should be expressed as either gust wind speeds or both gust and gust-equivalent mean wind speeds. The gust-equivalent mean is defined as the maximum between the mean and a gust-equivalent mean wind speed.

The latter is the gust wind speed divided by an appropriate gust factor. Initial tests should be carried out without the effect of vegetation to enable the wind engineering consultant to properly identify the prevailing wind flow mechanisms. It is also important to ensure that any recommendation suggested in the report shall be adequately modelled and tested in the wind tunnel. This is important since a solution that would work for one project may not necessarily be sufficiently effective for another project even if the wind flow mechanism is similar. Case Studies To ensure a viable Design, the formulation of strategies needs to be carried out in close collaboration with the architect or designer responsible for the project. Below are some examples of wind effects from projects undertaken by Wind-tech Consultants and details of solutions that were recommended after confirmation of their effectiveness through wind tunnel testing. Note that in some cases, more than one solution may be presented. Case Study 1 The tower illustrated in Figure 3 is for a 45-storey tower project in Melbourne.

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Fig. 3: Is for a 45-storey tower project in Melbourne The tower is located at a corner of a city block and the wide face fronts a narrow street as well as the prevailing wind direction for Melbourne (north). Furthermore, the site is relatively exposed in that direction. The result is that the tower can potentially generate a significant downwash and side-stream effect around the corner of that city block. Figure 6 shows a side profile of the tower with the wind incident from the north direction. Two options were presented. One required the tower to be set back from the lane. The second treatment required a small podium with a high wall to capture the down-washed winds and direct them to a permeable car parking level. Case Study 2 The development shown in Figure 4 is located in Delhi. This development is exposed to all 3 prevailing wind directions for Delhi.6

Fig. 4: Redevelopment of property at Civil Lines, located in Delhi The north-easterly winds and westerly winds were of particular concern for this development as the two towers are aligned in the north-south direction. This particular site happens to be situated near the top of a ridgeline in the land form that runs north-south. This results in potentially strong funneling effects between the two tower


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Fig. 6: Photographs of the model of the Waterloo, Sydney development in Windtech Consultants’ wind tunnel showing details of the optimum treatment for the effect of the westerly winds on the wind conditions at the north-western corner 1 Fig. 5: Transport Corporation of India Ltd, Gurgaon buildings that are well in excess of the safety limit. A number of treatment options were investigated including large canopies along the entire length of the two tower buildings and over the gap. This is possibly due to the significant contribution from the upwash of the ground level winds over the northern edge of the podium. This effect seems to have been accentuated in case by the fact that the site is situated at the apex of a saddle formation in the landform, being exposed to the north-east winds along the wide aspect. The only treatment that worked effectively was the least expensive. Case study 3 Transpor t Corporation of India Ltd, Gurgaon- Inward-looking compact form, with controlled exposure. Two types of windows designed: peep windows for possible cross-ventilation and view, the other being for day-lighting. The courts towards which the building has more transparency have structural framework to provide support for shading screens. Landscaping acts as a climate modifier. The window reveals of the peep window cut out summer sun and let in winter sun. Adjustable Venetian blinds in double window sandwich to cut of insulation and allow daylight. Polyurethane board insulation on wall and roof. Fountain court with water columns as environment moderator. Building systems designed so as to draw upon external environment to supplement the air-conditioning

system. Eco-friendly absorption technology adopted for air-conditioning. Careful planning of air distribution system. Air-conditioning standards set by acceptance level of office staff and not by international norms. Energy-efficient lighting system and daylight integration with controls. Optimization of structure and reduction of embodied energy by use of less energy-intensive materials6 Case Study 4 Another example is a development in Waterloo, Sydney fig. 6. The results indicate that this development will be subject to un-favourable wind conditions due to the effect of the westerly winds It was established that this is due to a combination of direct ground level winds as well as a side-stream effect that was accentuated by the effect of the proposed high colonnade at the northwest corner of the proposed building. This effect is further complicated by the fact that an outdoor café is proposed under the high colonnade at that corner of the building. The optimum solution involved the use of strategic tree planting along the western aspect of the development as well as a freestanding canopy under the north-western corner of the colonnade area to act a deflector. With this treatment the wind conditions were improved from exceeding the safety limit to being acceptable for seating and therefore acceptable for use as an outdoor café area.


AHMED & BHARAT, Curr. World Environ., Vol. 7(2), 267-273 (2012) Case Study 5 A wind environment study was conducted for the project in Abu Dhabi described in Fig. 7. This development includes 3 linked residential tower buildings with two 9-level high undercroft areas located below the linkages.

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A wind tunnel model study was carried out and indicated that a significant speed up effect occurs within these gaps due to the gap effect. For each gap, the effect was successfully ameliorated by means of a baffle screen located at each end of the gap. One of these screens served as a wall for a covered gazebo. Other areas that required treatment included one of the street corners and the base of one of the towers. The wind effects there were successfully ameliorated by means of strategic planting. Fig. 7. The Abu Dhabi development with the areas affected by the gap effect indicated. CONCLUSION This paper demonstrates how it is possible to plan for habitable wind environments, while still accommodating the architectural intent. The average airflow, the dynamic fluctuations, and the building scale turbulence are all closely related to the complicated geometry of the building. Features such as aerodynamic building forms, adequate podiums, provision of awnings, strategic planting should be encouraged in the design.

Fig. 7: The Abu Dhabi development with the areas affected by the gap effect indicated

With the proper modeling and simulation techniques and appropriate wind field study. it is possible to achieve a favourable outcome for both the owners and end users. Local authorities can also have a role in stipulating development controls without over-specifying the building form, which runs the risk of stifling innovation.

REFERENCES 1. 2.

3.

4.

Ahmed Siraj Wind Energy Theory and Practice, PHI Publication first edition (2010). BorisJay P.Dust in the Wind: Challenges for Urban Aerodynamics,, Laboratory for Computational Physics and Fluid Dynamics (2002). Campbell Neil et. al "Wind Energy For The Built Environment" Paper published in Procs. European Wind Energy Conference & Exhibition, Copenhagen, (2001). Davenport, A.G. An approach to human

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comfort criteria for environmental conditions, Colloquium on Building Climatology, (1972). Rafail, Tony "Developing habitable Built Environment" CUTBH 8th World Congress (2008). Representative designs of energy-efficient buildings in India Published by Tata Energy Research Institute (2001). Urban Wind Assessment in UK, An introduction to wind resource assessment in the urban environment, (2007).


Current World Environment

Vol. 7(2), 275-280 (2012)

Extracts of Kashmiri Saffron in Service to Human Race and Present Ground Realities MOHAMMAD IMRAN KOZGAR*and NEELOFAR JABEEN *Mutation Breeding Laboratory, Department of Botany, Aligarh Muslim University, Aligarh - 202 002, India. Department of Education, Government of Jammu and Kashmir, Srinagar, India. (Received: July 12, 2012; Accepted: September 17, 2012) ABSTRACT The Kashmir valley is well known for producing high quality of saffron (Crocus sativus L.) and represents one of the major saffron-producing areas of the world. Saffron has been traditionally used in preparation of indigenous medicines and also as a dye. The extracts of the parts of saffron plant is being used in cosmetics and in many drugs to cure different ailments. In present document the potential role of the saffron and its parts cultivated in Kashmir valley and the diseases like cancer to be cured from them are being discussed. Concerns on the low production rate due to urbanization and shrinking of the cultivated land and probable adoptions to be implemented to avoid the loss of economy are being discussed.

Kew words: Kashmir, Saffron, Cancer, Treatment, Crocin, Mechanism, Apoptosis.

INTRODUCTION Cancer represents the largest cause of the mortality, which claims over 6 million lives each year, in present world (Abdullaev 2012). Insensitivity of cancer types to most of the oncological therapies such as chemotherapy, radiotherapy and immunotherapy (Ghaneh et al. 2007, Sarkar et al. 2007) has forced to strengthen new therapeutic strategies to combat this deadly form of disease. A promising strategy to cure cancer is chemoprevention through natural agents. Natural agents, extracted from diverse sources like that of plants, had been extensively used for curing many ailments including cancer. Natural products and related drugs are used to treat 87% of all categorized human diseases infectious and noninfectious (Chin et al. 2006). Molecular epidemiological studies have provided evidence that an individualâ&#x20AC;&#x2122;s susceptibility to cancer like diseases is modulated by both genetic and environmental factors via. their interaction and their affect on enzymes involved in the metabolism of

carcinogens (Gattoo et al. 2011). Chemoprevention may act to cure cancer as per the possible mechanism illustrated in Fig. 1. One of the constituents which have shown the results of inducing apoptosis is Crocin (Fig. 2) extracted from the Kashmir Saffron, Crocus sativus L. (Bakshi et al. 2010) Outline of Kashmirri Saffron Kashmir, one of the biotic provinces of the Himalayas, supports a rich and unique floristic diversity, including at least 450 known medicinal plants species (Jabeen and Kozgar 2011) including saffron. Saffron is cultivated commercially to limited extent in India and mostly confined to this part (Kashmir), however, it is also found to be cultivated in Azerbaijan, France, Greece, Iran, Italy, Spain, China, Israel, Morocco, Turkey, Egypt, and Mexico with high commercial cost outputs (Negbi 1999). In Kashmir saffron cultivation is mostly seen in the table-land of Pampore, at the outskirts of Srinagar city, which is well known for quality saffron and represents one of the major saffron-producing


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areas of the world, and infact some authors reflect that the saffron originated from Kashmir from where Phoenicians introduced it to the Greek and Roman world (Alberini 1990; Winterhalter and Straibinger 2000) and to Britain world in XIV century (Caiola and Canini 2010).

Constituents and usages of Kashmiri Saffron Saffron belongs to the iris family (Iridaceae) and constitutes different chemical agents like crocin, crocetin anthocyanin, carotene and lycopene (Abdullaev and Espinosa-Aguirre, 2004), especially in its stigma parts of the flower

(Modified from Steinmeta and Potter 1996; Kelloff et al. 2000; Lampe 2003)

Fig. 1: Possible mechanisms for chemoprevention by the extracts of medicinal plants

Fig. 2: Chemical structure of Crocin


KOZGAR & JABEEN, Curr. World Environ., Vol. 7(2), 275-280 (2012) (Giaccio et al., 2004). These constituents are known to have various usages in relation to health related problems. They have pharmacological effects on different illness, including anti-tumor effects by inhibition of cell growth (Abdullaev 1993, Dhar et al. 2009). Bakhsi et al. (2010) has demonstrated that the crcocin extracted from the saffron cultivated in Pampore belt of Kashmir vale has potential role in inducing cell cycle arrest and henceforth could play a key role in cancer treatments (Fig. 3). In addition, the extract of this saffron has also revealed to inhibit cell proliferation (Fig. 4) and modulate signal transduction. All these factors viz. inducing apoptosis, inhibit proliferation of cell and/or

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modulating signal transduction are currently used in cancer treatment and Guzman (2003) reported that the combination of multi-chemopreventive agents or agents with multiple targets is considered to be more effective than a single agent. Cultivation problems and strategies for exploring saffron sustainably Over than three decades from now the land under cultivation of saffron in Pampore (Kashmir) region is shrinking rapidly due to encroachment of local people. Increase in urbanization and presence of anthropogenic pressures are other problems. In addition, the

(A)

(B)

Morphology of apoptotic cells control (a) vs treated with crocin (b) Hoechst stainx400 (Adopted from Bakshi et al 2011; Permission granted for using from Journal Editorial Offcie and also from Main author)

Fig. 3: Induction of Apoptosis and Cell Cycle Arrest


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genetic diversity is not upto so much extent in this particular plant as it reproduces vegetatively through corms. Due to absence of ample genetic diversity saffron plants are constantly under siege by a multitude of disease-causing organisms including bacteria, fungi, viruses and nematodes (Ahrazem et al. 2010). In addition, limited availability of daughter corms is also one of the major handicaps for the expansion of acreage under saffron (Sharma and Piqueras 2010).

In order to get full benefit from the extracts of the saffron plant of Kashmir cultivated one, various techniques and sustainable approached has to be introduced. Techniques like induced mutagenesis and tissue culture has to be implemented and reserving the land for its cultivation has to be promoted. Cultivation in indoor pots and promotion of its cultivation in kitchen gardens has to be enhanced. Hussiani et al. (2010) has advocated the need for using quality planting materials and a sprinkler irrigation system as one of the major means to enhance the production.

BxPC-3 cells (HPCL) treated with 10 Âľg/mL crocin (extracted from saffron) for 0,6, 12, 24, 36 h, induced DNA fragmentation in time dependant manner from 12 hours. Actinomucin D for 36 h was a positive control (PC) at a concentration of 10 Âľg/mL (Adopted from Bakshi et al .2011; Permission granted for using from Journal Editorial Office and also from Main author) Fig. 4: Agarose gel electrophoreses demonstrating DNA fragmentation CONCLUSION In order to obtain high economy from the saffron parts grown in Kashmir new areas should be covered under cultivation. Analysis of different constituents and their probable applications in the healthcare using cutting edge techniques, in a sustainable way, be promoted from all corners. Looking for procedures and their amplifications

should be increased, which directly or indirectly enhance the genetic diversity among the cultivars of saffron. Encroachment in the field of saffron cultivated belt, either for domestic life or for commercial purposes, should totally banned. Biophysiological studies for various types of stresses especially cold stress be analyzed to develop the variety resistant to cold, which is mostly following the later stages of saffron growth period.


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Abdullaev FI, Biological effects of saffron. Biofactors 4: 83-86 (1993). Abdullaev FI, Cancer chemopreventive and tumoricidal properties of saffron ( Crocus sativus L.). Experimental Biology and Medicine 227: 20-25 (2002) Abdullaev FI, Espinosa-Aguirre JJ, Biomedical properties of saffron and its potential use in cancer therapy and chemoprevention trials. Cancer Detection and Prevention Journal 28: 426-32 (2004). Abdullaev FI, Rivera LR, Roitenburd BV, Espinosa AJ, Pattern of childhood cancer mortality in Mexico. Archives of Medical Research 31(5): 526-531 (2000). Alberini M, Saffron: sapore e colore. Lo zafferano. Proceedings of the International Conference on Saffron (Crocus sativus L.). L’Aquilla, Italy, pp 39-46 (1990). Bakshi H, Sam S, Rozati R, Sultan P, Islam T, Rathore B, Lone Z, Sharma M, Triphati J,Saxena RC, DNA Fragmentation and Cell Cycle Arrest: A Hallmark of Apoptosis Induced by Crocin from Kashmiri Saffron in a Human Pancreatic Cancer Cell line. Asian Pacific Journal of Cancer Prevention 11: 675-679 (2010). Caiola MG, Canini A, Looking for saffron’s (Crocus sativus L.) parents. In: Husaini AM (Ed) Saffron. Functional Plant Science and Biotechnology 4(Special Issue 2), 1-14 (2010). Chin YW, Balunas MJ, Chai HB, et al., Drug discovery from natural sources. The AAPS Journal 8: 239-53 (2006). Dhar A, Mehta S, Dhar G, Dhar K, Banerjee S, Veldhuizen PV, Campbell DR, Bnerjee SK, Crocetin inhibits pancreatic cancer cell proliferation and tumor progression in a xenograft mouse model. Molecular Cancer Therapeutics 8(2): 315-323 (2009). Gatoo MA, Siddiqui M, Farhan AK, Kozgar MI, Owais M. Oral cancer and gene polymorphism: International Status with special reference to India. Asian Journal of Biochemistry 6(2): 113-121 (2011). Ghanesh P, Costello E, Neoptolemos JP,

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Biology and management of pancreatic cancer. Gut 56: 1134-1152 (2007). Giaccio M., Crocetin from saffron: an active component of an ancient spice. Critical Reviews in Food Science and Nutrition 44: 155-72 (2004). Guzman M, Cannabinoids: Potential anticancer agents. Nature Reviews Cancer 3: 745-755 (2003). Jabeen N, Kozgar MI, The Genus Aconitum in Kashmir Himalaya . LAP Lambert Academic Publishing GmbH & Co Saarbrücken Germany (2011). Kelloff GJ, Crowell JA, Steele VE, Lubet RA, Malone WA, Boone CW, Kopelovich L, Hawk ET, Lieberman R, Lawrence JA, Ali I, Viner JL, Sigman CC, Progress in cancer chemo-preventionm: Development of dietderived chemopreventive agaents. Journal of Nutrition 130(Suppl): 467S-471S (2000). Lampe JW, Spicing up a vegetarian diet: Chemopreventive effects of phytochemicals. American Journal of Clinical Nutrition 78(Suppl): 579S-583S (2003). Negbi M, Saffron cultivation: past, present and future prospects. In: Negbi M, Ed. Saffron Crocus sativus L. Amsterdam: Harwood Academic Publishers, pp 1-19 (1999). Sarkar FH, Banerjee S, Li YW., Pancreatic cancer: Pathogenesis, prevention and treatment. Toxicology and Applied Pharmacology 224: 326-36 (2007). Steinmetz KA, Potter JD, Vegetables, fruit, and cancer prevention: A review. Journal of American Dietetic Associatin 96: 1027-1039 (1996). Winterhalter P, Straubinger M, Saffronrenewed interest in an ancient spice. Food Reviews International 16: 39-59 (2000). Sharma KD, Piqueras A, Saffron (Crocus sativus L.) Tissue Culture: Micropropagation and secondary metabolite production. In: Husaini AM (Ed) Saffron. Functional Plant Science and Biotechnology 4(Special Issue 2): 15-24 (2010). Ahrazem O, Rubio-Moraga A, Castillo-López R, Mozos AT, Gómez-Gómez L, Crocus


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sativus Pathogens and Defence Responses. In: Husaini AM (Ed) Saffron. Functional Plant Science and Biotechnology 4(Special Issue 2): 81-90 (2010). Husaini AM, Hassan B, Ghani MY, Teixeira da Silva JA, Kirmani NA, Saffron (Crocus

sativus Kashmirianus) cultivation in Kashmir: Practices and problems. . In: Husaini AM (Ed) Saffron. Functional Plant Science and Biotechnology 4(Special Issue 2): 108-115 (2010).


Current World Environment

Vol. 7(2), 281-286 (2012)

Spatial Distribution of Ground water Quality in Some Selected parts of Pune city, Maharashtra, India using GIS SUVARNA TIKLE1, MOHAMMAD JAWID SABOORI2 and RUSHIKESH SANKPAL2 1

EME, Division, Mitcon Consultancy and Engineering Services ltd., Pune - 411 005, India. 2 Department of Environmental Science, University of Pune, Pune - 411 007, India. (Received: July 12, 2012; Accepted: September 17, 2012) ABSTRACT Pune is one of the major developing cities in India; its area is rapidly increasing as neighboring villages like Aundh, Baner, Pashan and Sutarvadi are merged into the Pune Municipal Corporation (PMC). Majority of the people are using the groundwater as a prime source for their domestic needs, besides the PMC is supplying them with an allocation of treated water. Assessing the quality of groundwater is an important issue in the modern times. Spatial variations in ground water quality in some selected parts of Pune Municipal Corporation, Maharashtra, India, have been studied using geographic information system (GIS) technique. 29 bore well water samples were collected representing the newly merged. The water samples were analyzed for physico-chemical parameters as prescribed by APHA, using standard techniques and compared with WHO (2006, 2008) drinking water quality standards (1, 2). The ground water quality information maps of the entire study area were prepared by GIS Inverse Distance Weighting (IDW) technique for all the above parameters. The results obtained in this study with the spatial database established in GIS will be helpful for monitoring and managing ground water quality and its pollution in the study area of Pune city.

Key words: Ground water, Spatial distribution, Physico-chemical parameters, Drinking water quality, GIS, inverse distance weighting technique.

INTRODUCTION

MATERIALS AND METHODS

Groundwater resources are dynamic in nature. These are affected by factors such as, the expansion of irrigation activities, industrialization and urbanization. Hence, monitoring and conserving this important resource is essential. The quality of water is defined in terms of its physical, chemical and biological parameters. Ascertaining the quality of groundwater is crucial before its use. Water may be used for various purposes such as drinking, agricultural, recreational and industrial activities3, 4. Groundwater assessment has been based on laboratory investigation, but the advent of Satellite Technology and Geographical Information System (GIS) has made it very easy to integrate various databases5.

The study area includes Aundh, Baner, Pashan and Sutarvadi. The Base map of study area was drawn from Survey of India topographic map no. Toposheets 41F/14. The bore well locations were identified. The samples were collected from 29 boreholes from selected locations. As part of the study, groundwater samples were collected from 29 bore wells. The samples collected during December 2011 were analyzed for various physicochemical parameters. Physico-chemical analysis was carried out as per the standard procedures prescribed by American Public Health Association (APHA), to determine Electrical Conductivity (EC), Total Dissolved Solids (TDS), Total Hardness (TH) , pH, HCO3-, Mg2+, Ca2+, K+, Na+, Cl-, SO42-, NO3- and F- 6-7. The results were compared with standard


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values recommended by World Health Organization WHO (2006 and 2008) guidelines for drinking water quality. GIS technology proved to be very useful for enhancing the accuracy. We obtained the location of the well by using the GPS and Arc GIS software. The IDW was applied to find out the spatial distribution of groundwater quality. In interpolation with the spatial analyst method of IDW, a weight is attributed to the point to be measured. The amount of this weight is dependent on the distance of the point to another unknown point6. These weights are controlled on the bases of power of ten. With increase of power of ten, the effect of the points that are farther diminishes. Lesser power distributes the weights more uniformly between neighboring points. In this method the distance between the points count, so the points of equal distance have equal weights7. The advantage of IDW is that it is intuitive and efficient. This interpolation works best with evenly distributed points. Similar to the SPLINE functions, IDW is sensitive to outliers. Furthermore, unevenly distributed data clusters result in introduced errors8. RESULTS AND DISCUSSION Understanding the groundwater quality is important as it is the main factor determining its suitability for drinking use9. The groundwater quality maps were prepared for each selected parameter. Electrical Conductivity (EC) The importance of EC is its measure of salinity; which greatly affects the taste. Thus EC has a significant impact on determining the potability of water9. The EC of water at 25°C is due to the presence of various dissolved salts. The EC varies with water sample and ranges between 469.2µS/cm and 1173µS/cm with an average of 800µS/cm. Knowing that the maximum limit of EC for drinking water is prescribed as 1,500µS/cm at 25°C, all the values are within the permissible limit. Figure 1 shows the spatial distribution of EC in the study area. pH In general, pH is the measure of acidity or alkalinity of water. It is one of the most important operational water quality parameters with the

optimum pH required often being in the range of 7.0-8.5 (10). The maximum permissible limit for pH for drinking water as given by the WHO is 9.2. The pH values in the groundwater samples collected varied from 7.05 to 7.76 with an average value of 7.27. This shows that groundwater of the study area is mainly neutral to slightly alkaline in nature. Spatial distributions of pH concentrations are shown in Figure 2. The values of pH show that all of the samples displayed a pH value within the maximum permissible limit. Total Dissolved Solids (TDS) TDS in water are represented by the weight of residue left when a water sample has been evaporated to dryness WHO (2006). TDS are compounds of inorganic salts (principally Ca, Mg, K, Na, HCO3-, Chlorides and SO42-) and of small amounts of organic matter that are dissolved in water. The TDS amount ranges between 50mg/l to 650mg/ l with an average of 367 mg/l. In this study, 3 samples (BW7, BW12 and BW18) showed the concentration of TDS exceeds the permissible limits. Figure 3 shows the spatial distribution of TDS in the study area. Carbonates and Bi-Carbonates With respect to HCO 3- 96.5 % of the sampling stations are exceeding the permissible limit set by the WHO (2006) Guidelines for drinking water limit of 240mg/l. The values of HCO3- range between minimum 196 mg/l to maximum 855 mg/l with an average of 423 mg/l. Figure 4 shows the spatial distribution of HCO3-. Calcium(Ca) And Magnesium (Mg) Ca and Mg are from natural sources like granitic terrain which contain large concentration of these elements. The result shows that Mg is exceeding the permissible limit of 30mg/l in more than 82% of the sampling stations, while Ca is within the permissible limits of 75 mg/l except one station (BW 15) where it is exceeding the permissible limit. Ca and Mg are ions of total hardness and hence they are interrelated. The values of Mg varies from 12 mg/l to maximum 125 mg/l with an average of 50 mg/l while the minimum value of Ca is 6 mg/l and maximum 80 mg/l with an average of 34 mg/l. Spatial distribution of Mg and Ca in the study area are represented in figures 5 and 6.


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Fig. 1: Spatial variation of EC in study area

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Fig. 2: Spatial variation of pH in study area

Fig. 3: Spatial variation of distribution of TDS in study area

Fig. 4: Spatial variation of distribution of HCO3- in study area

Fig. 5: Spatial variation of distribution of Mg in study area

Fig. 6: Spatial variation of distribution of Ca in study area


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Fig. 7: Spatial variation of distribution of Chloride in the study area

Fig. 8: Spatial variation of distribution of TH in the study area

Fig. 9: Spatial variation of distribution of sodium in study area

Fig. 10: Spatial variation of distribution of potassium in study area

Fig. 11: Spatial variation of distribution of Nitrate in the study area

Fig. 12: Spatial variation of distribution of Sulfate in study area


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Fig. 13: Spatial Fluoride distribution in the study area Chloride (Cl) Chloride occurs naturally in all types of water. Chloride in natural water may results from agricultural activities, industries and chloride rich rocks. The results obtained shows that all the sampling stations are well within the permissible limit of 250 mg/l guided by WHO (2008) guidelines for drinking water quality. The values vary from 21 mg/l minimum to 87 mg/l maximum with an average of 43 mg/l. Spatial distribution of Chloride concentration in the study area is shown in figure 7.

occurring naturally. The major source of both the cations may be weathering of rocks (11) besides the sewage and industrial effluents. Their values of study area show that both Na and K are well within the permissible limits. The values varies from minimum 45mg/l to maximum 77 mg/l with an average of 62 mg/l and 0.188 mg/l minimum to 10.73 mg/l maximum with an average of 0.88 mg/l respectively. Figure 9 and 10 shows the spatial variation of Na and K in the study area respectively.

Total Hardness (TH) The TH is an important parameter of water quality whether it is to be used for domestic, industrial or agricultural purposes. It is due to the presence of excess of Ca, Mg and Fe salts. The carbonate and bicarbonate concentrations are useful to determine the temporary hardness and alkalinity. Since the analysis of carbonate in this study has given negative results for most of the samples, the alkalinity is mainly due to bicarbonates. Figure 8 indicates the TH obtained shows that 25% of the samples are exceeding the permissible limit of 200 mg/l set by WHO (2008). The values vary from minimum 116 mg/l to maximum 590 mg/l with an average of 292 mg/l.

Nitrate (NO3-) The high nitrogen content is an indicator of organic pollution. It may results from the added nitrogenous fertilizers, decay of dead plants and animals, animal urine, or feces. They are all oxidized to nitrate by natural process and hence nitrogen is present in the form of nitrate. The increase in one or all the above factors is responsible for the increase of nitrate content (12). The ground water contamination is due to the leaching of nitrate present on the surface with percolating water. Figure 11 shows the spatial distribution of Nitrate in the study area. The values of nitrate in the study area vary from minimum 1.858 mg/l to 111 mg/l maximum with an average of 31 mg/l. The results show that 21% of the sampling stations are exceeding the permissible limit of 50 mg/l guided by WHO (2008).

Sodium (Na) and Potassium (K) Na and K are the most important minerals

Sulphate (SO42-) Sulphate is found in small quantities in


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ground water. Sulphate may come into ground water by industrial or anthropogenic additions in the form of Sulphate fertilizers. The results show that the values from the study area are all within the permissible limit of 250 mg/l guided by WHO (2008) for drinking water purpose. The values of sulfate ranges from 73 mg/l minimum to 77 mg/l maximum with an average of 74 mg/l (Figure 12).

anthropogenic activities the concentration of fluoride may have an increasing trend, as Bhosle et al., 2001 (14) has noted that the discharge of domestic wastes from the surrounding industries increases fluoride values. Fluoride distribution in the study area is shown in figure 13.

Fluoride (F) Fluoride occurs as fluorspar (fluorite), rock phosphate, triphite, phosphorite crystals etc. in nature. The factors which control the fluoride concentration includes the climate of the area and the presence of accessory minerals in the rock mineral assemblage through which the ground water is circulating (13). In the present study the concentration of fluoride is within the permissible limits of WHO (2008). They range from 1.094 mg/l minimum to maximum 1.128 mg/l with average of 1.1029 mg/l. from the results obtained it can be noticed that the values of fluoride are exceeding the desirable limit of 1 mg/l. with the increase

Spatial variations in ground water quality in the study area were studied successfully by using geographic information system (GIS). The results obtained in this case study and the spatial database established in GIS shows the same approach can be used for determining, monitoring and managing ground water quality and its pollution for wide areas. The database formed can be very useful for future research and reference.

CONCLUSION

ACKNOWLEDGEMENTS Authors sincerely acknowledge support provided by GSDA Pune.

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WHO, Guidelines of drinking water quality Recommendation: the 3rd edition. Geneva: World Health Organisation. 2 (2006). APHA.Standard methods for examination of water and waste water, 19th Edition. Washington, DC:American Public Health Association (1995). Khan, F., Husain T., and Lumb A., Environmental Monitoring and Assessment, 88: 221-242 (2003). Sargaonkar, A. and V. Deshpande, Environmental Monitoring and Assessment, 89: 43-67 (2003). MounaKetata-Rokbani, MoncefGueddari and RachidaBouhlila, Iranica Journal of Energy & Environment 2(2): 133-144 (2011). 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, Sunada, O.N. Choubey, Orient J. Chem., 26(1): 319-323 (2010).

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Balakrishnan P., Abdul Saleem and Mallikarjun, N. D., African Jour nal of Environmental Science and Technology , 5(12): pp. 1069-1084 (2011). Burrough PA, McDonnell RA, Principles of Geographical Information Systems Oxford: Oxford University Press, p. 333. (1998). Sivasankar, K., Gomathi, R. Water Quality Exposure Health,1: 123-134 (2009). Pradeep Jain, K., Poll. Res. 17(1): 91-94 (1998). Dahyia, S., Datta, D., Kushwaha, H. S., Environmental Geology, 8: 158-165 (2005). Singh, T. B., IndhuBala and D. Singh, Poll. Res. 18(1): 111-114 (1999). Rahman:,‘Groundwater quality of Oman’, Groundwater Quality, London, pp. 122-128 (2002). Handa BK, Ground Water 13: 275-28 (1975) Bhosle, A. B., Narkhede, R. K., BalajiRao and Patil, P. M., Eco. Env.&Conserv.7(3): 341–344 (2001).


Current World Environment

Vol. 7(2), 287-292 (2012)

Use of Industrial Waste Water for Agricultural Purpose: Pb and Cd in Vegetables in Bikaner City, India RAJENDRA SINGH1, R.S.VERMA2 and YOGITA YADAV3 1

Department of Chemistry, IGBN PG college Jhunjhunu India. Department of Chemistry, Government Dungar College Bikaner, India. 3 Department of Chemistry, Banasthaly Vidhyapeeth, Tonk, India.

2

(Received: July 12, 2012; Accepted: September 17, 2012) ABSTRACT Shortage of irrigation water resources is leading to the use of domestic and industrial waste water in agriculture especially. In urban areas. Being contaminated by metals and various toxic chemicals these waste waters leads to the exposure of heavy metals and hazardous chemicals and the subsequent human health hazards through agriculture products and live stocks. Increasing cases of cancer and kidney problems is also related with this aspect. In present study human health risk assessment taken in concern with the respect of some heavy metals of toxicological interest.

Key words: Waste water, Contaminated, Health hazards, Health assessment, Heavy metals.

INTRODUCTION Decreasing water level and shortage of water is being a major problem world wide. For agriculture purpose this problem gives rise to the use of alternative sources of water. Most of these water sources are affected by the dumping of waste from various types of industries like mining, textiles, chemical etc. Due to reason this waste water may contains many organic toxic substances that could have hazardous impact on human health. In addition, technological development has contributed to increase other industrial dumping that contaminates surface waters. The irregular disposal of industrial wastes has created pollution problems since this waste is disseminated in the environment or is accumulated in sediments, aquatic organisms, and water. There are many studies on the possible effects of chemical substances on humans through laboratory.

Experiments in animals and information are available on the incidence of cancer by prolonged exposure to toxic substances. Experiments in plants and insects, as the Drosophila (fruit fly), demonstrate that toxic substances of chemical origin induce genetic mutations and chromosome aberrations. These experiments demonstrate that exists a risk, but it is not simple to extrapolate these results to human beings. The population is exposed to toxic chemical compounds through the use of wastewater in agriculture. Theoretically, wastewater of industrial origin should not be used for this purpose but in developing countries formal and clandestine industries dispose of their effluents to the municipal sewerage with or without authorization and without any treatment. This exposes the population, to relatively small quantities for chemical compounds and may produce chronic intoxications with serious consequences. Another health hazard pose by inadequate disposal of wastewater is the use of


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sediments for soil improvement because they contain toxic elements that may accumulate (PAHO, 1989). The environmental impact of chemical residues in wastewater used for irrigation and the prediction of their effects on human health are a very complex matter. In addition, it should be considered that the standards of developed countries do not apply to areas with different characteristics. The factors that influence the nature and intensity of the impact on health are: the climate, nutritional status, genetic predisposition, type of work and exposure level. The indiscriminate use of pesticides also influences the deterioration of water quality. This resource can be contaminated by runoffs from crops, atmospheric precipitations and, to a lesser extent, by domestic sewage. Polychlorinated biphenyls (PCB), present in lager quantity in pesticides and other organochlorine compounds, are degraded very slowly in the environment and are bioaccumulative, thus, they represent a potential danger. Air and water are vehicles through which PCB are dispersed in the environment, although food also constitute an important vehicle. As a consequence, PCB residues are found in living organisms form many regions. The highest concentrations are usually present neat industrial areas . Industrialization and urban development without adequate planning increase human health hazards by exposure to chemical substances through air, water sediments, and food. The nature of this risk and its potential danger has been recognized a few years ago and its effects still have not been evaluated (PAHO, 1990). The identification and confirmation of such effects are difficult because epidemiological studies last long, the population migrates, and exposure time is unknown. In addition, chronic diseases can have various causes and, in many cases, they are not classified correctly. Usually, in developing countries there is not statistical information on the trends and causes of diseases produced by ingestion of chemical substances through agricultural and livestock

products. However, several studies have deconstructed adsorption of heavy metals by plants, such as wheat and rich that can affect the consumers (WHO, 1992). An epidemiological evidence was the case of Toyama, Japan, where the population was affected by the ingestion of cadmium contained in rice; the origin of this element was a nearby mine that contaminated the irrigation water. The nature of human health hazards by exposure to toxic chemical compounds varies considerably. In general, they increase birth defects, abortions and certain forms of cancer, and decrease the average weight of children at birth. Case study: wastewater use in agriculture in Bikaner, India The study “health risk evaluation due to wastewater use in agriculture” was conducted in four agricultural areas (Bikaner East, Karni Industrial area, central market, Reliance fresh retail outlet). General objective of the study To evaluated the chemical-toxicological level of contamination of the agricultural products irrigated with raw and treated wastewater. Specific objectives ´ To determine the concentration of toxic heavy metals and synthetic organic compounds (pesticides and polychlorinated biphenyls) in rivers, raw wastewater and treated wastewater used for irrigation. ´ To determine to concentration of toxic heavy metals, pesticides, and polychlorinated biphenyls in agricultural and livestock products (vegetables and milk) form areas irrigated with water of rivers, raw wastewater and treated wastewater. ´ To compare the potential risk associated with toxic chemical compounds present in waters of rivers, raw wastewater and treated wastewater used to irrigate agricultural and livestock products. ´ To train professionals in the measurement of metallic organic toxic substances and, thus, to increase the local analytical capacity. ´ However the present paper is mainly concerned with some heavy metals of toxicological interest.


SINGH et al., Curr. World Environ., Vol. 7(2), 287-292 (2012) Methodology The study was conducted in Bikaner, India to evaluate the presence and concentration of toxic chemical compounds in waters used for irrigation and in agricultural and livestock products from areas of reuses, a control area, and markets. In addition, soils and sludge were analyzed. The areas selected for the study were: Bikaner East, (control area), karni industrial area (use of industrial and domestic waste water) central market (use of ground water and canal water) reliance fresh retail outlet. Analyses of metals, pesticides, and PCB were carried out in all water samples. The following analytical procedures were applied Water The analytical methodologies proposed by the Health and Welfare, Ottawa, Canada, National Water Research (Burlington) and by the Standard Methods (15a. edition, 1985) were used.

253µg/1), copper (50 to 250µg/1), iron (1.800 to 6.400µg/1), and zinc (60 to 2.460µg/1), (see Figure 1). Chlorinated pesticides in different sampling points were very low (<700ng/1). With regard to PCB, the highest value was detected in Bikaner east (270µg/1). In general, removal of heavy metals, pesticides, and PCB is produced in stabilization ponds. The agricultural and livestock products selected for the study were: Reddish Potato, Brinjal, Carrot, Cabbage, and milk from the areas of study and nearby markets. The highest value of lead was detected in brinjal samples from markets (0,037µg/ ) (see Table 1). Cadmium does not constitute and problem in the areas studies. With regard to metal concentration and hygiene agriculture products available at Reliance fresh outlet were found to be best.

Agricultural products The recommendations of the Health Protection Branch Laboratory, Food Laboratory, Toronto, Canada, and the analytical methodologies of CEPIS developed with the support of JICA were applied. Soil and sludge The methodologies proposed by USPEA and by the standard Methods (15a. edition, 1985) were adopted. For analytical quality control, measurements were subject to an analytical quality control program developed by CEPIS laboratory and the methodology used by international authorities. Recovery tests were performed with selected samples to which known quantities of analite were added, in addition, control tests of distilled water and solvents for pesticides and PCB were done. RESULTS With respect to the results, in industrial wastewater high levels of heavy metals were found: arsenics (7 to 220µg/1), (5 to 43µg/1), lead (10 1

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Fig. 1: Metals of toxicological interest in irrigation water


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Table 1: Lead and cadmium in agricultural products Area

Sampling place

Bikaner east

Agricultural Area

Market

Species

Reddish Potato Brinjal Carrot Reddish Potato Brinjal Carrot Cabbage

Reddish Potato Brinjal Carrot Tomato

Karni industrial area Agricultural Area

Centeral Markets of Bikaner

Market

Reddish Potato Brinjal CarrotTomato Reddish Potato Brinjal Carrot Tomato

Reliance Fresh Retail outlet

Retail Chain shop

CONCLUSIONS The use of industrial wastewater in agriculture and livestock represent and potential risk for health, due to the toxic nature of chemical compounds and to the concentrations to which the products are exposed. Irrigation water with low levels of lead (around 30 µg/1) has a minimum influence in the toxicological quality of vegetables whose edible part grows beneath the soil. Vegetables growing at the soil surface level may be contaminated by atmospheric emissions containing lead.

Concentration Pb (µg/g)

Cd(µg/g)

<0.004 0.004 0.014 <0.002 <0.004 0.004 0.003 <0.002 <0.003

<0.013 <0.003 <0.003 <0.003 <0.033 <0.003 <0.033 <0.003 <0.003

0.004 0.003 0.037 <0,002 <0,002

<0,003 <0,003 <0,003 <0,003 <0,003

<0,003 <0,002 <0,003 <0,002 <0,002 <0,002 <0,002 <0,002 <0,002 <0,002

<0,003 <0,003 <0,003 <0,003 <0,003 <0,003 <0,003 <0,003 <0,003 <0,003

For irrigation water, the permissible limit values of toxic chemical compounds should not be regarded as absolute values, but should be adapted to the local conditions considering contributions from other sources. Wastewater treatment by means of stabilization ponds as well as commonly available treatment plants removes toxic elements when low concentrations are found in raw wastewater. ´ The establishment of permissible maximum limits of toxic substances should be studied for irrigation water considering conditions of soil, types of plant, and bioaccumulation. ´ Metal Toxicity seems to be a significant factor for the increasing cases of cancer and kidney


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´ ´

´

diseases. A continuous study with this respect and keen public awareness is required. A responsible planning implementation and strict regulation of environmental laws is required. State government seems to do only table

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and data work as posing itself aware with the respect of human health and environmental perspective on national und international desk. Delayed effects of this governmental and public unawareness may result as serious human health hazard.

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Anderson PR, Christensen TH., Distribution coefficients of Cd, Co, Ni and Zn in soils. J Soil Sci 39:15-22 (1988). Baes CF III, Sharp RD, Sjoreen AL, Shor RW. A Review and Analysis of Parameters for Assessing Transport of Environmentally Released Radionuclides through Agriculture. DE85-000287. Springfield, VA:US Departmen of Commerce, National Technical Information Service (1984). Calabrese EJ, Stanek EJ, Pekow P, Barnes RM., Soil ingestion estimates for children residing on a superfund site. Ecotox Environ Safe 36: 258-268 (1997). Chronopoulos J, Haidouti C, ChronopoulouSereli A, Massas I., Variations in plant and soil lead and cadmium content in urban parks in Athens, Greece. Sci Total Environ 196: 91-98 (1997). Dalenberg JW, Van Driel W., Contribution of atmospheric deposition to heavy-metals concentrations in field crops. Neth J Agrci 38: 396-379 (1990). DEFRA (Department of Environment, Food and Rural Affairs). Total Diet Study— Aluminium, Arsenic, Cadmium, Chromium, Copper, Lead, Mercury, Nickel, Selenium, Tin and Zinc. London:The Stationery Office (1999). DEFRA (Department of Environment, Food and Rural Affairs) and Environment Agency. Contaminated Land Exposure Assessment Model (CLEA): Technical Basis and Algorithms. Bristol, UK:Department for the Environment, Food and Rural Affairs and The Environment Agency.. 2002b. Contaminants in Soil: Collation of Toxicological Data and Intake Values for Humans. CLR9. Bristol

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(2002a). Hawley JK., Assessment of health risk from exposure to contaminated soil. Risk Anal 5: 289-302 (1985). Hérbert CD., Subchronic toxicity of cupric sulphate administered in drinking water and feed to rats and mice. Fundam Appl Toxicol 21: 461-475 (1993). Hough RL. 2002. Applying Models of Trace Metal Transfer to Hough RL, Young SD, Crout NMJ., Modelling of Cd, Cu, Ni, Pb and Zn uptake, by winter wheat and forage maize, froma sewage disposal farm. Soil Use Manage 19: 19-27 (2003). Keefer RF, Singh RN, Horvath DJ., Chemical composition of vegetables grown on an agricultural soil amended with sewage sludges. J Environ Qual 15: 146-152 (1986). Konz J, Lisi K, Friebele E., Exposure Factors Handbook. EPA/600/8-89/043. Washington, DC:U.S (1989). Northwood Geoscience Ltd., Vertical Mapper for MapInfoVersion 1.5. Nepean, Ontario, Canada:Northwood Geoscience Ltd (1996). Reilly C., Metal Contamination of Food. 2nd ed.speciation of Pb2+ and Cu2+. Environ Toxicol Chem 17: 1481-1489 (1991). Shao J., Linear model selection by crossvalidation. J Am Stat Assoc 88: 486-494 (1993). Stanek EJ, Calabrese EJ, Zorn M., Soil ingestion estimates for Monte Carlo risk assessment in children. Hum Ecol Risk Assess 7: 357-368 (2001). Sterrett SB, Chaney RL, Gifford CH, Meilke HW., Influence of fertilizer and sewage sludge compost on yield of heavy metal accumulation by lettuce grown in urban soils.


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Environ Geochem Health 18: 135-142 (1996). B.D. Gharde, Orient J. Chem., 26(1): 175-180 (2010). Trowbridge PR, Burmaster DE., A parametric distribution for the fraction of outdoor soil in indoor dust. J Soil Contam 6: 161-168 (1997). Teuschler LK, Dourson ML, Stiteler WM, McClure P, Tully H., Health risk above the reference dose for multiple chemicals. Regul Toxicol Pharm 30: S19-S26 (1999). Arokiyaraj, R. Vijayakumar and P. Martin, Orient J. Chem., 27(4): 1711-1716 (2011).

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Van Lune P., Cadmium and lead in soils and crops from allotment gardens in the Netherlands. Neth J Agric Sci 35: 207-210 (1987). Waalkes MP, Rehm S., Cadmium and prostate cancer. J Toxicol Environ Health 43: 251-269 (1994). Wang XJ, Smethhurst PJ, Herbert AM., Relationships between three measures of organic matter or carbon in soils of eucalypt plantations in Tasmania. Aust J Soil Res 34: 545-553 (1996).


Current World Environment

Vol. 7(2), 293-297 (2012)

Bioaccumulation of Heavy Metals in Different Components of two Lakes Ecosystem AMIYA TIRKEY*, P. SHRIVASTAVA2 and A. SAXENA1 1

M.P. Pollution Control Board, Bhopal - 462 016, India. Department of Life Sciences and Limnology, Barkatullah University, Bhopal, India.

2

(Received: July 12, 2012; Accepted: September 17, 2012) ABSTRACT Bioaccumulation of heavy metals (Cu, Cd, Ni, Fe and Pb) was examined by atomic absorption spectrophotometer in sediment, water and fish samples of two different lakes; freshwater and sewage fed water namely Upper and Shahpura Lake respectively of Bhopal, (M.P.) India. All these trace metals were greater in polluted lake as compared to freshwater lake, except Pb. The experimental results clearly indicated heavy metal accumulation in different trophic level of both lakes.

Key words: Bioaccumulation, heavy metals, Upper Lake, Shahpura Lake, trophic level.

INTRODUCTION Contamination of aquatic ecosystems by heavy metals has been observed in sediment, water and aquatic flora and fauna (Forstner and Whittmann, 1983). Different aquatic organisms often respond to external contamination in different ways, where the quantity and form of the element in water, sediment or food will determine the degree of accumulation (Langston & Spence, 1995). Heavy metals entering the aquatic ecosystem originate from different sources such as decay of plants and vegetation, atmospheric particulate, discharge of domestic and municipal wastes etc. (Abo et al., 2005, Fatma A.S.M., 2008). Like soils in the terrestrial system, sediment is the primary sinks for heavy metals in the aquatic environment. Heavy metals once absorbed on the sediments sre not freely available for aquatic organisms. Under changing environmental conditions (temp., pH, redox potential, salinity) of the overlying water these toxic metals are released back to the aqueous phase (Soares et al., 1999). Hence, the assessment of sediment is significant to study the risk of aquatic ecosystem. Similarly

fishes assimilate these heavy metals through ingestion of water, food materials and constant ion exchange process of dissolved metals across lipophilic membranes like gills or adsorption on surface membrane like skin. The region of accumulation of heavy metals within fish varies with route of uptake, heavy metal species and species of fish concerned. Their potential use as biomonitors is therefore significant in the assessment of bioaccumulation and biomagnifications of contaminants within the ecosystem. MATERIALS AND METHODS Study Area Two major artificial water resources were selected for the study. Both lakes are of commercial importance due to their beautiful location, but also face severe environmental stress. Shahpura Lake (23° 18' N, 77° 27' E) and 488 m above mean sea level. The lake covers an area of 2.6 km2, has a mean depth of 3.0 m and a catchment’s area of 8.3 km2. Approximately 110 tons / day solid waste is generated within the catchment and 9.6 millions litres per day of sewage enters the


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lake from residential areas in the catchment (Shrivastava et al., 2003). It is located in the south east of the city and receives heavy loads of domestic and municipal sewage. The lake water is used in pisciculture, idol immersion, cattle bathing, washing and minor irrigation. Upper Lake (23°12' E - 23°16’N, 77° 18' 77° 23' E) has an area of 31 km², and drains a catchment or watershed of 361 km². The watershed of the Upper Lake is mostly rural, with some urbanized areas around its eastern end. The topography of the lake indicates that the basin is natural, as northern and southern sides of the lake are hilly while the western end has flat contours and forms the agricultural land (Dixit S. et al., 2005). It is a major source of drinkable water for the residents of the city, serving around 40% of the residents with nearly 30 million gallons per day. The lake water is used for fishing, boating, idol immersion and irrigation. Field Sampling The sampling of water and sediment from Shahpura and Upper Lake were based on the principles and procedures outlined in standard methods for the examination of heavy metals in water (APHA, 1995). Sampling was done each month of summer season (March-May, 2010). Fish samples were collected from the local fishermen and brought to laboratory for dissection and further

heavy metal determination. Heavy metal determination Surface water was collected by dipping one litre capacity white jerricane. The water sample was acidified with 2ml HNO3 at the sampling site. The heavy metals in water samples were analysed by AAS. Sediment samples were dried at room temperature and ground with pestle and mortar. They were further sieved through 0.2mm mesh size filter and stored in clean polybags till analysis. With the help of stainless steel scalpel liver, gills and muscle tissues of fishes were removed. The acid digestion of sediment and fish tissues was done according to the standard methods. The concentrations of the heavy metals were estimated with Atomic Absorption Spectrophotometer (GBC Avanta PM, Australia). All reagents used were of AnalaR grade and all glass wares and polypropylene were properly cleaned with acid cleansing reagents and rinsed thoroughly with distilled deionised water. RESULTS AND DISCUSSION The concentrations of heavy metals estimated in sediment, water and fish samples collected from both lakes are given in Table 1. The concentrations of heavy metals varied in all different components.

Table 1: Heavy metal concentrations in different components of Upper Lake and Shahpura Lake (Mean ±SD) (n=4)

Water (mg/l) Upper Lake Shahpura Lake WHO (2004) Sediment (mg/kg) Upper Lake Shahpura Lake Fish muscle (mg/kg) Upper Lake Shahpura Lake WHO (2004) n: number of samples

Cu

Cd

Ni

Fe

Pb

0.00±0.00 0.001±0.001 1.0

0.00±0.00 0.00±0.00 0.05

0.032±0.015 0.785±0.209 0.025±0.01 0.567±0.128 0.05 1.0

0.109±0.007 0.00±0.00 0.05

32.75±19.88 233.45±238.54

0.00±0.00 0.05±0.10

29.0±19.51 47.0±14.94

14025±6709 56650±43888

364.25±307.28 50.20±38.05

0.7±0.2 0.61±0.17 3.0

0.726±0.045 0.41±0.19 2.0

0.33±0.57 2.0±1.0 0.6

22.11±4.01 82.66±4.50 10.0

1.76±0.25 0.00±0.00 2.0


TIRKEY et al., Curr. World Environ., Vol. 7(2), 293-297 (2012) Copper It is essential for human life, but in high doses it may cause anaemia, liver and kidney damage, stomach and intestinal irritation etc. The average concentration of Cu observed were, in water (0.00 ± 0.00 mg/l, 0.001 ± 0.001 mg/l) and fishes (0.7±0.2 mg/kg, 0.61±0.17 mg/kg) in Upper and Shahpura Lake respectively, which were within the limits of WHO (2004). In sediment samples Upper Lake accumulated 32.75±19.88mg/kg whereas Shahpura Lake accumulated 233.45±238.54mg/ kg of Cu (Fig. 1). Traces of Cu in drinking water may be due to the lining of copper pipes, as well as from additives used to control algal growth.

295

decades for humans) although it is eventually excreted. High exposure leads to obstructive lung disease and can even cause lung cancer. Cd produce bone defects in humans and animals. Cd was below detectable limit (0.00mg/l) in water of both lakes (Fig. 2). Fish muscles showed 0.726±0.045mg/kg and 0.61±0.17mg/kg of bioaccumulation respectively in Upper and Shahpura Lake. Nickel

Cadmium Cadmium derives its toxicological properties from its chemical similarity to Zn an essential micronutrient for plants, animals and humans. Cd is biopersistent and once absorbed by an organism, remains resident for many years (over

Small amount of Ni is needed by human body to produce red blood cells, however, in excessive amounts, it can become mildly toxic. Short term over exposure to Ni is not known to cause any health problems, but long term exposure can cause decreased body weight, heart and liver damage and skin irritation. Average concentration of Ni was 29.0±19.51 mg/kg and 47.0±14.94 mg/ kg in sediment, 0.032±0.015 mg/l and 47.0±14.94 mg/l in water and 0.33±0.57 mg/kg and 2.0±1.0

Fig. 1: Variation of Cu between Upper and Shahpura Lake

Fig. 2: Variation of Cd between Upper and Shahpura Lake

Fig. 3: Variation of Ni between Upper and Shahpura Lake

Fig. 4: Variation of Fe between Upper and Shahpura Lake


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mg/kg in muscles of fishes of Upper and Shahpura Lake respectively (Fig. 3). Fishes of polluted water body showed bioaccumulation of Ni and may be considered unsafe for human consumption. Iron Fe is essential for plant and animal metabolism. Fe overload in man is not common but may occur due to genetic defect. Such overload results in oxidative degradation of lipids, destruction of intercellular and extracellular proteins and DNA damage. Extreme values of Fe was detected in fish muscles i.e. 22.11±4.01 mg/kg and 82.66±4.50 mg/ kg in Upper and Shahpura Lake which is much higher than WHO (2004) limits. The reason may be because of absorption of Fe residues through the intestinal walls of fishes (Bu-Olayan A.H., 2008). Likewise sediment samples showed the concentration of 14025±6709 mg/kg and 56650±43888 mg/kg in Upper and Shahpura Lake respectively (Fig. 4). Water showed permissible limits for safe consumption of humans and aquatic life in freshwater and polluted lakes. Lead Lead in the environment arises from both natural and anthropogenic sources. Exposure can occur through drinking water, food, air, soil and dust from old paint containing Pb. High levels of exposure may result in biochemical effects in humans which

in turn cause problems in the synthesis of haemoglobin, effects on the kidneys, gastrointestinal tract, joints and reproductive system, and acute or chronic damage to the nervous system. The average concentration of Pb in sediment is 364.25 mg/kg and 50.20 mg/kg in Upper and Shahpura Lake respectively (Fig. 5). This value is very high when compared to the average Pb levels in Indian river sediment of about 14mg/kg (Dekov et al., 1999). The Pb concentration in water of Upper Lake, 0.109 mg/l is above the permissible limits for drinking water by WHO (2004). This indicates a high anthropogenic activity surrounding the lake which includes idol immersion, motor boats for recreation, traffic pollution. Fishes of Upper Lake showed higher bioaccumulation of 1.76±0.25mg/ kg as compared to Shahpura Lake. The results of this study showed that the water, sediment and fish of both lakes were contaminated by the heavy metals Cu, Cd, Ni, Fe and Pb. Sediments from both lakes showed high concentration of toxic metals. The results further showed that water could be used for irrigational purposes but unsafe for drinking as traces of Pb found in Upper Lake. These results agree with that obtained by Saxena A. et al., (1998) and Shahpura Lake is fit for pisciculture and minor irrigation. Fishes of Upper Lake are safe for human intake. It is proposed that continuous monitoring and intensive management in the area should be carried out to ascertain long term effects of anthropogenic impact and to assess the effectiveness of minimising the human activity to maintain our lake ecosystem. ACKNOWLEDGEMENTS The author would like to thank the staff of Central Laboratory, M.P. Pollution Control Board, Bhopal for providing support during sampling and laboratory facilities to fulfil my experiments. Special thanks to Dr. Sadhya Mokhle for her assistance in heavy metal analysis in AAS.

Fig. 5: Variation of Pb between Upper and Shahpura lake

REFRENCES 1.

Forstner, U. and G. T. Whittmann: Metal pollution in aquatic environment, SpringerVerlag, Berlin, Heidelberg, New York, Tokyo,

2.

pp 486 (1983). W.J. Langston and S.K. Spence: Metal speciation and bioavailability in aquatic


TIRKEY et al., Curr. World Environ., Vol. 7(2), 293-297 (2012)

3.

4.

5.

6.

7.

8.

systems. A Tessier & D.R. Turner, Editors, IUPAC Series on Analytical and Physical Chemistry of Environmental Systems, 3: Chapter 9 (1995). Abo El Ella, S.M., M.M. Hosny and M.F. Bakry: Utilizing fish and aquatic weeds infestation as bioindicators for water pollution in Lake Nubia, Sudan. Egypt. J. Aq. Biol Fish. 9: 6384 (2005). Fatma A.S. Mohamed: Bioaccumulation of selected metals and histopathological alterations in tissues of Oreochromis niloticus and Lates niloticus from lake Nasser, Egypt. Glob. Veter. 2(4): 205-218 (2008). Soares, H.M.V.M., R.A.R. Boaventura, A.A.S.C. Machado and J.C.G. Esteves da Silva: Sediments as monitors of heavy metal contamination in Ave river basin (Portugal): multivarioate analysis of data. Env. Poll. 105: 311-323 (1999). Shrivastava P., Saxena A. and Swarup A: Heavy metal pollution in a sewage fed lake of Bhopal, (M.P.) India. Lakes and Res, 8: 14 (2003). Dixit S., Gupta S.K. and Tiwari Suchi: A nutrient overloading of a freshwater lake in Bhopal, India. Earth Day, Issue 21 (2005). APHA: Standard methods for the examination of water and wastewater 19th Ed. American Public Health Association

9. 10.

11.

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13.

14.

15.

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(1995). P. Sannasi and S. Salmijah, Orient J. Chem., 27(2): 461-467 (2011). Dekov, V.M., Subramanian, V., Van Grieken, R.: Chemical composition of riverine suspended matter and sediments from the Indian sub-continent. In: Ittekkot, V., Subramanian, V. And Annadurai S. (Eds), Biogeochemistry of Rivers in Tropical South and Southeast Asia. Heft 82, SCOPE Sonderband Mitteilug aus dem GeologischPalaontolgischen Institut der Universitat, Hamburg, pp. 99-109 (1999). WHO: Guidelines for Drinking Water Quality, 3rd Ed. World Health Organisation, Geneva (2004). B.M. Bheshdadia, D.S. Kundariya and P.K. Patel, Orient J. Chem ., 27(2): 685-689 (2011). Bu-Olayan A.H., Thomas B.V. :Trace metals toxicity and bioaccumulation in mudskipper Periophthalmus waltoni Koumans 1941(Gobiidae: Perciformes). T. Jour. of Fisheries and Aquatic Sciences, 8 :215-218 (2008). Dixit S., Gupta S.K. and Tiwari Suchi: A nutrient overloading of a freshwater lake in Bhopal, India. Earth Day, Issue 21(2005). Saxena A. and Shrivastava P. And Swarup A.: Heavy metal pollution in a tropical wetland. Lakes and Res (1998).


Current World Environment

Vol. 7(2), 299-300 (2012)

Equilibrium Sorption Studies for Fluoride content in Drinking Water of Bore wells of Warud Region on Ferronia Elefuntum Fruit Shell U.E. CHAUDHARI Department of Chemistry, Mahatma Flue Mahavidyalaya, Warud – 444 906, India. (Received: October 12, 2012; Accepted: December 05, 2012) ABSTRACT Major water supply for agriculture and domestic purpose in Warud Region is from Upper Wardha and Shekhadari Dam Water. Even then, resident of most of the areas are mainly dependent on bore well water for domestic and Agriculture purpose especially in summer season. Hence large numbers of bore wells are existed. Fluoride content of selected bore-well water in an around of Warud was analyzed in the month of May, 2011. The study reveals that the fluoride concentration is within the permissible limits in few places as prescribed by BIS and WHO. But in some places it is more than prescribed by BIS and WHO. Hence it is essential to remove these excess fluorides by adsorption.

Key words: Bore well water Fluoride concentration, Fluorosis Adsorption

INTRODUCTION Warud is a Taluka place located on the border of Maharashtra and M.P. States. It is situated at the base of satpuda Ranges and covered by dense woods with many medicinal plants and water bodies. It is famous for oranges and commonly known as “California of Vidarbha”. The major crops of the district is ‘Oranges’. The famous historical and holy place salbardi is only 30Km, away from Warud. The main water supply is from Uppar Wardha Dam and Shekhdari dam water to this Warud Region. Water is most common and important resource on the earth (Suther et al., 2001). However, the availability of water varies from place and time to time. As a result, there is a persistent scarcity of water is many parts of the world. Exponential growth in population creates an ever increasing demand of water for irrigation, industry and domestic use (Shankar et al., 2004, Wright 2007). Due to the population growth of this area and in the villages, the scarcity of water arises especially during summer season Warud Region is famous for orange crops. Farmers of this area using 50% land for orange irrigation purpose. From last 100 years ago they are using water for arigation purposes. Due to this water level of this region become deeper and deeper. Upper Wardha Dam water is insufficient to provide it for agriculture as

well as drinking purposes to this area. As a result, a large number of bore well existed in this area to meet the water demands. Now a days, these Bore well is 500 to 800 feets deep. it is found that water from these bore well contain fluoride. The poor quality or drinking water is more due to the contamination than due to natural inferiority of the sources. Fluorides are present in both surface water and ground water. Most of the fluoride found in ground water result from weathering and circulation of water in rocks and soils. The chemical quality of ground water varies even at short distances. This variation may be attributed to the variations in the hydro chemical process (Maniraju, 2006). Fluoride in small dosages has remarkable influence on the dental system inhibiting denta curies, while consumption of high dosage fluoride water causes fluorosis (Shukla et al., 2004). In India about 62 million people including 6 million children, suffer from fluorosis due to high content of Fluoride in water (Susheela, 1990). The present analysis is an attempt to evaluate the fluoride content of bore well water in Warud Region. Adsorbent Preparation The Ferronia Elefuntum Fruit Shell was first died at a temperature of 160°C for 6 hours. After grinding it was sieved to obtain average particle size of 200 mesh. It was then washed several times with distilled water to remove dust and other impurities. Finally it was dried again in an ovan at


CHAUDHARI et al., Curr. World Environ., Vol. 7(2), 299-300 (2012)

300

50°C for hours. The adsorbent was then stored in desiccator for final studies. MATERIAL AND METHODS In the present study, fifteen bore well water samples of selected areas in and around Warud analyzed. The samples were collected in clean polythene bottles of 2 ltr. capacity. The bottles were first rinsed with distilled water and then two to three times by the sample water before collecting for analysis. Initial Fluoride concentration in water samples were determined using the parameters prescribed in standard methods for the Examination of water and wastewater APHA (1995). In reagent bottle two hundred ml. of this Table 1: Fluoride ion concentration in bore well water samples before and after adsorption in ppm Samples

S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 S11 S12 S13 S14 S15

Initial concentration 0.8 0.9 1.0 0.95 0.75 0.89 1.6 0.85 0.92 0.56 0.60 1.32 0.92 0.97 0.76

water is mix with 100 mg of Granular tree bark and shake for 3 hour. After shaking filteral it with whatmann filtered paper and content is analised and final flourides concentration is given in table 1. RESULTS AND DISCUSSION Fluoride has little significance in industrial water, where as ingestion of excess fluoride in drinking water can cause fluorosis (Shukla et al., 2004), which affects the teeth and bones. Below the permissible, limits, it is an effective preventive of dental curies, but above the permissible limits may causes disfigurement of teeth and severe skeletal flurosis. Such water should be defluorinated to reduce fluoride concentration by the process of adsorption on Ferronia Elefuntum Fruit shell to the acceptable levels for drinking purpose. The observed results were compared with the standard values of BIS and WHO (i.e. 0.6 â&#x20AC;&#x201C; 1.5 ppm.) CONCLUSION

Final concentration of fluoride 0.60 0.65 0.75 0.67 0.65 0.82 1.2 0.65 0.67 0.50 0.52 0.95 0.62 0.67 0.55

The present analysis concludes that, the fluoride concentration (Table 1) of few samples are well within the permissible limits as prescribed by BIS and WHO and the results reveals that the some bore wells water of Warud are fit for drinking without any pretreatment for fluoride contents. But few sample cantain excess concentration than prescribed by BIS and WHO. These excess concentration were removed by adsorption of fluoride on FEFS. These cheap and efficient absorbents can carry to cater the need of population in the rural areas and the population in the industrial area where safe drinking water is not available. But other physico-chemical parameters of these borewells water have to be analyzed for its suitability.

REFERENCES 1.

2.

3.

APHA: AWWA and WEF, Standard methods of examination of water and waste waster (19 th edition) American Public Health Association, Washington, D.D. (1995). BIS : Specification for drinking water IS : 10500 : Bureau of Indian Standards, New Delhi (1991). Maniraju, Y.M., Vijrappa, H.C. and Nellakantrama, J.M. Fluoride concentration of water in Vrishabharathi river Basin, Bangalore District, Karnataka, Indian J. Environ. and Ecoplan, 12: 665-668 (2006).

4.

5.

6. 7.

Shukla, J.B. and Kaur, H., Environmental Chemistry, Meerut, India. Susheela, A.K. 1999. Fluorosis management programme in India. Curr. Sci., 77: 1250-1256 (1994). Susheela, A.K. Fluorosis management programme in India. Curr. Sci., 77: 12501256 (1999). WHO, Guidelines for drinking water quality 1 (1984). W.H.O. Guide lines for drinking water quality, 3 rd Edition, would Health Organisation Geneva (2004).


Current World Environment

Vol. 7(2), 301-303 (2012)

A Study on Seasonal Variation in the Physico-chemical Assessment of MPN and Fluoride Analysis of Drinking Water of Gandhinagar Area of Bhopal H.C. KATARIA1 and SANTOSH AMBHORE2 1

Department of Chemistry, Government Geetanjali Girls College, Bhopal - 462 038, India. Department of Chemistry, Government Motilal Vigyan Mahavidalaya, Bhopal - 462 003, India.

2

(Received: July 12, 2012; Accepted: September 17, 2012) ABSTRACT Determination of fluoride concentration of sampling stations from different sites in and around villages near Gandhinagar of Bhopal was carried out by using selective fluoride ionelectode. Determination of coliform bacteria/MPN of drinking water samples collected from various places by using H2S paper strip method and checked form black coloration in paper strip.

Key words: Determination, Fluoride ion concentration, Drinking water, Fluorosis, Coliforms, MPN (myeloproliferative neoplasm)

INTRODUCTION Bhopal the capital of Madhya Pradesh territory the largest state of India. Bhopal is situated on 23°16’N Latitude and 77°25' Longitude and is located on Hard pink sand stone of Vindhya region Fluoride concentration in India, creates health problems and fluorosis. The disease previously called as “Mottled teeth” reported in Madras City (1933). Most of the population of 18 states out of 35 states in India are well affected with dental, skeletal and non-skeletal fluorosis, which southern India is badly affected by “Fluorosis”. Fluoride in drinking water is 1.0-1.5 mg/l recommended by WHO (2004). Fluoride concentration has analyzed by using ion selective electrode and ORION 407A meter followed by standards as prescribed by APHA (1992) . The water samples was preserved by adding total ionic strength adjustment Buffer (TISAB) in 1:1 radi and analysis for fluoride levels is calculate by standard curve platted on a semilog graph conc.(Log axis) vs mV. Teofia and Teofia index (TTI 1991) has commonly used to score dental fluorosis in several endemic areas of this country

The present investigation describe the qualitative and quantitative assessment of different water samples collected different sampling stations of study are collected from various sampling places in 2011-2012. by using H2S paper strip method and checked for black coloration in paper strip. A total of 5 types of bacterial colonies were identified by biochemical, cultural and microscopic examination technique. Escherichia coli , enterobacter were dominant followed by Klebsiella pneumonae , Salmonella typhi , and Proteus vulgeris. concentration of bacterial colonies was maximum in October followed by November, December and minimum in May. The goal of household water treatment programs, like the CDC safe water system, is to reduce diarrheal disease in users by improving the microbiological quality of stored household water. Thus, testing for microbiological contaminants is useful to determine it: ´ Household drinking water is contaminated before program initiation; and ´ An intervention improves the microbiological quality of stored household water.


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Microbiological indicators are bacteria shown to be associated with disease-causing organisms, but do not cause disease themselves. The three common micorbiological indicators are : (1) total coliform bacteria; (2) fecal (thermotolerant) coliform bacteria; and (3) Escherichia coli. A fourth indicator, production of hydrogen sulfide, has recently been used as well. Total Coliform Bacteria Disease-causing organisms can be present in water in small numbers and pose a human health risk. Because of this, indicators of disease-causing organisms present in higher concentrations were initially developed to assess drinking water safety. Because there are numerous coliform bacteria in the intestinal tracts of humans, and each person discharges between 100-400 billion per day, this group was initially chosen as the indicator organism for drinking water safety. Fecal (Thermotolerant) Coliform Bacteria To provide a more accurate indicator of human health risk, the fecal coliform group was developed. This group is also defined by the laboratory method, and includes those Gramnegative rod bacteria that, at 44 ± 0.2 degrees Celsius, either: 1) ferment lactose with gas production (for MPN and P/A testing), or 2) produce a distinctive colony on a suitable mediu (for MF testing). This subgroup includes the genus Escherichia, and some species of Klebsiella, Enterobacter, and Citrobacter. The terms fecal coliform bacteria and thermotolerant coliform

bacteria are used interchangeably.

E. coli. Escherichia coli (E. coli) is a bacteria that colonizes the gastrointestinal tract of humans and other mammals shortly after birth and is considered part of our normal intestinal flora. Some types of E. coli, such as E. coli O157:H7 possess virulence factors and can cause diarrheal disease in humans, but most types of E. coli are harmless. A single gram of fresh feces may contain as many as 1,000,000,000 E. coli. The mammalian gut is the normal habitat for E. coli, and, unlike other coliform bacteria, they are not normally found in uncontaminated waters. This makes E. coli an ideal indicator for human health risk. WHO states, “The presence of E. coli in water always indicates potentially dangerous contamination requiring immediate attention” (4). Due to its high prevalence and disease-causing properties, E. coli is a solid microbiological indicator. However, in some less contaminated environments, there is not enough E. coli present to calculate treatment process efficiency. When sampling for both human health risk and treatment efficiency a combined total coliform/fecal coliform bacteria test and E. col i test may need to be completed. The World Health Organisation (WHO) and united states environmental protection Agency (USEPA) both use microbiological indicators as the guideline value or standard for safe drinking water. The WHO guideline value is that E. coli and thermotolerant (Fecal) Coliform bacteria “Must not

Table 1: Physico-chemical assessment of drinking water of Gandhi Nagar Area of Bhopal City 2011-12 Mean Seasonal Value (Pre and Post monsoon ) Parameters Unit

SS1

SS2

SS3

SS4

SS5

SS6

SS7

SS8

Fluoride MPN

0.16 64

0.27 98**

0.18 90

0.40** 65

0.30 36

0.28 70

0.20 44

0.10* 32*

ppm No./100ml

SS1 = Pardi Mohalla SS2 = Jhirniya SS3 = Jodhpur Dhaba SS4 = Pipalner **= maximum value

*=

SS5 = Badbai SS6 = Sector no. 5 SS7= Dawarika Dham SS8= Nai Basti minimum value


KATARIA & AMBHORE, Curr. World Environ., Vol. 7(2), 301-303 (2012) be detectable in any 100 ml sample” of water intended for drinking (1) The guidelines also note that “immediate investigative action must be taken if E. coli are detected”, and that “medium-term targets for the progressive improvement of water supplies should be set” in developing countries having difficulties meeting the standards. Hydrogen Sulfide production A relatively new microbiologic indicator test is measuring hydrogen sulfide production. Some bacteria excrete hydrogen sulfide in their metabolic processes. Because hydrogen sulfide is easy and inexpensive to measure, this has been suggested as a new indicator. However, hydrogen sulfide can

303

be produced via other mechanisms than bacterial metabolism, and so hydrogen sulfide production is, in effect, measuring an indicator (Hydrogen sulfide presence of bacterial) of an indicator (bacteria of human health risk). The finding are similar with Kataria (1996) (2000) most of value found within the permissible limit as recommended by WHO 1978. The value of faceal/coliform recommended 10/100 ml index by WHO. Some values are found beyond the limits. Hence water samples analysed in the present study has found a suitable for drinking after proper required treatment.

REFERENCES

1. 2.

3.

4.

5.

6.

Kataria, H.C., Gupta S.S. and Jain, O.P. Poll Res. 14(4): 455-562 (1996) Kataria, H.C. Preliminary study of drinking water of Pipariya township, Poll, Res, 19(4): 645-649 (2000) Rangwala, K.S. and Rangwala P.S., water supply and sanitary, engineering character pub. House Anand (vely), India, 12th ed. 4344 (1927). BIS : Specification for drinking water IS : 10500: Bureau of Indian Standards, New Delhi (1991). Kataria, H.C., Analytical study of trace elements in groundwater of Bhopal city. Ind. J. Environment Prot. IJEP, 24(12): 894-896 (2004) Kataria, H.C., et al., Physiochemical analysis

7. 8. 9.

10.

11.

of water of Kubza river of Hoshangabad, Orient J. Chem., 11(2): 157-159 (1995). WHO, Guidelines for drinking water quality 1 (1984). K.C. Gupta and Jagmohan Oberai, Orient J. Chem., 26(1): 215-221 (2010). APHA : Standard methods for the examination of water and waste water, Americal Public Health association (Greenberg, AE, Clexeri, L.S. and Eaton A.D., 18th ed. Washington DC.) (1992) Kataria, H.C., et al., Flurosis with special reference to fluroide contents in drinking water of Bhopal city (M.P.) Research Link, 143(4): 12: 13 (2004) Teotia, SPS and Teotia, Endemic Fluoride, Bomes and teeth update, J. Environ. Toxicol 1: 1-16 (1991).


Current World Environment

Vol. 7(2), 305-308 (2012)

Studies in the Applicability of Organic Polymer for Pretreatment of Industrial Waste DHANANJAY DWIVEDI1, KIRTI YADAV2 and VIJAY R. CHOUREY3* 1

P.M.B. Gujarati Sc. College, Indore, India. Government Autonomous Holkar Science College, Indore - 452 001, India 3* 2603-E Sudama Nagar, Indore - 452 009, India.

2

(Received: July 12, 2012; Accepted: September 17, 2012) ABSTRACT The applicability of organic polymer in form of polyeletrolytes as a pretreatment material for deionizer have been studied in the laboratory prepared electroplating waste solutions. Load of metal and non metal ions, present together or alone in the waste can be reduced by flocculation of waste with organic polymer. Change in the concentration of TDS and dissolved oxygen have been studied. The paper also describes the effect of pH on the flocculation process.

Key words: Organic polymer, polyelectrolyte, flocculation.

INTRODUCTION Hazardous waste effluents coming out from the Process industries creating lot of environmental problems. Waste effluent from metal plating, refining, battery and power source are found to have varying degree of contaminants with high toxicity 1. There are various methods and techniques available for treatment of toxic waste to maintain the toxic material below the prescribed disposable limit. However, these techniques suffer the load of physical and chemical pollutants. For the fastness of main treatment process and to increase the efficiency of full fledged treatment process a kind of prior treatment can be given to waste in form of flocculation and coagulation. By pretreatment the size of impurities increases to such extent that they can be easily filtered out from the effluents. Generally in the pretreatment of electroplating waste many inorganic coagulants or flocculants are used but they have some disadvantages with them i.e. they may increase the unwanted ionic load. To avoid such

type of unrequired ionic loading the organic polymers can be used as flocculation agents2-4. Organic polymers or polyelectrolyteâ&#x20AC;&#x2122;s are water soluble. They may be synthetic or natural in origin like cellulose derivatives, starch product etc. They are nontoxic and their small dosing is required for the flocculation5-6. MATERIALS AND METHODS SS-120 is an anionic polymer with high molecular weight and in form of white granulated powder is used as flocculation agent. It was supplied by Thermax India Pvt. Ltd. Other chemicals as NiCl2, CuSO4, EDTA, ZnCl2, CuCl2 etc. were used of AR grade. All the solutions were prepared in doubly distilled water. Experimental Procedure The stock solution of organic polymer SS120 was prepared as 1 mL of this stock solution to give 1mg/L of polyelectrolyte concentration when added to the 1 liter of test solution. For required


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dosing different mL of stock solution have been used. The mixture of required amount of polymer in distilled water was kept on the magnetic stirrer to get homogenous solution which should be viscous in nature. Ion containing test solutions were prepared by dissolving their required amount in distilled water.

kept for 10 minutes to get settled. The flocs formed by flocculation get separated by routine methods. The filtrate was tested for ions, TDS, DO and pH estimation. Ni +2, Cu +2 and Cl - were tested by complexometrically, iodometrically and argentometrically respectively6-7. RESULTS AND DISCUSSION

Treatment procedure Required dosing of organic polymer from stock solution was added to definite amount of prepared waste solution. For complete and constant mixing it is continuously stirred for 25 minutes then

Experiments were performed and their findings and related discussions have been summarized below:

Table 1: Removal of Ni+2, Cu2+, Cl - individually and Ni+2 + Cu2+ while present together S. No.

Species/ Parameter

1. 2. 3. 4.

Ni+2 ion Cl- (pH 7) ion Cu+2 ions Cu+2 Ni+2 present together

5. 6.

DO pH Acidic Medium

7.

pH alkaline medium

Ni+2 Cu+2 Cu+2 Ni+2 Cu+2 Ni+2

Experiment was also carried out to see the change in flocculation efficiency with changing pH. For this effluent with Cu+2 & Ni+2 ions were treated with organic polymer in two different pH ranges a) between 2 to 3 pH (acidic range) b) at 7.3 pH (slightly alkaline range) From the result it has been observed that in the acidic pH range there is no change in the initial concentration after treatment while in alkaline pH range change in concentration is observed. Ni+2 reduced from 168 mg/L to 34 mg/L & Cu2+ from 200 mg/L to 20 mg/L with reduction percentage of 80% & 90% respectively. The observation exhibit that increase in the solubility of metal ions in acidic medium reduces

Initial Conc. mg/L

After treatment Conc. mg/L

Reduction/change in value %

168 250 200 260 160 5.5 200 168 200 168

140 200 146 240 138 6.4 200 168 20 34

16.50 20.00 27.00 7.60 13.75 16.50 No Change No change 91.00 74.76

the flock formation with polyelectrolyte, while in alkaline medium metal ions precipitated as hydroxide. Hydroxides are colloidal in nature and quickly form flocks with organic polymer and get settled. Hence high change in the value is obtained in alkaline range. Concentration of dissolved oxygen was also tested in the untreated and treated (with biopolymer) electroplating waste effluent. The results of this filtrate were recorded. There is an increase of DO by 16.5% in the biopolymer mixed effluent. The studies has also been carried out for the determination of TDS (Total Dissolve Solids) at solution pH level in untreated Cu+2 and Ni+2 mixed


DWIVEDI et al., Curr. World Environ., Vol. 7(2), 305-308 (2012) effluents and in the effluent treated with biopolymer. The value of TDS reduced from 5260 mg/L to 1315 mg/L with 75% reduction. These studies also show that addition of aluminum sulphate in the treated effluent increases the TDS.

307

It has also been observed that if pH is adjusted to slightly alkaline side then TDS decreased from 5260 mg /L to 684 mg /L. The results are given in the table 2

Table 2: Determination of TDS Without Adjusting pH Condition

Total Dissolved Solids (TDS)In mg/L

Initial TDS in Untreated mixed After treatment with polyelectrolytes After addition of aluminium sulphate in treated effluents After adjusting pH to slightly alkaline side TDS in Ni++ and Cu++ mixed effluents after pH adjustment Observation reveals that SS-120 biopolymer reduces the TDS, while addition of Al2(SO4)3, increases the TDS7. TDS decreases after adjusting pH to slightly alkaline side because of the metal hydroxide gets precipitated.

5260 1315 2130 684

Work has also been performed on the effect of polyelectrolyte, Al2(SO4)3 and of pH on the sludge volume. Results are given in the table -3.

Table 3: Sludge volume at different conditions S. No.

Conditions

1 2. 3. 4.

When the biopolymer is present When both biopolymer and Al2(SO4)3 are present. At pH 7.5 in presence of biopolymer At pH 7.5 when both biopolymer and Al2(SO4)3 are present.

It shows that presence of biopolymer and alum affect the sludge volume in greater extent.

Total volume of the effluent in mL

Sludge Volume in mL

105 89 105 200

7 28 8 18

% of sludge formed

6.60 31.46 7.60 9.00

with ions. For these solutions containing different metal and non metal ions were used. The results of visual observations are given in the table - 4

Work has also been carried out to know the tendency of the biopolymer to form the flock Table 4: Tendency of biopolymer to form the flock with ions S. No.

Ions

Magnitude of flock

1. 2. 3.

Non-metal Ions Metal Ions Metal ion with 0.2 gm. Alum

Na2SO4 > H3PO4 > NaCl (no flock formed) ZnCl2> NiCl26H2O >CuCl2.2H2O CuCl2.2H2O and ZnCl2 >NiCl2


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These results confirmed that biopolymer SS-120 is more active than other metal ions as the flock of zinc formed has greater magnitude. In case of non-metal ions biopolymer exhibit more affinity towards the sulphate ion than chloride ions. After the pretreatment of effluent, now it was treated by one of the selected full flagged treatment process. Here it was applied on ion exchange technique. In first step it was allowed to pass through the cationic exchanger for removal of Cu 2+ and Ni 2+ and then through the anionic exchanger to remove Cl- ions. With This experiment complete removal of anions and cations has been observed. The experiment was also monitored for any adverse effect of biopolymer on resin, but no such adverse effect was noticed. It is assumed that the capacity of biopolymer to trap the colloidal pollutants is due to

their long chain structure. The colloidal particles entangle or trapped with them and form compact and big size flocks. The work performed, confirm that pretreatment of industrial waste by use of biopolymer not only reduces various pollutants to remarkable extent but faster the main treatment process by quite and good margin. The method is very much useful to minimize the load of impurities in the industrial effluents having high concentration of metal ions and anions by using biopolymer. ACKNOWLEDGEMENTS Authors are thankful to authority of PMB Gujarati Science College, Indore for providing research facilities.

REFERENCES

1. 2. 3.

4. 5.

S.S. Rogers and P. Venema, Biopolymer, 82(3): 241 (2006). K. Nakanura and Rawarnura, Bul.Chem. Soc., Japan, 44: 330 (1971). K.E. Langford and J.E. Parkar, Analysis of electroplating and related solutions Robert Draper Ltd. Teddngton, (1971). N.V. Parathasardhy, Environ. Health, 11, 358, (1969). Nusoibah Naahidhan Rukman, Siti Zaleha

6. 7. 8. 9.

SA'AD and Rozana Mohd Danan, Orient J. Chem., 28(2): 741-748 (2012). M. Sadeghi and M. Yarahmadi, Orient J. Chem., 27(1): 13-21 (2011). C.E. Van Hall and V.A. Stranger, Anal.Chem., 35: 315 (1963). E.W. Meeker and E.C. Wagner, 2 nd Eng. Chem. Anal. Ed. , 5: 396 (1993). M. Ali and N. Deo, Indian J. Environ. Protect., 12(3): 202 (1992).


Current World Environment

Vol. 7(2), 309-311 (2012)

Pre and Post-monsoon Physico-chemical Assessment of Drinking Water Quality of Gandhinagar Area of Bhopal H.C. KATARIA1 and SANTOSH AMBHORE2 1

Department of Chemistry, Government Geetanjali Girls College, Bhopal - 462 038, India. Department of Chemistry, Government Motilal Vigyan Mahavidalaya, Bhopal - 462 003, India.

2

(Received: July 12, 2012; Accepted: September 17, 2012) ABSTRACT Physico-chemical assessment of drinking water quality of Gandhi Nagar area of Bhopal has evaluated in various stations for one year 2011-2012 in pre and post monsoon season. In this present study temperature, pH, BOD, COD, EC, free CO2, T-H, Ca-H, Mg-H, total alkalinity has analyzed. The present study has its significance for public hygiene in public interest.

Key words: Parameters, physico-chemical assessment, pre and post monsoon, Hygiene, treatment, drinking water.

INTRODUCTION The history of human civilization reveals that water supply and civilization are almost synonymous. several cities and civilizations have disappeared due to water shortage originating from climatic and other changes. The absence of water has resulted in the absence of life on the moon. Water, The nectar of life is one of the most important natural resource for all living organisms, whether unicellular or multicellular ,since it is required for their various metabolic activities. In fact life on the earth is possible only because of the presence of abundant water. An understanding of water chemistry is the basis of knowledge of the multi dimensional aspects of aquatic environmental chemistry, which involve the source composition, reaction and transport of water. More than 71% of the earth’s surface is covered by water,97% of water is in oceans and not generally useful without treatment. The remaining 3% is fresh water and is found in rivers, lakes, and underground aquifers and locked up as ice. In fact, 79% of fresh water is in the form of ice mainly in two polar ice sheets and in the high mountain glaciers.

Rivers, lakes, man made reservoirs and underground water are our water wealth. Some centuries ago, water from these sources was clean and potable, but due to heavy industrialization, excessive use of fertilizers and pesticides, unscientifically disposal of sewage now a day’s water pollution is the main problem for all living organisms. Water quality is commonly defined by its physical, chemical, biological and aesthetic (appearance and smell) characteristics. A healthy environment is one in which the water quality supports a rich and varied community of organisms and protects public health.” The quality of drinking water is maintained by individual water bodies of all the metropolitan cities. Sydney Water and Hunter Water are the two large organisations that aim to provide high quality drinking water for all in these regions. Drinking water is treated to meet the Australian Drinking Water Guidelines(ADWG). ADWG is concerned with the safety and aesthetic quality of drinking water for human consumption. Drinking water does


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not need to be absolutely pure to be safe, as water is such a good solvent, pure water containing nothing else is almost impossible to attain. What is required is that drinking water should be safe to drink for people in most stages of normal life, including children over six months of age and the very old. It should contain no harmful concentrations of chemicals or pathogenic microorganisms, and ideally it should be aesthetically pleasing in regard to appearance, taste and odour.

suspended materials. Organic materials such as pesticides, fertilizers, plastics, detergents, gasoline, oil, factory waste water, and fossil fuels are among the most severe pollutants.

Water quality has also become a big issue. The amount of clean water that is available has decreased within the past decade. Although some types of water pollution occur through natural processes, most of the pollution is caused by human activities. The water we use is taken from rivers, lakes and underground, and these are the same places the water returns to after we have finished using it – or actually, not finished using it but finished contaminating it. Water pollutants categorizes into four basic categories: pathogens and other organic materials, chemicals including organic and inorganic toxic substances, thermal heat, and

Present district of Bhopal was carved out of Sehore district in 1972. Bhopal is the picturesque capital of Madhya Pradesh and known as “city of lakes”. Water is one of the very precious substances on the earth. it is very essential for the existence and survival of life. As population grows and their need for water increases, the pressure on our ground resources also increases . in many areas of the world ground water is now being over extracted, in some places massively so, the results is falling water levels and declining well yield ,land subsidence and ecological damage such as the drying out of wetlands.

Many researchers have studied in detail the physic-chemical characteristics of groundwater ,rivers, lakes, water reservoirs and other water resources. The findings of some such work are relevant to the present study.

Table 1: Physico-chemical assessment of drinking water of Gandhi Nagar Area of Bhopal City 2010-11 Parameters

Mean Seasonal Value (Pre and Post monsoon ) Unit

Temperature pH Electrical conductivity

°C µmhos /cm Free CO2 ppm Total Alkalinity ppm Total Hardness ppm Calcium Hardness ppm Magnesium Hardness ppm Dissolved Oxygen ppm B.O.D. ppm C.O.D. ppm

SS1

SS2

SS3

SS4

SS5

SS6

SS7

19 5.00 220

18* 4.5* 212*

21 6.24 310

20 6.50 418**

19 5.80 232

24** 6.40 278

22 23 7.4** 7.20 232 384

6.42 216 212 117 95 2.12 4.92** 13.20

6.20* 240** 224 130 94 2.40** 1.52 12.12*

8.42 232 420** 290** 130** 1.82 2.18 17.20

9.12 182 312 208 104 2.10 1.60 52.2**

7.42 152 216 110* 106 1.10* 3.28 16.80

11.80** 220 284 190 94 2.32 2.16 14.10

10.94 142 210* 114 96 1.72 1.42* 17.40

SS1 = Sant Aasharam Bapu Asharam SS2 = Tagore ward SS3 = Gondipura SS4 = Rajiv Gandhi technology university **= maximum value *=

SS5 = Sector no. 11 SS6 = Parewakhedi SS7= Dobra SS8= Chandpur minimum value

SS8

11.20 110* 238 178 60* 2.26 4.60 12.80


KATARIA & AMBHORE, Curr. World Environ., Vol. 7(2), 309-311 (2012) Water samples of bore-wells are collected in 2 litre clean polythene jerry-cane after flushing the bore wells to analysis. The procedure has adopted as prescribed by APHA (1985), NEERI(1986), presterilized bottles are used to collect DO and BOD samples. In present study temperature varied from 18-24 째C. pH ranges as 4.50-7.40 indicates the intensity of acidity.Free CO2 ranges from 6.20-11.80 ppm, Electrical conductivity 212-418, total alkalinity 110-240 ppm, DO, BOD and COD ranges as 1.10-2.40,1.42-4.92, and 12.12-52.20 .Total Hardness, Ca-H, Mg-H ranges as 210-420,110-290, and 60-130 ppm respectively as summarized in table-1. eight sampling stations are as follows:

1. 2. 3. 4. 5. 6. 7. 8.

311

Sant Aasharam Bapu aashram Tagore ward Gondipura Rajiv Gandhi Technology University Sector No-11 Parewakhedi Dobra Chandpur

The above findings are similar with those of Handa (1994), Kataria (1995); 2000, 2004. Most of the parameters are found well with in the recommended limits of BIS and some parameters are found beyond the limits. Hence water samples analyzed in present study has found suitable for drinking purpose after proper required treatment.

REFERENCES 1.

2.

3.

4. 5.

6

Standard method for the examination of water and waste water APHA, 13th Ed. New York (1985). NEERI: manual on water and waste water analysis, national environmental engineering research institute Nagpur 340 (1986). BIS: specification for drinking water IS: 10500: Bureau of Indian standards, New Delhi (1991). WHO: guideline for drinking water quality volume 1 (1984). B.M. Bheshdadia, D.S. Kundariya and P.K. Patel, Orient J. Chem. , 27(2): 685-689 (2011). Kataria, H. C., Analytical study of trace elements in ground water of Bhopal City Ind. J. Environment Prot. IJEP, 24(12): 894-896 (2004).

7.

8. 9.

10.

11.

12.

Kataria, H.C. Preliminary study of drinking water of Pipariya township, Poll, Res, 19(4): 645-649 (2000). WHO, Environmental health criteria, 5, Genewa (1978). APHA : Standards methods for the examination of water and waste water, American Public Health Association (Greenberg, AE, Clexri, L.S. and Eaton A.D., 18 th ed. Washington DC. ) (1992) Iqbal S.A.,Khan S.S.,Chaghtai S.A. and Irfan Husain; Assesment of pollution levels of river Betwa, J.Sci.Res., 6(3): 165-170 (1984). C.N. Sawyer, et.al, chemistr y for Environmental Engineering and Science, Fifth edition by Tata McGraw-Hill 659-665 (2003). B.D. Gharde, Orient. J. Chem., 26(1): 175180 (2010).


Current World Environment

Vol. 7(2), 313-315 (2012)

Analysis and Physico-Chemical Parameters of Sarvar Devla Sugar Mill Studies of Effluents JANESHWAR YADAV1* and R.K. PATHAK2 1

Jawaharlal Institute of Technology, Borawan, Khargone - 451 228, India. 2 New G.D. College, Moti Tabela, Indore, India. (Received: July 12, 2012; Accepted: September 17, 2012) ABSTRACT

The physico-chemical characteristics contents in the effluents discharged from Neoly sugar mill have been explored. The physico-chemical parameters such as colour, odour, temperature, pH, electrical conductivity, COD, BOD, alkalinity, total hardness,Ca+2, Mg+2, chloride, of the effluent collected from the various sites between the exit point at the mill and discharge point In, have been determined.

Key words: Sugar mill effluents, Physico-chemical parameters.

INTRODUCTION

MATERIAL AND METHODS

The recent studies have indicated that the water bodies becoming increasingly Contaminated due to the domestic and industrial wastes. The effluent discharge from sugar Mill consists of a number of chemical pollutants that can bring about changes in temperature, Humidity and oxygen supplies amounting to a partial or complete alteration in the physical, chemical and physiological sphere of the biota. Such changes disrupt the ecological cycle of Living organisms. Further, the letting of effluents sugar mill run into the natural water is responsible for bad quality water which affects aquatic life severely. It is, therefore, very essential to study the physico-chemical parameters and heavy metal contents of the effluents to ensure their proper treatment prior to their disposal into open land or natural water Resources.

Samples of sugar mill effluents were collected from the different points on the drain viz. point-1 (the exit in the premises) point-2 (1/2 km. from point-1) and point-3 (1/2 km. from point-2) in the month of February 2012. The physico-chemical analysis of sugar mill effluents was carried out as per the standard methods for analysis of water, waste water and industrial effluents. All the testing were done at our institute laboratory. Where alkalinity. Hardness, chloride content determined by standard titration methods.

The present paper deals with the estimation of physicochemical parameters of sugar mill effluents collected from Neoly Sugar Mill, district Khargone M.P (India). This study was conducted during the December to January month 2012, when sugar mill remained in its full crushing capacity.

RESULTS AND DISCUSSION Physico-chemical parameters The results related to the physicochemical parameters of the sugar mill effluents collected at different time intervals from the various sites have been listed in the given table 1. Colour The colour of the effluent was found variable at different points. The effluents are yellow in colour and intensity decrease from Point-1 to Point-3.


314

YADAV & PATHAK, Curr. World Environ., Vol. 7(2), 313-315 (2012)

The odour of effluents of the mill was found sweet to alcoholic from Point-1 to Point-3.

concentration of Ca2+ and Mg2+ ions only. It is expressed in terms of calcium carbonate. Total hardness varied from 760 to 800 mg/L.

Temperature The temperature is the highest at Point-3 and decreases appreciably up to Point -1.

Calcium (Ca2+) Calcium values range from 160.32 to 200.4 mg/L.

pH

Magnesium (Mg2+) Magnesium values range from 599.68 to 625.5 mg/L, which are higher than the ISI limits.

Odour

The pH value of the effluent sample varies from 5.32 to 5.89. pH values are increased with increase in the distance travelled by the effluent. The ISI permits a range of pH from 5.5 to 9 for the effluents that could be released into any natural water source (ISI 1974). TH (Total hardness) The term ‘Total hardness’ indicates the

Alkalinity Alkalinity found at varying distance during winter season is of the order 83 to 90 mg/L. It is evident that the alkalinity at all the sampling sites was much greater than the recommended value, 50 mg/L.

Table 1: Physico-chemical analysis of Neoly sugar mill effluents at different time intervals Parameter

Point 01

Point 02

Point 03

Colour Odour pH Temperature Total hardness Ca hardness Mg hardness Alkalinity Chloride content

yellow Light sweet 5.32 32 760 160.32 599.68 83 78.1

Light yellow Light sweet 5.45 34 785 165.2 602.32 85 63.9

Light yellow Light alcoholic 5.89 35 800 200.4 625.5 90 71.0

(All concentration are reported in ppm (mg/L) except pH, temperature in (°C)

Chloride (Cl–) The concentration values of chloride in the effluent samples ranged over 63.9 to 78.1 mg/L. It is explicit from the data that the pH of the effluents increases. The values for alkalinity and the concentration of the magnesium as well as ions are higher than the recommended value for the industrials effluents. The present study exhibits that the

treatment of the effluent is being done regularly before its disposal into the natural water sourse. However, the maintenance of the treatment plant as well as the periodic training of the workforce are required. ACKNOWLEDGEMENTS The Authors are thankful to the Principal, Jawaharlal Instituite of Technology Borawan for providing thenecessary facilities.


YADAV & PATHAK, Curr. World Environ., Vol. 7(2), 313-315 (2012)

315

REFERENCES

1. 2.

3. 4. 5. 6.

7.

C. Manas, Ind. Chem Man, 14(3): 13-14 (1979). R. Deshbandu, et al. Ecology and Development, Vth (Eds), Indian Env. Soc., New Delhi, 178-190 (1979). S. R. Verma and G. R. Shukla, the Env. Health, 11: 145-162 (1969). B. K. Behra and B. N. Mishra, Ind. Res., 37: 390-398 (1985). S. Khurshid et al., Indian J. Environ, Health, 40(1): 45 (1998). N. Manivaskam, Physico-chemical Examination of Water Sewage and Industrial Effluents, IIIrd (Eds), Pragati Prakashan Meerut (1996). ISI, Tolerance Limits for Industrial Effluents discharged into Inland Surface Water IS,

8.

9.

10.

11.

12.

2490, New Delhi (1974). BIS, Specifications for Drinking Water, IS, 10500, Bureau of Indian Standards, New Delhi (1991). P. R. Pratt, Quality Criteria for Trace Elements in Irrigation Waters, University of California Experiment Station, Riverside, California (1972). Vibha Agrawal, S.A. Iqbal and Dinesh Agrawal, Orient J. Chem., 26(4): 1345-1351 (2010). B.M. Bheshdadia, D.S., Kundariya and R.K. Patel, Orient J. Chem ., 27(2): 685-689 (2011). M. Hussain, T.V.D. Prasad Rao, H.A. Khan and M. Satyanarayan, Orient J. Chem., 27(4): 1679-1684 (2011).


Current World Environment

Vol. 7(2), 317-319(2012)

A Study on Seasonal Variation in the Physico-chemical Assessment of MPN and Fluoride Analysis of Drinking Water of Gandhinagar Area of Bhopal H.C. KATARIA1 and SANTOSH AMBHORE2 1

Department of Chemistry, Government Geetanjali Girls College, Bhopal - 462 038, India. Department of Chemistry, Government Motilal Vigyan Mahavidalaya, Bhopal - 462 003, India.

2

(Received: July 12, 2012; Accepted: September 17, 2012) ABSTRACT Determination of fluoride concentration of sampling stations from different sites in and around villages near Gandhinagar of Bhopal was carried out by using selective fluoride ionelectode. Determination of coliform bacteria/MPN of drinking water samples collected from various places by using H2S paper strip method and checked form black coloration in paper strip.

Key words: Determination, Fluoride ion concentration, Drinking water, Fluorosis, Coliforms, MPN (myeloproliferative neoplasm)

INTRODUCTION Bhopal the capital of Madhya Pradesh territory the largest state of India. Bhopal is situated on 23°16’N Latitude and 77°25' Longitude and is located on Hard pink sand stone of Vindhya region Fluoride concentration in India, creates health problems and fluorosis. The disease previously called as “Mottled teeth” reported in Madras City (1933). Most of the population of 18 states out of 35 states in India are well affected with dental, skeletal and non-skeletal fluorosis, which southern India is badly affected by “Fluorosis”. Fluoride in drinking water is 1.0-1.5 mg/l recommended by WHO (2004). Fluoride concentration has analyzed by using ion selective electrode and ORION 407A meter followed by standards as prescribed by APHA (1992) . The water samples was preserved by adding total ionic strength adjustment Buffer (TISAB) in 1:1 radi and analysis for fluoride levels is calculate by standard curve platted on a semilog graph conc.(Log axis) vs mV. Teofia and Teofia index (TTI 1991) has commonly used to score dental fluorosis in several endemic areas of this country

The present investigation describe the qualitative and quantitative assessment of different water samples collected different sampling stations of study are collected from various sampling places in 2011-2012. by using H2S paper strip method and checked for black coloration in paper strip. A total of 5 types of bacterial colonies were identified by biochemical, cultural and microscopic examination technique. Escherichia coli , enterobacter were dominant followed by Klebsiella pneumonae , Salmonella typhi , and Proteus vulgeris. concentration of bacterial colonies was maximum in October followed by November, December and minimum in May. The goal of household water treatment programs, like the CDC safe water system, is to reduce diarrheal disease in users by improving the microbiological quality of stored household water. Thus, testing for microbiological contaminants is useful to determine it: ´ Household drinking water is contaminated before program initiation; and ´ An intervention improves the microbiological quality of stored household water.


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KATARIA & AMBHORE, Curr. World Environ., Vol. 7(2), 317-319 (2012)

Microbiological indicators are bacteria shown to be associated with disease-causing organisms, but do not cause disease themselves. The three common micorbiological indicators are : (1) total coliform bacteria; (2) fecal (thermotolerant) coliform bacteria; and (3) Escherichia coli. A fourth indicator, production of hydrogen sulfide, has recently been used as well. Total Coliform Bacteria Disease-causing organisms can be present in water in small numbers and pose a human health risk. Because of this, indicators of disease-causing organisms present in higher concentrations were initially developed to assess drinking water safety. Because there are numerous coliform bacteria in the intestinal tracts of humans, and each person discharges between 100-400 billion per day, this group was initially chosen as the indicator organism for drinking water safety. Fecal (Thermotolerant) Coliform Bacteria To provide a more accurate indicator of human health risk, the fecal coliform group was developed. This group is also defined by the laboratory method, and includes those Gramnegative rod bacteria that, at 44 ± 0.2 degrees Celsius, either: 1) ferment lactose with gas production (for MPN and P/A testing), or 2) produce a distinctive colony on a suitable mediu (for MF testing). This subgroup includes the genus Escherichia, and some species of Klebsiella, Enterobacter, and Citrobacter. The terms fecal coliform bacteria and thermotolerant coliform

bacteria are used interchangeably.

E. coli. Escherichia coli (E. coli) is a bacteria that colonizes the gastrointestinal tract of humans and other mammals shortly after birth and is considered part of our normal intestinal flora. Some types of E. coli, such as E. coli O157:H7 possess virulence factors and can cause diarrheal disease in humans, but most types of E. coli are harmless. A single gram of fresh feces may contain as many as 1,000,000,000 E. coli. The mammalian gut is the normal habitat for E. coli, and, unlike other coliform bacteria, they are not normally found in uncontaminated waters. This makes E. coli an ideal indicator for human health risk. WHO states, “The presence of E. coli in water always indicates potentially dangerous contamination requiring immediate attention” (4). Due to its high prevalence and disease-causing properties, E. coli is a solid microbiological indicator. However, in some less contaminated environments, there is not enough E. coli present to calculate treatment process efficiency. When sampling for both human health risk and treatment efficiency a combined total coliform/fecal coliform bacteria test and E. col i test may need to be completed. The World Health Organisation (WHO) and united states environmental protection Agency (USEPA) both use microbiological indicators as the guideline value or standard for safe drinking water. The WHO guideline value is that E. coli and thermotolerant (Fecal) Coliform bacteria “Must not

Table 1: Physico-chemical assessment of drinking water of Gandhi Nagar Area of Bhopal City 2011-12 Mean Seasonal Value (Pre and Post monsoon ) Parameters Unit

SS1

SS2

SS3

SS4

SS5

SS6

SS7

SS8

Fluoride MPN

0.16 64

0.27 98**

0.18 90

0.40** 65

0.30 36

0.28 70

0.20 44

0.10* 32*

ppm No./100ml

SS1 = Pardi Mohalla SS2 = Jhirniya SS3 = Jodhpur Dhaba SS4 = Pipalner **= maximum value

*=

SS5 = Badbai SS6 = Sector no. 5 SS7= Dawarika Dham SS8= Nai Basti minimum value


KATARIA & AMBHORE, Curr. World Environ., Vol. 7(2), 317-319 (2012) be detectable in any 100 ml sample” of water intended for drinking (1) The guidelines also note that “immediate investigative action must be taken if E. coli are detected”, and that “medium-term targets for the progressive improvement of water supplies should be set” in developing countries having difficulties meeting the standards. Hydrogen Sulfide production A relatively new microbiologic indicator test is measuring hydrogen sulfide production. Some bacteria excrete hydrogen sulfide in their metabolic processes. Because hydrogen sulfide is easy and inexpensive to measure, this has been suggested as a new indicator. However, hydrogen sulfide can

319

be produced via other mechanisms than bacterial metabolism, and so hydrogen sulfide production is, in effect, measuring an indicator (Hydrogen sulfide presence of bacterial) of an indicator (bacteria of human health risk). The finding are similar with Kataria (1996) (2000) most of value found within the permissible limit as recommended by WHO 1978. The value of faceal/coliform recommended 10/100 ml index by WHO. Some values are found beyond the limits. Hence water samples analysed in the present study has found a suitable for drinking after proper required treatment.

REFERENCES

1. 2.

3.

4.

5.

6.

Kataria, H.C., Gupta S.S. and Jain, O.P. Poll Res. 14(4): 455-562 (1996) Kataria, H.C. Preliminary study of drinking water of Pipariya township, Poll, Res, 19(4): 645-649 (2000) Rangwala, K.S. and Rangwala P.S., water supply and sanitary, engineering character pub. House Anand (vely), India, 12th ed. 4344 (1927). BIS : Specification for drinking water IS : 10500: Bureau of Indian Standards, New Delhi (1991). Kataria, H.C., Analytical study of trace elements in groundwater of Bhopal city. Ind. J. Environment Prot. IJEP, 24(12): 894-896 (2004) Kataria, H.C., et al., Physiochemical analysis

7. 8. 9.

10.

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of water of Kubza river of Hoshangabad, Orient J. Chem., 11(2): 157-159 (1995). WHO, Guidelines for drinking water quality 1 (1984). K.C. Gupta and Jagmohan Oberai, Orient J. Chem., 26(1): 215-221 (2010). APHA : Standard methods for the examination of water and waste water, Americal Public Health association (Greenberg, AE, Clexeri, L.S. and Eaton A.D., 18th ed. Washington DC.) (1992) Kataria, H.C., et al., Flurosis with special reference to fluroide contents in drinking water of Bhopal city (M.P.) Research Link, 143(4): 12: 13 (2004) Teotia, SPS and Teotia, Endemic Fluoride, Bomes and teeth update, J. Environ. Toxicol 1: 1-16 (1991).

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Current World Environment Journal Volume 7 Number 2

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