Distribution and binding behaviour of trace metals in marine ecosystem of Thane Creek, Mumbai

Journal Pre-proof Distribution and binding behaviour of trace metals in marine ecosystem of Thane Creek, Mumbai

Sukanta Maity, P. Sandeep, S.K. Sahu, A. Vinod Kumar PII:

S2590-1826(20)30003-5

DOI:

https://doi.org/10.1016/j.enceco.2020.01.003

Reference:

ENCECO 11

To appear in:

Environmental Chemistry and Ecotoxicology

Received date:

2 December 2019

Revised date:

24 January 2020

Accepted date:

26 January 2020

Please cite this article as: S. Maity, P. Sandeep, S.K. Sahu, et al., Distribution and binding behaviour of trace metals in marine ecosystem of Thane Creek, Mumbai, Environmental Chemistry and Ecotoxicology(2020), https://doi.org/10.1016/j.enceco.2020.01.003

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© 2020 Published by Elsevier.

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Distribution and binding behaviour of trace metals in marine ecosystem of Thane Creek, Mumbai 1

Sukanta Maity, Sandeep P., S. K. Sahu and A. Vinod Kumar Environmental Monitoring and Assessment Division, Health Safety and Environment Group, Bhabha Atomic Research Centre, Mumbai-400085, India 2 Homi Bhabha National Institute, Anushaktinagar, Mumbai-400094, India Corresponding author: Tel. +91-22-2552375; fax: +91225505151 E-mail address: [email protected] (S. K. Sahu)

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Abstract

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Thane Creek, Mumbai, India receives discharges from various industries which can contaminate the marine ecosystem. Binding behaviour of trace metals (Pb, Cu, Cd and Co) was studied in sediment samples collected across the Thane Creek area, Mumbai, India using sequential extraction procedure. All the studied metals were found to be mainly associated with residual fraction in varying percentages. Trace metal contribution in the easily exchangeable and acid extractable fraction (bioavailable fraction) was observed to be lowest, an exception was observed for Cd. Distribution of trace metals in biota samples (Lizardfish, shrimps, prawn and crab) collected from the same locations was also studied. The concentration order of Pb, Cu and Co in the studied biota samples was found as follows Lizardfish
Fig. 1. Graphical abstract. Key words: Trace metal, marine sediment, sequential extraction, marine biota, hazard index 1.

Introduction

Sediment is generally considered as a sink for trace metals [1]. Trace metals after releasing into the aquatic systems are bound to particulate matter, which eventually settles and becomes incorporated into sediments. In recent years, persistence, abiotic degradation, toxicity, and bioaccumulation properties of trace metals in the environment have become a topic of considerable concern [2, 3]. Trace metals in the sediment can be released into the overlying 1

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water, due to the changing environmental conditions [4, 5]. The released metals in water can be consumed by the marine organism and can accumulate to hazardous levels. Total metal concentrations in sediment poorly reflect the mobility and bioavailability in aquatic systems [6]. Knowledge on the chemical partitioning (binding nature) of trace metals in sediment samples is important in determining the bioavailability of trace metals [7]. The bioavailable fraction of trace metals can be consumed by marine biota and can give potential health risk to the public through the food chain. The Community Bureau of Reference Sequential Extraction Procedure (BCR-SEP) had been widely used to investigate trace metal fractionation according to binding behaviour in various environmental matrices, such as soil [8], freshwater sediments [9], and saltwater sediments [10]. To evaluating environmental risk from trace metals and to estimate the potential damage they could cause to sediment-dwelling organisms, the Risk Assessment Code (RAC) has been used by various researchers [6, 11]. Metal concentrations in fish can act as an environmental indicator as biota is often the top consumers in aquatic ecosystems [12]. Via food chain biota is exposed to a variety of toxic elements and may eventually become potentially harmful to humans [13]. The gastrointestinal pathway is the primary route (90%) of the total trace metal uptake, while gills and skin also serve as routes for trace metal intake for fish [14, 15]. Pb, Cu, Cd and Co can be accumulated to high concentrations in biota samples depending on their bioavailability in the marine aquatic system and can show toxicity under some conditions [16]. Most of the chemical forms of Pb is toxic and affects biota and living organisms. Pb affects hematopoietic, vascular, nervous, renal and reproductive systems in human being. Cu can pose toxicity to fishes, invertebrates and aquatic plants when the rate of absorption exceeds the rate of excretion. Cu is highly toxic to most fishes, invertebrates and aquatic plants. Reproduction and growth in plants and animals are reduced due to Cu [17]. Cd is one of the most toxic and mobile trace metals [18]. Higher bioavailability of Cd increases it’s toxicity in living organisms compared to other divalent metals. Various adverse health effects have been seen due to overexposure of Co although it is essential for the living being. The health effects include cardiovascular, neurological and endocrine deficits [19]. Thane Creek, Mumbai is surrounded by various industries. About 25 large scale and 300 medium and small-scale hazardous chemical industries are there out of total of 2000 units at present. Discharges from the medium and the small-scale industries are thrown to the Thane Creek except for a few major industries. Domestic sewage discharges also contribute to the Thane Creek from suburbs of Mumbai City from the west side. The metal smelting and refining industries, plastic and rubber industries, dyeing and printing of textiles, and various consumer products contribute trace metals (Pb, Cu, Cd and Co) to the Thane creek [20]. Total metal concentration does not give real pollution scenario. Hence, there is a need to identify the chemical binding nature of metals to gain knowledge on the bioavailability of metals in the sediment sample for real pollution level assessment. The objective of the work is to investigate the trace metal binding behaviour and the associated mobility in sediments from the coastal area of the Thane Creek, Mumbai, India using the BCR-SEP. The calculated RACs are used to assess the potential ecological risk associated with the trace metals present. To understand the correlation between bioavailability of trace metals in sediment and metal concentration in the biota samples, distribution of trace metals in the biota mainly feeding on sediments were also estimated.

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Materials and Methods

2.1. Study area and sample collection

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The stretch of the Thane Creek is about 20 km long and 2 km wide. In the south, Thane Creek opens to the Arabian Sea. Mainly brackish water is present in Thane creek. The details of sampling locations are represented in Figure 2 which was discussed in our previous publication [21]. The details of sampling locations with latitude and longitude are represented in Table 1. Fourteen grab sediment samples were collected from different locations across Thane Creek area, using a Van Veen grab sampler and transferred to polyethylene bags and brought to the laboratory in cooler boxes at 0 - 4 ◦C. The polyethylene bags were treated prior with electronic grade hydrochloric acid (HCl) (1 mol/l) (Merck Life Science Private Limited, Mumbai, India) and rinsed with distilled water to avoid any loss of trace metals through surface adsorption. Biota samples (Lizardfish, shrimps, prawn and crab), mainly sediment grazing were purchased from local fishermen who had collected from different locations of the Thane creek.

Fig. 2. Sampling location.

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Journal Pre-proof Table 1 Details of sampling locations with latitude and longitude. Latitude

Longitude

Location 1

19° 6'50.06"N

72°58'36.40"E

Location 2

19° 4'47.18"N

72°58'53.64"E

Location 3

19° 3'19.04"N

72°59'28.17"E

Location 4

19° 1'46.48"N

72°59'56.96"E

Location 5

19° 0'16.62"N

72°59'51.30"E

Location 6

18°59'38.13"N

73° 1'28.92"E

Location 7

18°58'37.92"N

73° 0'30.55"E

Location 8

18°58'20.22"N

72°58'25.73"E

Location 9

18°58'45.38"N

72°56'55.37"E

Location 10

18°59'25.00"N

72°51'51.00"E

Location 11

18°59'33.40"N

72°54'0.90"E

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Sampling Location

Location 12

72°56'2.91"E

19° 1'43.72"N

72°57'38.23"E

19° 4'23.00"N

72°57'35.04"E

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Location 13

19° 0'10.76"N

2.2. Sample processing

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Sediment samples were freeze-dried and sieved below 2 mm using an electromagnetic sieve shaker (EMS 8, Electrolab, Navi Mumbai, India). The fraction of < 2 mm (grab sediment) was used for sequential extraction. Biota samples were washed under tap water to remove sediment particles adhering to the body of the organism. Later, cleaned with distilled water and dried at room temperature. The edible part of biota samples was segregated, freeze-dried and ground to make fine powder for homogenization and stored in the deep fridge (- 200 C) till analysis. Sequential extraction was carried out in the collected sediment samples to understand the binding behaviour of Pb, Cu, Cd and Co. Biota samples were acid digested for analysis of trace metals using the method detailed in Maity et al. 2017b [22]. In the present study BCR-SEP, which uses a series of selective extractants, separating the trace metals into four forms, has been used as an evaluative tool [23]. Fraction 1 (F1) represents easily exchangeable and acid extractable fraction (EE&AEF) also known as a bioavailable fraction, fraction 2 (F2) represents reducible fraction (RedF), fraction 3 (F3) represents oxidizable fraction (OF), and fraction 4 (F4) represents residual fraction (ResF).

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Journal Pre-proof 2.3. Quality assurance Supra-pure grade reagents were used for analysis. To remove cross-contamination, the relevant laboratory apparatus was soaked in nitric acid followed by rinsing thoroughly with distilled water. Reagent blanks were prepared and subsequently analysed for metals of interest for blank correction. For precision of the analytical methods and instruments, triplicate samples were analyzed. 2.4. Sample analysis

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Pb, Cu, Cd was analyzed simultaneously in Differential Pulse Anodic Stripping Voltammetry (DPASV) (663 VA Stand Metrohm). Whereas Co was analyzed using Differential Pulse Cathodic Stripping Voltammetry (DPCSV) (663 VA Stand Metrohm) in presence of dimethylglyoxime and ammonia solution through standard addition method. The details of the analysis procedure are represented in Table 2. Voltammetry was found to be the choice of instrument for the determination of trace metals in a complex environmental matrix-like estuarine sediment [24]. The typical voltammogram of the sample for Pb, Cu and Cd is presented in Figure 3.

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Pb 60 90 7 -0.9 0.05 50 0.04 0.1 0.0595 -0.38 -

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Parameters Initial purging time (s) Deposition time (s) Equilibration time (s) Start potential (V) End potential (V) Pulse amplitude (mV) Pulse time (s) Voltage step time (s) Sweep rate (mV/s) Peak potential (V) No. of standard additions

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Table 2. The details program of voltammogram for analysis of Pb, Cu, Cd and Co in voltammetry

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Cu 60 90 7 -0.9 0.05 50 0.04 0.1 0.0595 -0.6 -

Cd 60 90 7 -0.9 0.05 50 0.04 0.1 0.0595 -0.01 -

Co 60 60 5 -0.8 -1.15 50 0.04 0.4 0.0099 -1.06 2

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Fig. 3. Pb, Cu and Cd analysis in DPASV. 2.5. Data treatment

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The Risk Assessment Code (RAC) is defined as the exchangeable and acid extractable fraction or bioavailable fraction of metal (i.e., the percentage of the metal found in F1 for the BCR method) in sediment samples. Perin et al. (1985) [25] described that RAC of less than 1% indicates that there is no risk to the aquatic environment from the metal, RAC of 1–10% indicates low risk, RAC of 11–30% indicates medium risk, and that RAC of 31–50% indicates high risk. RAC of more than 50% means that the sediment poses a very high risk to the aquatic environment and should be considered dangerous because the trace metals will be able to enter the food chain easily. Maximum Allowable Concentration (MAC) for a specific metal in the tissue of the biota represents the highest concentration that can occur without causing harm to human beings. The MAC in food based on the Reference Dose (RfD) is calculated using the equation for the intake of a contaminant. (1) Where, CF is the contaminant concentration in fish, (mg kg-1 wet weight); IR is the ingestion rate (kg d-1); EF is the exposure frequency (d y-1); ED is the exposure duration (y); BW is the body weight (kg); AT is the averaging time (period over which exposure is averaged in days). If the hazard quotient (HQ), defined as the ratio of daily intake to the RfD, is less than 1, toxic effects are not expected to occur. The RfD is an estimated single daily chemical intake rate that appears to be without risk if ingested over a lifetime. The ingestion rates were chosen to represent the average consumption rates of fish by an adult person (14 g d -1) (ICMR, 1986) [26]. 6

Journal Pre-proof Hazard Index (HI) is the summation of HQ for all the metals in a particular species. Hazard Quotient (HQ) and Hazard Index (HI) are calculated using the following equations given below. (2) (3)

∑ 3.

Results and Discussion

3.1. Trace metals binding behavior in sediment

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Pb, Cu, Cd and Co were found in different percentages in the four sequentially extracted fractions as represented in Figures 4, 5, 6 and 7. The metals studied were mainly associated with residual fraction in varying percentages like 59.4 – 63.4 %; 60 – 62.8 %; 46.6 – 49.6 % and 72.4 to 76.8 % for Pb, Cu, Cd and Co respectively in different sampling locations. The dominance of the residual fraction is probably due to the fact that trace metals come from the parent material of geological origin and may exist in the residual form in the sediments. This indicates that the contribution of anthropogenic sources is less important for studied trace metals in collected sediments. High levels of trace metals in the residual phase reveal that these metals are relatively insensitive to any change of surrounding conditions. Bastami et al. (2016) [27] also discussed that residual phase of trace metals (Co, Cr, Cu, Ni, Pb, Zn, V and Cd) was dominated in sediment samples at all sampling sites. Pb, Cu and Co contribution in the first fraction of the sequential extraction procedure was observed to be lowest in varying percentages like 0.64 – 0.91 %; 1.23 – 2.45 % and 2.10 to 3.40 % in the sampling locations, exception observed for Cd (27.4 – 28.5 %). The bioavailable fraction is higher for Cd compared to other studied metals. The bioavailable fraction demonstrates that, when the right pH and redox conditions are favourable, the metal will be soluble and will be taken up by aquatic biota which then will cause environmental toxicity [9]. The percentage of Pb associated with different fractions was in the order: residual>reducible>oxidizable>bioavialable. This result is in agreement with the other studies [28, 29]. Co association in different fractions was observed similar to Pb. Association of Cu in different fractions was observed in slightly different order like residual>oxidizable> reducible > bioavailable. Except for the residual fraction, the next important phase of Cd in sediment was the bioavailable fraction. Sum of concentrations of all the four fractions in the sequential extraction procedure for each studied metal was compared with the total metal concentrations in the sediment samples across Thane creek area [30]. Results indicate that more than 87% of the total concentration is recovered in the sequential extraction procedure as presented in Table 3.

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% Residual Fraction % Oxidizable Fraction % Reducible Fraction % Bioavailable Fraction

80 70 60 50

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Percentage Fractionation of Pb

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Fig. 4. Percentage distribution of Pb in different fractions of sequential extraction procedure in sediment.

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% Residual Fraction % Oxidizable Fraction % Reducible Fraction % Bioavailable Fraction

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Percentage Fractionation of Cu

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Fig. 5. Percentage distribution of Cu in different fractions of sequential extraction procedure in sediment.

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Percentage Fractionation of Cd 20

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Fig. 6. Percentage distribution of Cd in different fractions of sequential extraction procedure in sediment.

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80

% % % %

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Residual Fraction Oxidizable Fraction Reducible Fraction Bioavailable Fraction

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% Residual Fraction % Oxidizable Fraction % Reducible Fraction % Bioavailable Fraction

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Percentage Fractionation of Co

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Fig. 7. Percentage distribution of Co in different fractions of sequential extraction procedure in sediment.

Pb (ng/g) Cu (ng/g) Cd (ng/g) Co (ng/g)

Total concentration 19805 - 23610 76001-160102 85.6 – 352.2 16501 – 23014

Reference

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Table 3 Mass balancing of trace metals concentrations in sequential extraction procedure.

[30] [30] [30] [30]

Concentration in sum of the fractions 17903 - 22405 71395-156906 75.3 – 309.9 15004 – 21909

Recovery (%) 90.4 – 94.9 93.9 – 98.0 87.9 - 88.0 90.9 – 95.2

3.2. Trace metal pollution characteristics The sediments analyzed in this study had RAC values of Pb below 1 % in all the samples, indicating that the mobility of this metal is very less in the creek. All the samples had RAC values within 1-10% for Cu and Co indicating a low risk. Cd showed medium risk with RAC values in the range of 11 - 30%, in all the sediment samples. The results suggested that Cd was comparatively easily released by the sediments into the water in the creek, and therefore may enter the food chain. Results obtained by Nemati et al. (2011) [6], using sediments from Sungai Buloh (Malaysia), highly polluted by contaminants contained in industrial effluents also showed 11

Journal Pre-proof that 33% of Cd was present in the bioavailable fraction, resulting in a high risk to the environment. 3.3. Trace metals in marine biota

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Trace metal concentrations were determined in the edible part of biota (Lizardfish, shrimps, prawn and crab). Pb, Cu, Cd and Co concentrations in the edible part of biota are represented in Table 4. It is observed that Pb, Cu and Co concentrations in the biota samples increases in the following order Lizardfish
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Table 4 Trace metal concentrations in the edible part of biota (wet weight basis). Metal

Shrimps 89 ± 1.6 1520 ± 43 54 ± 1.4 107 ± 2.6

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Lizardfish 78 ± 1.5 757 ± 22 85 ± 2.1 93 ± 2.4

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Pb (ng/g) Cu (ng/g) Cd (ng/g) Co (ng/g)

Biota Prawn 103 ± 2.6 3680 ± 105 66 ± 1.6 184 ± 3.5

Crab 170 ± 3.8 6540 ± 212 101 ± 2.5 307 ± 5.7

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3.4. Intake, hazard quotient and hazard index calculation

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Intake of trace metals (Pb, Cu, Cd and Co) was calculated through the consumption of the edible part of different types of studied biota and is represented in Table 5. It is observed that intake of Pb, Cu, Cd and Co due to consumption of biota collected across Thane Creek area, Mumbai, India are much lower than the reference dose values prescribed by international agencies like USEPA-IRIS, 2007 [31] and Ontario Ministry of the Environment and Energy, 2001 [32]. Table 5 Intake (mg/kg/d) and reference dose (mg/kg/d) of trace metals through consumption of biota. Metal Pb Cu Cd Co

Lizardfish 2.4E-06 2.4E-05 0.27E-05 2.9E-06

Intake (mg/kg/d) Shrimps Prawn 2.8E-06 3.1E-06 4.8E-05 11.5E-05 0.17E-05 0.21E-05 3.3E-06 5.8E-06

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Reference Dose (mg/kg/d) Crab 5.3E-06 20.5E-05 0.32E-05 9.6E-06

0.004 0.04 0.001 0.06

[31] [31] [31] [32]

Journal Pre-proof HQ and HI are calculated considering 50th and 95th percentile and are represented in Table 6 to understand the health hazard in human beings. Although bioavailability of Cd was higher in the sediment samples, but HQ did not exceed the hazard limit. The metal concentrations in biota showed that steady consumption of biota found in this study is not hazardous. For all cases, HQ ≤ 1 and HI ≤ 1 indicate non-hazardous nature of the trace metals (Pb, Cu, Cd and Co) in the study area. Table 6 Hazard Quotient (HQ) and Hazard Index (HI) of trace metals in biota samples.

Prawn 80E-05 288E-05 206E-05 9.6E-05 583E-05

Crab 133E-05 512E-05 315E-05 16E-05 975E-05

75E-05 203E-05 217E-05 7.6E-05 487E-05

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Shrimps 69E-05 119E-05 167E-05 5.6E-05 361E-05

HQ (95th Percentile) 133E-05 512E-05 315E-05 16E-05 975E-05

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Lizardfish 61E-05 59E-05 267E-05 4.8E-05 391E-05

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Pb Cu Cd Co HI

HQ (50th Percentile)

Hazard Quotient (HQ)

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The present study investigated the Pb, Cu, Cd and Co binding behaviour in sediment samples and their distribution in biota samples collected across Thane Creek area, Mumbai India. Sequential extraction procedure revealed that Pb, Cu, Cd and Co are mainly associated with residual fraction indicating their geological origin. The bioavailable fraction of Cd was found to be higher compared to other studied metals. This was further supported by the trace metals concentrations data in the edible part of the biota samples. The concentration of Cd was observed higher in the aquatic biota (lizardfish) compared to benthic biota (shrimps and prawn) maybe because of higher bioavailable fraction of Cd. Although it was observed that bioavailability of Cd was higher in the sediment samples but, the concentration is not sufficient to pollute Thane creek. This is supported by the trace metals concentrations in biota samples. Trace metals concentration in biota showed that steady consumption of biota found in this study is not hazardous. It can be inferred that consumption of fish or biota as a whole as such is not hazardous from the given location for the reported trace metals. Results suggest that the risks to human beings from the consumption of biota from the study area are low and within safe limits. Conflict of interest On behalf of all authors, the corresponding author states that there is no conflict of interest. References 1. E.D. Passos, J.C. Alves, I.S. dos Santos, J.D.H. Alves, C.A.B. Garcia, A.C.S. Costa, Assessment of trace metals contamination in estuarine sediments using a sequential extraction technique and principal component analysis, Microchem. J. 96 (2010) 50–57. 2. E.P. Nobi, E. Dilipan, T. Thangaradjou, K. Sivakumar, L. Kannan, Geochemical and geostatistical assessment of heavy metal concentration in the sediments of different coastal ecosystems of Andaman Islands, India, Estuar. Coast. Shelf Sci. 87 (2010) 253–264. 13

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20. P.U. Singare, S.S. Bhattacharjee, R.S. Lokhande, Analysis of the heavy metal pollutants in sediment samples collected from Thane Creek of Maharashtra, India, Int. J. Sustainable Society 5(3) (2013) 296-308. 21. S. Maity, S.K. Sahu, G.G. Pandit, Determination of Traces of Pb, Cu and Cd in Seawater around Thane Creek by Anodic Stripping Voltammetry Method, Bull. Environ. Contam. Toxicol. 98 (2017a) 534-538. 22. S. Maity, Studies on transfer factors of trace metals in marine ecosystem, 2017b; PhD Thesis. 23. A. Filgueiras, I. Lavilla, C. Bendicho, Comparison of the standard SM&T sequential extraction method with small-scale ultrasound-assisted single extractions for metal partitioning in sediments, Anal. and Bioanal. Chem. 374(1) (2002b) 103–108. 24. S. Maity, S.K. Sahu, G.G. Pandit, Determination of Heavy Metals and Their Distribution in Different Size Fractionated Sediment Samples Using Different Analytical Techniques, Soil and Sediment Contam. 25(3) (2016) 332-345. 25. L. Perin, L. Craboledda, M. Lucchese, R. Cirillo, L. Dotta, M.L. Zanette, A.A. Orio, Heavy metal speciation in the sediments of Northern Adriatic Sea- a new approach for environmental toxicity determination, in: T.D. Lekkas (Ed.), Heavy Metal in the Environ, 2 (1985) 454–456. 26. ICMR, 1986, Studies on Preschool Children, ICMR Technical Report, Series No. 26, New Delhi. 27. K.D. Bastami, Md.R. Neyestani, M. Esmaeilzadeh, S. Haghparast, C. Alavi, S. Fathi, N. Shahram, E.S. Ali, R. Parhizgar, Geochemical speciation, bioavailability and source identification of selected metals in surface sediments of the Southern Caspian Sea, Mar. Poll. Bul. 114(2) (2016) 1014-1023. 28. H.Y. Zhou, R.Y.H. Cheung, K.M. Chan, M.H. Wong, Metal concentrations in sediments and Tilapia collected from inland waters of Hong Kong, Water Res. 32 (1998) 33313340. 29. C. Kabala, B.R. Singh, Fractionation and Mobility of Copper, Lead, and Zinc in

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Soil Profiles in the Vicinity of a Copper Smelter, J. Environ. Qual. 30 (2001) 485492.

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30. US-EPA, Framework for Metals Risk Assessment, Office of the Science Advisor, Risk Assessment Forum, Washington, DC, (2007) EPA 120/R-07/001. 31. USEPA, Integrated Risk Information System (IRIS) – Database. Philadelphia; Washington, DC (2007). 32. Ontario Ministry of the Environment and Energy, 2001. Appendix VI, Toxicological profiles of the metals of concern for human health. Phase II Moria River impacts of the former Deloro Mine site on the Moria River system. The Deloro Mine Site/Moria River Publication. Technical Studies and Reports Catalogue, Government of Ontario, Canada.

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CRediT author statement Sukanta Maity: Conceptualization, Methodology, Writing- Original draft preparation; Sandeep Police: Sample preparation and analysis, data interpretation; S. K. Sahu (Sanjay Kumar Sahu): Supervision; A. Vinod Kumar: Reviewing and Editing.

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Pb, Cu, Cd and Co were found to be mainly associated with residual fraction in the sequential extraction procedure indicating mostly geological origin.

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Bioavailable fraction of Cd was found to be higher compared to other studied metals and further confirmed

in biota results.

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The trace metals in biota showed that steady consumption of biota found in this study is not hazardous.

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