Seasonal variation of heavy metals in water and sediments in the Halda River, Chittagong, Bangladesh

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Seasonal variation of heavy metals in water and sediments in the Halda River, Chittagong, Bangladesh Md. Simul Bhuyan & Muhammad Abu Bakar

Environmental Science and Pollution Research ISSN 0944-1344 Environ Sci Pollut Res DOI 10.1007/s11356-017-0204-y

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Author's personal copy Environ Sci Pollut Res DOI 10.1007/s11356-017-0204-y

RESEARCH ARTICLE

Seasonal variation of heavy metals in water and sediments in the Halda River, Chittagong, Bangladesh Md. Simul Bhuyan 1 & Muhammad Abu Bakar 2

Received: 22 March 2017 / Accepted: 12 September 2017 # Springer-Verlag GmbH Germany 2017

Abstract The present study was carried out to assess the contamination levels of heavy metals (Pb, Cd, Cr, Cu, Hg, Al, Ni, Co, Zn, Mn) in surface water and sediment of the Halda River. The observed order of heavy metal concentration in water for Al > Ni > Zn > Mn > Cu > Cd > Pb > Cr > Co > Hg (mg/l) and for sediments Al > Mn > Zn > Ni > Cr > Pb > Cu > Co > Cd > Hg (mg/kg), respectively. The concentrations of Pb, Cd, Cr, Cu, Hg, Al, Ni, Co, Zn, and Mn in water, whereas in sediment Pb, Cu, Al, Ni, Co, Zn, and Mn were found above the permissible limit (WHO 2004; USEPA 2006; EPA 1986, 2002 and ECR 1997). Significant variations in the concentrations of Al and Ni were found in water (p < 0.05) while Cr, Cu, Pb, Co, Mn, and Ni showed substantial changes in sediment (p < 0.05). Principal component analysis (PCA) and correlation matrix revealed anthropogenic intrusions of Pb, Cd, Cr, Cu, Hg, Al, Ni, Co, Zn, and Mn in water and sediment. In case of water, very strong linear relationship was found in Hg vs Pb (0.941), Mn vs Zn (0.939), and Ni vs Cu (0.922) at the significance level 0.01. In sediment, very strong linear relationships were found in Mn vs Cr (0.999), Co vs Ni (0.999), Ni vs Cu (0.994), Zn vs Pb (0.993), Co vs Cu (0.992), Cu vs Cr (0.990), Mn vs Cu (0.989), Mn vs Ni (0.975), Mn vs Co (0.975), Ni vs Cr (0.974), Co vs Cr (0.972), Mn vs Pb (0.951), Cr vs Pb

Responsible editor: Philippe Garrigues * Md. Simul Bhuyan simulbhuyan@gmail.com

1

Institute of Marine Sciences and Fisheries, University of Chittagong, Chittagong, Bangladesh

2

Bangladesh Council of Scientific and Industrial Research, Chittagong, Bangladesh

(0.948), Zn vs Cr (0.944), and Mn vs Zn (0.941) at the significance level 0.01 which direct that their common origin entirely from industrial effluents, municipal wastes, and agricultural activities. The study shows that seasonal water flows/water discharge (pre-monsoon, monsoon, and post-monsoon) have an impact on the mobility of metals. Elevated levels of metals were detected during monsoon in sediments (Pb, Cr, Cu, Al, Ni, Co, Zn, Mn) and postmonsoon in water (Cd, Hg, Ni, Co, Mn). The detection of high-risk metals in the Halda River may demonstrate that metals can cause significant effects on fry and fingerlings of the Gangetic carp fishery and prawn fishery (via sublethal and lethal effects and bioaccumulation or secondary poisoning of metals to fish and prawn). Keywords Heavy metal . Contamination . Surface water . Sediment . Halda River

Introduction In Bangladesh, the Halda River is one of the most important river due to natural breeding ground and major sources of seedling of fresh water fishes. Indian major carps spawn naturally which makes this river a unique heritage of this country (Tsai et al. 1981; Patra and Azadi 1985; Kabir et al. 2013). Mostly, fishermen used to collect fertilized eggs (Ali et al. 2010) of Rohu (Labeo rohita), Katla (Gibelion catla), and Mrigal (Cirrhinus cirrhosus) from the Halda River (Tsai et al. 1981). Halda fry are mostly disease resistant, inbreeding free, have high survival rate, and able to live in stressed conditions (Kabir et al. 2013), but the river is being polluted day by day (Hossain et al. 2015). Both natural and anthropogenic activities are largely liable for the heavy metal abundance in the environment (Wilson


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and Pyatt 2007; Khan et al. 2008). In present times, there has been an unprecedented increase in the level of these metals due to human activities. Huge amounts of toxic heavy metals are discharged by man-made activities (Gao et al. 2009; Nduka and Orisakwe 2011; Hossain et al. 2015; Kibria et al. 2016a, 2016b) as well as by natural actions that contribute metal impurity in aquatic ecosystem (Tarra-Wahlberg et al. 2001; Jordao et al. 2002; Sekabira et al. 2010; Zhang et al. 2011; Bai et al. 2011; Grigoratos et al. 2014; Martin et al. 2015). Geological weathering; municipal, industrial, and agricultural waste; the disposal of metals and metal components; and leaching of metals from garbage, solid waste heaps, and animal and human excreta are major sources of heavy metals (Shanbehzadeh et al. 2014). Sediments have been extensively regarded as environmental sinks for the assessment of metal pollution in the water course (Islam et al. 2015a). The concentrations of heavy metals are higher in sediment than the water column (Sultan and Shazili 2009) because of metals tendency to amass in bottom deposits (He et al. 2009; Nobi et al. 2010). Increasing contamination by heavy metals has a significant adverse effects to humans and aquatic organisms (Yi et al. 2011; Islam et al. 2014; Islam et al. 2015b; Ahmed et al. 2015). However, the level of the risks is tough to accurately measure, due to the difficulty of biologic and chemical interactions that is hugely responsible for the alteration of the bioavailability of metals (Ideriah et al. 2012). Mostly, the soluble forms of the heavy metals may be found in crustaceans, finfish and shellfish (NNPC and RIP 1986) and ultimately can be transferred to humans via the food chain pathways (Banerjee et al. 2011; Pan and Wang 2012; Rahman et al. 2013; Fang et al. 2014; Islam et al. 2015c). In recent times, metal contamination becomes the major problematic issue in many fast growing countries like Bangladesh (Islam et al. 2015a; Kibria et al. 2016a, 2016b; Ali et al. 2016; Bhuyan et al. 2016). The discharge of municipal wastes, untreated effluents from various industries, and agricultural inputs in the rivers have created alarming situation in Bangladesh (Hossain et al. 2015; Golam et al. 2016a, b; Khadse et al. 2008; Islam et al. 2015a, 2015b). This river receiving huge amount of untreated effluents from various industries such as textile crafts, dying industries, spinning mills, cotton, steel mills, oil refineries, and others as it passes through the industrial zone. Consequently, the pollution is increasing day by day especially heavy metal pollution. There was a published report or scientific research regarding heavy metal pollution in water and sediment of the Halda River (Hossain et al. 2015). Therefore, the objectives of the present study are to determine the heavy metal concentrations in water and to assess the heavy metal contamination aspects in sediments. Also, to assess temporal and spatial variation of heavy metals with respect to water flows during pre-monsoon, monsoon, and post-monsoon.

Materials and methods Sampling sites The present study was conducted in Halda river which lies between 22° 25′ 13″–22° 48′ 51.37″ N and 91° 45′ 00″–91° 52′ 33″ E. The samples were collected from Kalurghat (22° 24′ 58″ N and 91° 53′ 22.67″ E) and Modhunaghat (22° 26′ 02.18″ N and 91° 52′ 24.93″ E) of the Halda River (Fig. 1). Kalurghat is located several miles north of the port city of Chittagong, mostly well-known for several heavy industries. Modunaghat is also famous for some heavy industries located within Chittagong Division and is east of Madan Ghat, northeast of Purba Sikarpur and northwest of Uttar Burischar. Industrial wastes, sewage discharge, and sand extraction are the main polluters of the river that carried by canals (Mondakini, Madari, Cheng khali, and Khondakia canal). Asian paper mills, PHP spinning mill, Hathazari Piking power plants, local brick field, etc. are the major land-based pollution sources of the Halda River. A rapid increase of tobacco farming near the river is a devastating cause of the river pollution. Moreover, setting up of a rubber dam on the river’s upstream disrupts its natural flow. Sampling procedures were performed in three phases: firstly, September 2015 (monsoon-rainy season); secondly, January 2016 (post-monsoon-winter season), and thirdly, March 2016 (pre-monsoon-dry season). Sample collection and preservation A total of 12 surface water sample and 12 surface sediment samples were collected at two selected sites (Kalurghat and Modhunaghat) in September 2015 (rainy season), January 2016 (winter season), and March 2016 (pre-monsoon). Kalurghat is the polluted site and Modhunaghat is the reference site. From each site (Kalurghat and Modhunaghat), 2 l of surface water sample was collected. Immediately after collection, water sample acidified with nitric acid (pH = 2) were transferred to the laboratory. Samples were carefully handled to avoid contamination. Glassware was properly cleaned by chromic acid and distilled water. Analytical grade chemicals and reagents were used throughout the study. Reagents blank determinations were used to correct the instrument readings. One hundred milliliters water of each water sample was taken in a beaker. Then, the water samples were digested with adding 5 ml cons. HNO3 on a hot plate. After that, the samples were filtrated into a 100-ml volumetric flask using Whatman No. 44 filter paper and made up to the mark with distilled water, while sediment samples were dried at 450 °C in muffle furnace to avoid the organic matter. The samples were ignited in a muffle furnace at 450 °C for at least 8 h. After, sediment samples were digested in 50% nitric acid on a hot plate. Then, the samples were filtrated into a 100-


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Chittagong

Fig. 1 Map showing sampling points of the Halda River (map created by ArcGIS v.10.3)

ml volumetric flask using Whatman No. 44 filter paper and washed the residue. The heavy metal contents of collected water and sediments were determined by AAS (Table 1) (Model-iCE 3300, Thermo Scientific, designed in the UK, made by China) and by complying standard procedures (APHA 1995).

of monthly stream flow of the river. PCA delivers strategies on spatial and temporal distribution of resultant factors. According to Singh et al. (2004), Pearson’s product moment correlation matrix was executed to identify the relation among parameters to make the result strong obtained from multivariate analysis.

Statistical analysis One way analysis of variance (ANOVA) of the data shows the variations in concentration of heavy metals in terms of seasons. Graph was used for graphical presentation of heavy metal against seasons and sites (SPSS v.22). According to Dreher (2003), principal component analysis (PCA) was performed on the original data set (without any weighting or standardization). PCA was performed to find out the standard features of variations in dataset with simplification and classification of raw data. Noori et al. (2008) used PCA technique with the SVM to forecast the weekly generated waste of Mashhad city and reported that it is a potential tool for predicting waste generation. Noori et al. (2010a) used PCA technique for the analyses of surface water quality of the Karoon River, Iran. Noori et al. (2010b) used PCA for the prediction

Table 1 Spectral lines used in emission measurements and the instrumental detection limit for the elements measured by using AAS Elements

Wavelength (nm)

Instrumental detection limit (mg/l)

Hg Pd Cr Co Cd Mn Ni Zn Cu Al

253.7 217.0 357.9 240.7 228.8 279.5 232.0 213.9 324.8 309.3

0.013 0.0054 0.01 0.0028 0.0016 0.008 0.0033 0.0045 0.028


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Results and discussion The finding in the present study reveals that the concentrations of Pb, Cd, Cr, Cu, Hg, Al, Ni, Co, Zn, and Mn in water were above the permissible limit as set by WHO 2004 and others (USEPA 2006, EPA 1986, 2002 and ECR 1997) with the exception of Cu and Co (Table 3). In sediment, the concentration of Pb, Cu, Al, Ni, Co, Zn, and Mn was exceeded the allowable limit as set by WHO 2008 and others (USEPA 1999 and FAO 1985), though observed Cd, Cr, and Hg concentrations were below the permissible limit (Table 6). Seasonal variation of heavy metal levels in surface water samples The amount of Pb was recorded between 0.1 and 0.01 mg/l in the present study. The highest concentration was found 0.1 mg/l at Kalurghat during post-monsoon season (Table 2). Aderinola et al. (2009) found 0.26 mg/l Pb at the Lagos Lagoon. Ahmad et al. (2010) recorded Pb concentration 0.07 mg/l in the Buriganga River and Ali et al. (2016) recorded 0.01 mg/l in the Karnaphuli River. Moreover, Hassan et al. (2015) found the Pb concentration below detection limit from the Meghna River, Bangladesh. The lowest concentration 0.01 mg/l was recorded at Kalurghat and Modhunaghat during monsoon season (Table 2). The concentration of Cd ranged between 0.03 and 0.20 mg/l (Table 2). The maximum amount of Cd was recorded (0.20 mg/l) above the tolerable limit set by USEPA (2006) and ECR (1997) (Table 3). Ahmad et al. (2010) found 0.009 mg/l Cd in the Buriganga River water. Ali et al. (2016) recorded 0.008 mg/l Cd in water sample of the Karnaphuli River, Bangladesh. Hassan et al. (2015) found the Cd concentration 0.0030 mg/l in the Meghna River, Bangladesh. The minimum amount was recorded at Kalurghat and Modhunaghat during monsoon season (Table 2). The concentration of Cr in the present study was found between 0.01 and 0.12 mg/l. The highest amount was recorded 0.12 mg/l that exceeded allowable limit set by WHO (2004), USEPA (2006) and ECR (1997) (Table 3). Ali et al. (2016) found 0.08 mg/l Cr in the Karnaphuli River. 0.19 mg/l Table 2

Cr was recorded by Shanbehzadeh et al. (2014) in the upstream of the Tembi River. Moreover, Alam et al. (2003) reported that higher concentration of Cr was found in the major river system of Bangladesh in rainy season (3–13 mg/l) than the concentration of dry season (1.2–8 mg/l). These results are higher than the present result. The lowest amount was recorded 0.01 mg/l at Kalurghat during monsoon (Table 2). In the present study maximum concentration of Cu was found (0.15 mg/l) that far below the admissible limit set by WHO (2004), EPA (2002), EC (1998) and ECR (1997) (Table 3). Aderinola et al. (2009) found 0.20 mg/l Cu at the Lagos Lagoon. 0.47 mg/l Cu was recorded by Shanbehzadeh et al. (2014) in the upstream of the Tembi River. Minimum concentration was found 0.05 mg/l at Kalurghat during monsoon (Table 2). The US Environmental Protection Agency’s suggested that below 5.8 ng/mL Hg is considered to be safe (Choi et al. 1981; Ballatori and Clarkson 1985). While WHO (ASTDR 2004) reported that an acceptable concentration of Hg in human hair is less than 6 μg/g. In the present study, the concentration of Hg varied between 0.001 and 0.01 mg/l (Table 2). The highest concentration 0.01 mg/l was found above the limit set by WHO (2004), ECR (1997) and USEPA (2006) (Table 3). The concentrations of Al ranged between 4.2 and 11.9 mg/l. The highest concentration was recorded 11.9 mg/l at Modhunaghat during monsoon (Table 2). All the metal concentrations exceeded the admissible limit (0.2 mg/l) set by ECR (1997) (Table 3). The lowest amount of Al found 4.2 mg/l during pre-monsoon season at Kalurghat. Balkis et al. (2010) found 2 mg/l Al from Gokova Bay, Turkey. Ni amount varied for 0.03–0.62 mg/l in the study area (Table 2). Maximum amount of Ni was found (0.62 mg/l) at Modhunaghat during post-monsoon that exceeded the allowable limit set by WHO (2004) and ECR (1997) (Table 3). Minimum value of Ni was found (0.03 mg/l) at Kalurghat during monsoon. Ahmad et al. (2010) recorded 0.0088 mg/l in the Buriganga River. Faisal et al. (2014) recorded 1.53 mg/l from river water in Savar industrial area. Mean concentrations (mg/l) of heavy metals in water during three seasons shown in Fig. 2.

Heavy metal concentration (mg/l) in water of the Halda River

Sites

Seasons

Pb

Cd

Cr

Cu

Hg

Al

Ni

Co

Zn

Mn

Kalurghat Modhunaghat Kalurghat Modhunaghat Kalurghat Modhunaghat

Pre-monsoon

0.1 0.01 0.01 0.01 0.2 0.1

0.05 0.04 0.03 0.03 0.04 0.03

0.07 0.06 0.01 0.12 0.05 0.04

0.12 0.13 0.05 0.06 0.1 0.15

0.004 0.002 0.002 0.001 0.005 0.003

4.2 5.2 11.2 11.9 4.5 5.4

0.55 0.61 0.03 0.04 0.6 0.62

0.05 0.03 0.04 0.03 0.06 0.07

0.2 0.35 0.3 0.48 0.3 0.48

0.04 0.2 0.05 0.28 0.06 0.3

Monsoon Post-monsoon


Author's personal copy Environ Sci Pollut Res Table 3 The heavy metal concentrations (mg/l) in freshwater and its comparison with international standards

Heavy metals

ECR 1997

WHO 2004

USEPA 2006

EC 1998

EPA 1986

EPA 2002

Present study

Pb Cd

0.05 0.005

0.01 –

0.0025 0.0025

10 5

– –

0.05 0.01

0.07 0.03

Cr Cu

0.05 1

0.05 2

0.1 0.013

– 2

– –

– 1.3

0.06 0.10

Hg

0.001

0.001

0.002

0.003

Al Ni

0.2 0.1

– 0.02

– –

– 20

– –

– –

7.06 0.41

Co Zn

– 5

– –

– 0.12

– –

– 5

– –

0.05 0.35

Mn

0.1

0.4

0.1

0.16

Co concentration was measured between 0.03 and 0.07 mg/l from the study area. The highest concentration was found 0.07 mg/l at Modhunaghat during post-monsoon (Table 2). The lowest concentration was found 0.03 mg/l at Modhunaghat during monsoon and pre-monsoon (Table 2). The Co is favorable to health but excess level of Co may pose lung and heart effects and dermatitis (ATSDR 2004). Fig. 2 Graph showing mean concentrations (mg/l) of heavy metals in water during three seasons

Zn was found between 0.2 and 0.48 mg/l. The highest concentration was recorded 0.48 mg/l at Modhunaghat during monsoon and post-monsoon (Table 2). This amount exceeded the limit set by USEPA (2006) but below the limit set by ECR (1997) and EPA (1986). Hassan et al. (2015) recorded the Zn concentration 0.0311 mg/l in the Meghna River, Bangladesh. 0.20 mg/l Zn was recorded by Shanbehzadeh et al. (2014) in the Pb Cd Cr Cu Hg Al Ni Co Zn Mn

15.00

Mean concentration

10.00

5.00

0.00

Pre-Monsoon

Monsoon

Post-Monsoon

Seasons Error Bars: +/- 2 SD


Author's personal copy Environ Sci Pollut Res Table 4

Comparison of heavy metal concentrations (mg/l) of the Halda River water with other rivers of Bangladesh

River

Pb

Cd

Cr

Cu

Hg

Al

Ni

Co

Halda

0.03

0.04

0.03

0.1

0.001

7.06

0.41

0.01

0.35

0.16

Present study

Buriganga

0.07

0.009

0.59

0.163

0.008

Ahmad et al. 2010

Buriganga

0.112

0.059

0.114

0.332

0.157

Bhuiyan et al. 2015

Balu

0.001

0.008

0.01

0.02

0.03

Mokaddes et al. 2013

0.15

Zn

Mn

References

Dhaleshwari

0.05

0.006

0.44

0.15

0.007

Ahmed et al. 2009

Dhaleshwari

0.20

0.00

0.13

0.00

Ahmed et al. 2012

Khiru

0.02

0.13

0.004

0.006

0.17

Rashid et al. 2012

Karatoa

Trace

0.005

Trace

0.005

Trace

0.101

Zakir et al. 2012

Karnofuly

0.14

0.01

0.25

0.05

0.28

0.12

Islam et al. 2013

Meghna

BDL

0.003

0.035

BDL

0.036

0.009

Hassan et al. 2015

Shitalakhya

0.001

0.01

0.005

0.02

0.05

Mokaddes et al. 2013

Shitalakhya

0.05

0.003

0.08

0.04

Turag

0.002

0.01

0.004

0.02

0.72 –

Islam et al. 2014b

0.02

0.06

Mokaddes et al. 2013

Bangladesh. Islam et al. (2014) found 28.36 mg/kg from the Shitalakhya River. Banu et al. (2013) recorded 32.78 mg/kg in the Turag River. Ahmad et al. (2010) reported that maximum value of Pb (77.13 mg/kg) was found from the Buriganga River during pre-monsoon. The lowest concentration was found 6.3 mg/kg at Kalurghat during pre-monsoon (Table 5). The concentrations of Cd ranged between 0.02 and 0.1 mg/kg (Table 5). Maximum amount was found 0.1 mg/kg at Kalurghat during post-monsoon. Minimum amount was found 0.02 at Kalurghat and Modhunaghat during premonsoon (Table 5). The results are below the permissible limit set by WHO (2004) and USEPA (1999) (Table 6). Higher amount of Cd than the present study was found by Islam et al. (2015b) (1.20 mg/kg), Islam et al. (2014) (5.01 mg/kg), Ahmed et al. (2012) (2.08 mg/kg), and Ahmad et al. (2010) (3.33 mg/kg) (Table 7). Cr concentrations varied between 4.95 and 16.8 mg/kg, where the highest value 16.8 mg/kg was found at Modhunaghat during monsoon season. The concentration of Cr below the allowable limit set by WHO (2004) and USEPA (1999) (Table 6) but exceeded the limit set by WHO (2008) and FAO (1985). Aderinola et al. (2009)

upstream of the Tembi River. The lowest concentration was found at 0.2 mg/l at Kalurghat during pre-monsoon (Table 2). Mn concentration varied between 0.05 and 0.28 mg/l. The highest concentration of Mn was recorded (0.28 mg/l) at Modhunaghat during monsoon that above the permissible limit set by WHO (2004), ECR (1997) and EPA (1986) (Table 3). This concentration also above the value recorded by Mokaddes et al. (2013) in the Buriganga River, Turag river, Balu river, Meghna river, and Shitalakshiya river. Hassan et al. (2015) recorded the Mn concentration 0.00854 mg/l in the Meghna River, Bangladesh (Table 4). Seasonal variation of heavy metal levels in surface sediment samples The concentration of Pb ranged between 6.3 and 15 mg/kg. The highest concentration of Pb recorded 15 mg/kg at Modhunaghat during monsoon (Table 5). This result is above the limit set by FAO (1985) but lower than the limit set by USEPA (1999). Ali et al. (2016) recorded 43.685 mg/kg Pb in the Karnaphuli River, Bangladesh. Hassan et al. (2015) found the Pb concentration 9.4702 mg/kg from the Meghna River,

Table 5

Heavy metal concentration (mg/kg) in sediment of the Halda River

Sites

Seasons

Pb

Cd

Cr

Cu

Hg

Al

Ni

Co

Zn

Mn

Kalurghat Modhunaghat Kalurghat Modhunaghat Kalurghat Modhunaghat

Pre-monsoon

6.3 7 11 15 6.2 7.1

0.02 0.02 0.03 0.03 0.10 0.04

5.7 4.71 15.1 16.8 5.8 4.95

4.7 4.1 9.25 9 4.5 3.9

0.001 0.001 0.0012 0.001 0.003 0.002

7501 8200 12.700.00 11,700.00 7500.00 8300.00

12.7 11.3 25 22.5 12.8 11.5

3.4 3.1 8.7 7.6 3.5 3.2

17.3 15.8 135 275 17.5 16.9

82 77 245 269 85 79

Monsoon Post-monsoon


Author's personal copy Environ Sci Pollut Res Table 6 Comparison of the observed values of heavy metals in the sediments of the Halda River with international standard

Heavy metals

WHO 2008

WHO 2004

USEPA 1999

FAO 1985

Present study

Pb

40

5

8.80

Cd

6

0.6

0.04

Cr Cu

0.05 –

25 –

25 –

0.1 0.2

8.84 5.90

Hg

0.001

Al Ni

– –

– 20

– 16

5 0.2

9316.83 15.97

Co

0.05

0.05

4.92

Zn Mn

5.0 0.5

123 –

110 30

2 0.2–10

79.58 139.5

found 0.62 mg/kg Cr at the Lagos Lagoon. One hundred sixty-seven milligrams per kilogram Cr was recorded by Shanbehzadeh et al. (2014) in the upstream of the Tembi River. The lowest value 4.95 mg/kg was found at Modhunaghat during post-monsoon (Table 5). The concentration of Cu ranged between 3.9 and 9.25 mg/kg (Table 5). The maximum value was recorded

Fig. 3 Graph showing mean concentrations (mg/l) of heavy metals in water at two sampling sites

9.25 mg/kg at Kalurghat during monsoon season. This results exceeded the permissible limit set by FAO (1985) (Table 5). Aderinola et al. (2009) found 0.60 mg/kg Cu at the Lagos Lagoon. 51.5 mg/kg Cu was recorded by Shanbehzadeh et al. (2014) in the upstream of the Tembi River. Hg concentration recorded between 0.001 and 0.003 mg/kg. The highest concentration was recorded 0.003 mg/kg at

Pb Cd Cr Cu Hg Al Ni Co Zn Mn

20.00

Mean concentration

15.00

10.00

5.00

0.00

-5.00

Kalurghat

Modhunaghat

Sites Error Bars: 95% CI


Author's personal copy Environ Sci Pollut Res Fig. 4 Graph showing mean concentrations (mg/kg) of heavy metals in sediment during three seasons

Pb Cd Cr Cu Hg Al Ni Co Zn Mn

Mean concentration

20,000.00

10,000.00

0.00

-10,000.00

Pre-Monsoon

Monsoon

Post-Monsoon

Seasons Error Bars: +/- 2 SD

Kalurghat during post-monsoon. The lowest concentration 0.001 was found at Kalurghat and Modhunaghat during premonsoon and monsoon season (Table 5). Al concentration ranged between 7500 and 12,700 mg/kg from the study area (Table 5). The highest amount was recorded 12,700 mg/kg at Kalurghat during monsoon. The lowest amount was found 7500 mg/kg at Kalurghat during post-monsoon season (Table 5). Both lowest and highest concentration of Al far above the permissible limit set by FAO (1985) (Table 6). Mean concentrations (mg/kg) of heavy metals in sediment during three seasons shown in Fig. 4. Ni amount was found to be varied between 11.3 and 22.5 mg/kg. Maximum value 22.5 mg/kg was recorded at Modhunaghat during monsoon. This concentration was above the allowable limit set by WHO (2004), USEPA (1999), and FAO (1985) (Table 6), while minimum value 11.3 mg/kg was found at Modhunaghat during pre-monsoon (Table 5). Aderinola et al. (2009) found 0.87 mg/kg Ni at the Lagos Lagoon. Ahmad et al. (2010) recorded 200.45 mg/kg in the Buriganga River. Hassan et al. (2015) recorded 76.116 mg/kg in the Meghna River, Bangladesh.

In the present study, the concentrations of Co found between 3.1 and 8.7 mg/kg. The highest amount was recorded 8.7 mg/kg at Kalurghat during monsoon. The lowest amount was recorded at Modhunaghat during pre-monsoon (Table 5). These results are more or less similar to the results found by Topcuoglu et al. (2004) and Balkis et al. (2007). The present concentrations exceeded the admissible limit (0.05 mg/kg) set by WHO (2008) and FAO (1985) (Table 6). Mean concentrations (mg/kg) of heavy metals in sediment at two sites shown in Fig. 5. Zn concentration varied between 15.8 and 275 mg/kg in the sediment samples. Maximum concentration 275 mg/kg was recorded at Modhunaghat during monsoon (Table 5). These concentrations are found above the limit set by WHO (2008), WHO (2004), USEPA (1999), and FAO (1985) (Table 6). Minimum amount 15.8 mg/kg was recorded at Modhunaghat during pre-monsoon (Table 5). The present results are far below than the results found by Rahman et al. (2014) (117.15 mg/kg), Banu et al. (2013) (139.48 mg/kg), and Saha and Hossain (2011) (502.26 mg/kg).


Author's personal copy Environ Sci Pollut Res Fig. 5 Graph showing mean concentrations (mg/kg) of heavy metals in sediment at two sampling sites

Pb Cd Cr Cu Hg Al Ni Co Zn Mn

15,000.00

Mean cfoncentration

10,000.00

5,000.00

0.00

-5,000.00

Kalurghat

Modhunaghat

Sites Error Bars: +/- 2 SD

Heavy metal concentrations (mg/kg) of the Halda river sediment with other rivers of Bangladesh shown in Table 7.

Table 7

The concentration of Mn recorded between 77 and 269 mg/kg. The highest amount 269 mg/kg of Mn was recorded at Modhunaghat, and the lowest amount 77 mg/kg was

Comparison of heavy metal concentrations (mg/kg) of the Halda river sediment with other rivers of Bangladesh

River

Pb

Cd

Cr

Cu

Hg

Al

Ni

Co

Zn

Mn

References

Halda Buriganga

8.80 69.75

0.04 3.33

8.84 177.5

5.90 27.85

0.001 –

9316.833 –

15.97 200.5

4.92 –

79.58 –

139.5 –

Present study Ahmad et al. 2010

Buriganga Buriganga

79.8 31.4

0.8 1.5

101.2 173.4

184.4 344.2

– –

– –

– 153.3

– –

502.3 481.8

– 4036

Saha and Hossain 2011 Mohiuddin et al. 2015

Bangshi

59.99

0.61

98.1

117.15

483.4

Rahman et al. 2014

Dhaleshwari

15.79

2.08

27.39

37.45

Ahmed et al. 2012

Khiru

5.60

2.05

34.7

97.77

28.56

Rashid et al. 2012

Karnofuly

4.96

0.24

0.76

1.22

16.30

15.30

Islam et al. 2013

76.1

79.02

442.6

Hassan et al. 2015

Karatoa

58

1.20

109

Meghna

9.47

0.23

31.74

Shitalakhya

28.36

5.01

63.22

25.67 –

95

Islam et al. 2015b

39.22

Shitalakhya

74.82

143.7

Turag

1.64

1.4

0.44

1.576

75

Islam et al. 2014b

30,432.4

13.37

200.6

Islam et al. 2016

1.08

Banu et al. 2013


Author's personal copy Environ Sci Pollut Res Table 8

Correlation matrix of heavy metals in water Pb

Cd

Cr

Cu

Hg

Al

Ni

Co

Pb

1

Cd

0.393

Cr Cu

− 0.156 0.373

0.112 0.391

1 − 0.094

Hg Al

0.941 − 0.665

0.610 − 0.710

− 0.304 0.177

0.416 − 0.857

1 − 0.772

Ni

0.612

0.571

− 0.149

0.922

0.673

− 0.977

Co Zn

0.787 − 0.280

0.050 − 0.789

− 0.413 0.332

0.535 0.036

0.721 − 0.563

− 0.558 0.393

0.560 − 0.201

1 0.004

Mn

− 0.333

− 0.572

0.440

0.275

− 0.561

0.199

− 0.006

− 0.041

Zn

Mn

1 1

found at Drenerghat during pre-monsoon (Table 5). The concentrations exceeded the permissible limit set by WHO (2008), USEPA (1999), and FAO (1985) (Table 6), but the results are below than the concentration found by Hassan et al. (2015) (442.596 mg/kg) and Rahman et al. (2014) (483.44 mg/kg). Analysis of variance (ANOVA) in water and sediment Significant variations in the concentrations of Al and Ni were found in terms of seasons (p < 0.05). However, no substantial differences (p > 0.05) were found in Cr, Cu, Pb, Cd, Hg, Co, Zn and Mn levels across the water. Moreover, prevalent variations (p < 0.05) in the concentrations of Zn and Mn were recorded in terms of sites (p > 0.05). Substantial changes in the concentrations of Cr, Cu, Pb, Co, Mn, and Ni were found in sediment in terms of seasons (p < 0.05). However, no significant variations (p > 0.05) were found in Cd, Hg, Zn, and Al levels across the sediment. In terms of sites, no significant variations were found in the metal concentrations (p > 0.05). Correlation matrix of heavy metals in water and sediment In aquatic environment, the interrelationship among metals in water and sediment provides significant Table 9 Correlation matrix of heavy metals in sediment Pb Cd Cr Cu Hg Al Ni Co Zn Mn

1 1 1

.

0.939

1

information of sources and pathways of variables (heavy metals). The result of correlations between heavy metals acquiesced with the results obtained by PCA and CA that confirm some new associations between parameters. Very strong, strong, and moderate correlation indicates that their sources of origin are similar especially from industrial effluents, municipal wastes, and agricultural inputs. In case of water, very strong linear relationship was found in Hg vs Pb (0.941), Mn vs Zn (0.939), and Ni vs Cu (0.922) at the significance level 0.01 (Table 8). Strong relationship was observed in Cu vs Pb (0.787) and Co vs Hg (0.721) at the alpha level 0.01. Very strong negative relationship was found between Ni vs Al (− 0.977) and Al vs Cu (− 0.857) at the significance level 0.05 and 0.01 (Table 8). In sediment, very strong linear relationships were found in Mn vs Cr (0.999), Co vs Ni (0.999), Ni vs Cu (0.994), Zn vs Pb (0.993), Co vs Cu (0.992), Cu vs Cr (0.990), Mn vs Cu (0.989), Mn vs Ni (0.975), Mn vs Co (0.975), Ni vs Cr (0.974), Co vs Cr (0.972), Mn vs Pb (0.951), Cr vs Pb (0.948), Zn vs Cr (0.944), and Mn vs Zn (0.941) at the significance level 0.01 (Table 8). Moreover, Cu vs Pb (0.900), Zn vs Cu (0.891), Co vs Pb (0.863), Ni vs Pb (0.859), Zn vs Ni (0.845), and Zn vs Co (0.843) showed very strong linear relationship at the significance level 0.05 (Table 9).

Pb

Cd

Cr

Cu

1 − 0.507 0.948 0.900 − 0.634 0.101 0.859 0.863 0.993 0.951

1 − 0.402 − 0.364 0.577 0.056 − 0.379 − 0.420 − 0.418 − 0.443

1 0.990 − 0.544 − 0.182 0.974 0.972 0.944 0.999

1 − 0.543 − 0.309 0.994 0.992 0.891 0.989

Hg

− − − −

1 0.037 0.510 0.533 0.566 0.572

Al

Ni

Co

Zn

Mn

1 − 0.400 − 0.404 0.151 − 0.193

1 0.999 0.845 0.975

1 0.843 0.975

1 0.941

1


Author's personal copy Environ Sci Pollut Res Table 10 Component matrix of two factors model with strong to moderate loadings in water and sediment

Water

Sediment

Eigenvalues (0.5)

Component

Eigenvalues (0.6)

Component

PC 1

PC 2

PC 1

PC 2

Pb

0.824

0.567

Pb

1.000

− 0.014

Cd Cr

0.889 0.960

− 0.458 − 0.281

Cd Cr

− 0.864 1.000

− 0.503 0.013

Cu

0.973

− 0.231

Cu

0.999

− 0.033

Hg Al

0.928 − 1.000

0.373 − 0.010

Hg Al

− 0.834 − 1.000

0.551 − 0.004

Ni Co

0.992 0.841

0.127 0.541

Ni Co

1.000 1.000

0.011 0.020

Zn

− 0.541

0.841

Zn

1.000

0.005

Mn Eigenvalue

− 0.048 7.185

0.999 2.815

Mn Eigenvalue

1.000 9.440

0.020 0.560

% total variance Cumulative %

71.845 71.845

28.155 100.000

% total variance Cumulative %

94.404 94.404

5.596 100.000

Principal component analysis The extraction method was executed to find out the principal components in PCA analysis that were eigenvalues. In water, the components were taken as principal components whose eigenvalues greater than 0.5 were taken into account. Two PCs were extracted by using correlation matrix which reflects the processes influencing the heavy metals composition having 100.0% of total sample variance (Table 10). The total variance of the PCs were 71.845 and 28.155% for PC 1 and PC 2, respectively. PC 1 is strongly correlated with Pb, Cd, Cr, Cu, Hg, Ni, and Co and PC 2 with Zn and Mn (Table 10). The source of PC 1 and PC 2 can be deliberated as different source from both lithogenic and anthropogenic inputs. In sediment, the components were considered as principal components whose eigenvalues were higher than 0.6. Two PCs were extracted by using correlation matrix which reflect the processes influencing the heavy metals composition having 100.0% of total sample variance (Table 10). The total variance of the PCs was 94.404 and 0.560% for PC 1 and PC 2, respectively. PC 1 is strongly correlated with Pb, Cr, Cu, Ni, Co, Zn, and Mn, and PC 2 showed moderate relation with Hg (Table 10). The source of PC 1 and PC 2 can be considered as mixed source from anthropogenic inputs particularly from industrial effluents and agricultural activities in the study area.

Conclusion The study shows that seasonal water flows/water discharge (pre-monsoon, monsoon, and post-monsoon) have an impact on the mobility of metals. Most of the metals exceeded the permissible limit both in water and sediment set by different

international organizations. The discharge of untreated effluents from the various industrial, urban as well as the agricultural activities occurred in the vicinity of the Halda River is a prime responsible agent for this elevated level of heavy metals. The detection of high-risk metals (toxic and bioaccumulative metals) may demonstrate that metals can cause significant effects on the Gangetic carp fishery (Labeo rohita, Gibelion catla, Cirrhinus cirrhosus) and prawn fishery (Macrbrachium rosenbergii) and the livelihoods of the people associated with fishing in the Halda River in Bangladesh. Thus, the present research suggested that the sources of trace metals adjacent to the Halda River should be strictly monitored to protect the river ecosystem. Acknowledgements The authors are grateful to the Bangladesh Council of Scientific and Industrial Research (BCSIR), Chittagong. The proposed research is a major contribution of Biodiversity, Environment and Climate Change Research Laboratory, Institute of Marine Sciences and Fisheries, University of Chittagong. Authors also express heartiest thanks to the reviewers for their valuable guidelines to improve the paper quality.

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