Project Report Submitted to Mangrove Cell, Maharashtra & GIZ, Mumbai

Carrying out Ecotoxicology of Fishes, Crabs and Bivalves at Thane Creek

Project report

submitted to

Mangrove Cell, Maharashtra & GIZ, Mumbai Office.

Sálim Ali Centre for Ornithology and Natural History (SACON) Anaikatty (PO), Coimbatore - 641108, Tamil Nadu

In collaboration with B.N. Bandodkar College of Science, Thane

Carrying out Ecotoxicology of Fishes, Crabs and Bivalves at Thane Creek

Project Report

Project Investigator Dr. Goldin Quadros

Co-Investigators Dr. P.A. Azeez, Dr. Mahendiran Mylswamy, Dr. Manchi Shirish S.

In Collaboration With Prof. Dr. R.P. Athalye B.N. Bandodkar College of Science, Thane

Research Team Mr. Siddhesh Bhave, Ms. Sonia Benjamin, Ms. Janice Vaz, Mr. Amol Tripathi, Mr. Prathamesh Gujarpadhaye.

Sálim Ali Centre for Ornithology and Natural History (SACON) Anaikatty (PO), Coimbatore - 641108, Tamil Nadu

2016

Acknowledgement

At the outset we would like to thank Mr. N Vasudevan, IFS, CCF, Mangrove cell, Maharashtra for sanctioning the project to conduct “Carrying out Ecotoxicology of Fishes, Crabs and Bivalves at Thane Creek”. This unique ecosystem, one of the largest creek from Asia is also known for its pollution and the industrial belt as well as the urban settings it is surrounded with. Here, we also take the opportunity to thank all the officials from the Mangrove Cell (Maharashtra), and Ms. Meghna Davar Lagate, Mr. Bhaskar Paul, Mr. P Vaidya and Dr. Manas Manjrekar from the GIZ Mumbai office for extending their timely help during the work. The present study involved interactions with a number of research institutions, educational institutions, NGO’s and community, all of whom were cooperative in sharing information and helped us. On the field we were immensley helped by Mr. Pravin Koli and his family who always removed time for the study. Our collaborative institution namely V.P.M’s B.N.Bandodkar College of Science, Thane has always helped right from the beginning of the project. The Laboratory space, the administrative and logistic support helped in completing the taks at hand. We also thank Drs. M.U.Borkar, N.N. Patil, S.D. Rathod and P.N. Kurve for their help in the laboratory procedures. This was mainly facilitated by the diligent efforts of the Principal Dr. M.K.Pejaver and her team from the office and Zoology department. Lastly we are grateful to the Director, SACON Dr. K Sankar for permitting us to undertake the short term project and facilitating our field and report writing work. We also thank the administrative and the finance department for coordination during field work. Finally, we take this opportunity and acknowledge with gratitude the faculty, support staff and researchers from SACON for their interest in our work and the necessary encouragement. It is highly appreciated.

Goldin Quadros P.A.Azeez R.P.Athalye Shrish S. Manchi Mahendiran Mylswamy Siddhesh D Bhave Sonia Benjamin Janice Vaz Amol Tripathi Prathamesh Gujarpadhaye

Executive Summary Thane Creek (TC), which is adjacent to Mumbai harbour bay, lies between latitude (19.5°N- 19°N) and longitude (72.5°E-73°E). It is a triangular mass of brackish water which widens out and opens to the Arabian Sea in the South. The creek is narrow at the Northern end, where it is fed partially by river Ulhas. Along the east and west sides of the creek, many industrial units have come up. The GoI-GIZ-CMPA Maharashtra Project intends to improve the protection of biodiversity by promoting participatory approaches to the conservation and management of coastal and marine protected areas (CMPA), and supporting the creation of new protected areas in the future. By involving stakeholders at local, state and national levels, it is expected to make a significant contribution to the conservation of areas rich in biodiversity, without compromising the resource use and livelihood options of the local population. The objective of this study is to assess the impact of pollution on the biodiversity and bio resources of Thane creek due to pollution and on the communities dependent on the ecosystem for their livelihoods. To achieve the objective we undertook the estimation of pesticide and heavymetals from different biotic and abiotic components of the creek. The samples for Heavy metals were processed in the laboratory of B.N. Bandodkar College of Science, Thane and the analysis was undertaken at SAIF, IIT Powai, Mumbai. Whereas the Pesticides were processed and analysed at the Wool Research Institution, Govt. Of India Laboratory, Thane. Based on our secondary literature we assessed the Organochlorine pesticides like Alpha BHC (alpha HCH), Gamma BHC, Beta BHC, Delta BHC, Heptachlor, Aldrin, Dieldrin, Endrin, Endosulphan, DDE, DDT, Methoxychlor. However all these chemicals did appear in the graph but were below the detection limits of 0.500 mg/gm , hence have not been elaborated further. The Heavy metals estimated include Cd, Co, Cr, Cu, Fe, Ni, Pb, Zn, As and Hg in all the biotic and abiotic components. Cadmium a toxic element known to affect kidney and bones was below the detection levels in water and sediment but was reported from the benthos and fish samples and varied between 0.0012 to 0.00412 mg/gm. Cobalt known to adversely affect neuromuscular transmission was reported in all the biotic and abiotic components studied and varied between 0.001 to 0.0545 mg/gm. Cromium damages the liver, kidney and blood cells causing liver, renal failure, in the present study varied between 0.0006 to 3.74 mg/gm in the benthic organisms and fish while in water and soil it varied between 0.0031 to 10.38 mg/l. Copper is an essential trace nutrient that is required in small amounts which can be toxic when in large quantities. In the present study the concentration of Copper varied between 0.01 to 1.79 mg/gm in sediment and benthos while in water it varied between 0.34 to 46.69 mg/l. The iron requirement in humans varies with age, however an overload of the element can cause disorders such as 'hemochromatosis' damage to heart, liver etc. In the creel iron content varied from 0.34 to 49.85 mg/gm in the sediment, benthos and fish while the water showed values between 2.04 to 485 mg/l. Nickel is a wide spread metal and nutritionally essential trace metal. However excess or deficiency can cause toxicity. Thane creek had marginal variations of Nickel between 0.0005 to 0.11 mg/gm in the sediment, benthos and fish while the water levels varied between 0.20 to 0.83 mg/l. Lead is a poisonous metal that can damage the nervous connections and cause blood and brain disorder. In Thane creek the concentration varied between 0.0007 to 0.504 mg/gm in the faunal components while the water showed fluctuations between 0.19 to 3.13 gm/l. Zinc is a most important trace metal for a number of physiological functions in humans. In marine

ii organisms it is readily bioaccumulated and can pose a threat to both fish and birds. In our study we observed the zinc values between 0.045 to 1.33 mg/gm in sediment and the faunal groups while in water it varied between 0.35 to 48.34 mg/L. Arsenic is a widely distributed mineral in nature and is both toxic as well as have therapeutic value. In the creek the values were very low ranging between 0.0009 to 0.012 mg/gm in the sediment and faunal groups and 0.11 to 0.34 in the water. Mercury is a metal of major concern the world over was also found in thane creek in significant amounts in all the abiotic and biotic components varying between 0.0007 to 0.116 mg/gm in sediment and faunal groups and 0.21 to 0.39 mg/l in water. Further what was interesting was the occurrence of all the metals in the varying concentrations in the Feathers of Birds including that of Mercury and Arsenic indicating a cause for concern about the Flamingo sanctuary. The metals studied were all above the National standards set for marine waters as per the Environment (Protection) Rules, 1986. The status of the creek from the toxicological point of view indicates detrimental conditions that can have long term effects on the local community also affecting their livelihood.

iii

Contents

S.No. Topic Pg. No.

Acknowledgement i Executive summary ii 1. Introduction 01. 2. Objectives 02. 3. Area of Study 02. 4. Methodology 03. 5. Results and Discussion 07. Pesticides 07. Heavy Metals 07. 6. References 25.

Citation: Goldin Quadros, P.A.Azeez, R.P.Athalye,, Shrish S. Manchi, Mahendiran Mylswamy, Siddhesh D Bhave, Sonia Benjamin, Janice Vaz, Amol Tripathi, Prathamesh Gujarpadhaye. 2016. Ecotoxicology of Fishes, Crabs and Bivalves at Thane Creek. Project report submitted to Mangrove Cell, Maharashtra & GIZ, Mumbai Office by Sálim Ali Centre for Ornithology and Natural History (SACON) and B.N. Bandodkar College of Science, Thane. pp 25 .

Introduction Estuaries are areas of high productivity, crucial to the life processes of many fish, invertebrates, and birds for example, and the sustainability of estuarine biodiversity is vital to the ecological and economic health of coastal regions. On the other hand, estuarine ecosystems are exposed to toxic anthropogenic effluents transported by rivers from remote and nearby conurbations and industrial and agricultural concerns. It is important, therefore, to have techniques that enable society to assess the degrees of exposure of estuaries to anthropogenic toxic contamination and the significance of such exposure to the ecology of the biota living there, especially the biota of commercial significance.

Thane Creek connected with the Ulhas River receives discharge from many industries and is an important part of Mumbai's environment, and study on metal and the pesticide residues in the ecosystem components of the creek can be useful as an indicator of pollution.

Pesticides and other contaminants including the heavy metals that get into the natural environment can affect plants and animals. Heavy metals and pesticides may directly affect organisms far from the site of application or release. Such pollutants that are bound to soil particles may be carried into streams with runoff. While heavy metals are recalcitrant, some pesticides last long in the environment, and may pose risks to living things many years after they were last released. Insecticides such as DDT, chlordane, and dieldrin don’t break down easily, and they are still found in soil, plants, and animals. Ecotoxicological research is important as it looks at the impacts of contaminants on individuals, populations, natural communities, and ecosystems.

While, in natural aquatic ecosystems, heavy metals occur in low concentrations, in recent times, however, metal contamination in excess of natural loads has become a problem of increasing concern. This situation has arisen because of rapid growth of population, increased urbanization and exploitation of natural resources, extension of irrigation and other modern agricultural practices as well as lax implementation of environmental regulations.

The GoI-GIZ-CMPA Maharashtra Project intends to improve the protection of biodiversity by promoting participatory approaches to conservation and management of coastal and marine protected areas (CMPA), and supporting creation of new protected areas in the future. By involving stakeholders at local, state and national levels, it is expected to make a significant contribution to conservation of areas rich in biodiversity, without compromising the resource use and livelihood options of the local people. The overall objective of the project is ‘to contribute to the improvement of the conservation and sustainable use of biodiversity in the pilot protected areas, while taking into consideration the economic circumstances of the local population’.

Thane Creek is one of the sites of the GoI-GIZ-CMPA Maharashtra project. Originating at its northern extremity from the Ulhas River, it extends over a distance of 26 km opening at the Southwest in Mumbai’s Harbor. It is a triangular mass of brackish water which widens out and opens to the Arabian Sea in the South. Along both sides of the creek, many industrial units have come up. Thane creek is the eventual recipient of all the liquid discharges from those industries.

The discharges into the creek on its Western side are dominated by sewerage from Mumbai city and effluents from the industrial complexes. The Thane creek is one of the biggest natural creeks in India and it is one at the top of the most polluted water bodies in the country.

Despite the pressures of discharge of domestic sewage and industrial effluents, Thane creek supports a rich diversity of flora and fauna. As a first step in the drive towards developing a comprehensive plan to address the pollution at Thane Creek, the project intends to explore the level of pollutants in the Creek and their bio-magnification through the food chain which poses serious health hazards in humans.

Objectives

The objective of this study is to assess the impact of pollution on the biodiversity and bio resources of Thane creek due to pollution and on the communities dependent on the ecosystem for their livelihoods.

Area of Study Thane Creek (TC), which is adjacent to Mumbai harbour bay, lies between latitude (19.5°N- 19°N) and longitude (72.5°E-73°E). It is a triangular mass of brackish water which widens out and opens to the Arabian Sea in the South. The creek is narrow at the northern end, where it is fed partially by river Ulhas. Along the east and west sides of the creek, many industrial units have come up and the creek is the immediate recipient of all the liquid discharges from these industries. The discharges into the creek on its western side are dominated by Mumbai city sewerage and effluents from the industrial complexes, including the textile mills of South and Central Mumbai, the petrochemical, fertilizer and thermal plants at Chembur and the pharmaceutical and chemical complexes at Vikhroli, Bhandup and Mulund. The Trans-Thane Creek Industrial Area was developed as a chemical zone by the Maharashtra Industrial Development Corporation. The area houses a number of major, medium and small scale industrial units largely involved in the manufacture, storage and use of chemicals, petrochemicals, pharmaceuticals and fine chemical products, pesticide formulation, etc. Of the 1800 odd industries registered in the area, nearly 50 could be termed as major and the rest as small and medium scale. The effluent discharges both treated and untreated are let into the creek.

The samples for the study have been collected from the Thane creek including the Flamingo sanctuary area (Fig. 1 & 2) during November 2015 to March 2016.

Fig 1: The location of Thane creek in Mumbai

Methodology A preliminary literature review has been undertaken to decide the eco-toxicological parameters to be assessed. We have observed that the creek has been assessed for heavy metal pollution since 1970’s; however, the studies on the pesticides have been undertaken sporadically since 1990’s. The pesticides estimated include the DDT and HCH. The heavy metals frequently assessed over the years include Cr, Co, Cd, Mn, Zn, Pb, and Fe.

For the present study the creek was visited several times to collect the samples of soil, water, benthos, fish and fallen bird feathers. As per our proposal we had planned to divide the creek into five zones based on the salinity; however the salinity did not vary much during the spring and neap tides nor during the high and low tide. This indicates that there is either reduced tidal influence in the creek or high release of effluent load into the creek. Hence, to assess the ecotoxicological aspects multiple sampling points were selected based on point and non-point sources and divided into eight zones and the samples were along the Creek for further analysis (Fig 2).

S.No. Parameter Proposed activity Analysis done for 1 Water during High tide and The creek will be sub divided The creek is divided into Low tide of the lunar phase into five zones and the eight zones and 16 samples will be collected as samples are processed the water is dynamic and for estimation heavy flowing. Hence a total 20 metals while eight for samples will be estimated for pesticides eco-toxicants. 2 Sediment samples from the Based on the length of the 24 samples are processed three tidal Zones creek a minimum of 10 for the estimation of sampling stations will be heavy metals while eight determined and a minimum of for pesticide analysis 30 samples will be estimated over eight sampling for analysis stations 3 Benthic organisms from The benthic organisms The benthic organisms the intertidal region collected will be sorted into a have been divided into collected and sorted as per minimum of dominant six five groups (sea the groups, wherever groups for the analysis. This anemones, bivalves, possible the taxa will be will include a maximum of 50 gastropods, annelid sorted up to the generic samples. polychaeta, crustacean level and barnacles). From these groups 48 samples were analyzed for heavy metals and 6 for pesticides 4 Bivalves, Fish and Crabs The edible bivalves, fish and We have documented 14 crabs will be purchased from species of finfish and the local fishers from the five crustacean species and zones demarcated for water two edible bivalve sampling. A probable total of species. However, we 20 species will be analyzed for could procure substantial accumulation of pollutants in quantities of only one different tissues like muscle, species of bivalve liver, digestive system and species, five species of exoskeleton. fin fish and one species

of edible crab. All of these seven species are processed and estimated for heavy metals from muscle, liver and exoskeleton while the entire animal (Five species) is analyzed for pesticides 5. Fallen feathers of birds Since procuring permissions We could gather feathers wherever available, for bird trapping is a long of only three species of especially of resident process we will collect the birds i.e. Flamingos, waders and flamingoes fallen feathers of birds from Gulls and Black kite. from the intertidal region the intertidal region and While we could not and mangroves mangroves. The feathers will collect the feathers of be identified for the bird other species in species and the pollutants will quantities enough for be estimated. We plan to estimation, these three analyze a minimum of ten bird are processed for heavy species. metal and two for pesticide residues

Fig. 2: Sampling locations along the Thane creek

The samples for estimation of heavy metals were pre-treated using concentrated Nitric acid and Perchloric acid and digested. The final volume was made to 50 ml and filtered using Whatman paper to remove suspended substances. The analysis was carried using Inductively Coupled Plasma - Atomic Emission Spectrometer at SAIF (Sophisticated Analytical Instrument Facility) at IIT, Powai, Mumbai. Initially the metals and elements present in the samples were detected; of them, those that were occurring in significant quantity and were important to estimate were further analyzed quantitatively.

The Pesticides were analysed at Wool Research Association (Linked to Ministry of Textiles, Thane, Government of India). The samples for the estimation were handed over to the WRA for the determination of Organochlorine pesticides.

Results and Discussions We have conducted a preliminary scan for deciding the pesticides and heavy metals to be assessed. The pesticides that signs of their presence in the scan included the BHC, Aldrin, Endrin, DDT and DDE, whereas the heavy metals analysed include Cd, Cr, Zn, Cu, Pb, Fe and As seen in detectable quantities. The available literature indicates that Thane creek has been estimated for pesticides from water and sediment only. The present study will be the first one covering the broad food chain, probably impacting human wellbeing.

Pesticides The pesticides that we selected for estimation are Alpha BHC (alpha HCH), Gamma BHC, Beta BHC, Delta BHC, Heptachlor, Aldrin, Dieldrin, Endrin, Endosulphan, DDE, DDT and Methoxychlor.

These pesticides are known to affect man in several ways through regular and long term contact or accidental consumption. Some of the symptoms from the intoxication may include headache, dizziness, nausea, general malaise and vomiting, followed by muscle twitching, myoclonic jerks, and convulsions. Occupational exposure to Aldrin, in conjunction with Dieldrin and Endrin, has been associated with a significant increase in liver and biliary cancer. The International Agency for Research on Cancer (IARC) has classified HCH (all isomers) as possibly carcinogenic to humans.

There is some evidence to suggest that DDT may be suppressive to the immune system, possibly by depressing humoral immune responses. Perinatal administration of weakly estrogenic pesticides such as DDT produces oestrogen-like alterations of reproductive development, and there is also limited data that suggest a possible association between organochlorines, such as DDT and its metabolite DDE, and the risks of breast cancer. Endosulfan affects the central nervous system, curtailing normal neural function. Hyperactivity, nausea, dizziness, headache, or convulsions have been observed in adults exposed to high doses. Severe poisoning may result in death.

The study during 2014 for pesticides from Thane creek water and sediment gives the following average values. α- HCH – 2.87 ng/g; β- HCH – 1.006 ng/g; γ- HCH – 4.74 ng/g; T-HCH – 8.63 ng/g; DDE – 1.52 ng/g; DDD – 0.29 ng/g; DDT – 2.58 ng/g; T-DDT – 4.4 ng/gm. During the present study although we did receive spectra indicating the presence of several pesticides in the biotic and abiotic components they were all below the detection limits of 0.500 ppm possible at the WRA. Hence they are not elaborated further here. However we do not rule out their occurrence in minute quantities, which may have impact on long-term exposure.

Heavy Metals The heavy metals that we have processed for analysis are Cd, Co, Cr, Cu, Fe, Ni, Pb, Zn, As and Hg. These metals have been frequently assessed for different components from Thane creek and will be useful in understanding the changes in accumulation in a long-term perspective. Studies during 2013 for heavy metals from sediment of Thane creek gives the following ranges: As – 140 -197 ug/g, Ni- 60 -80 ug/g, Cd – 53-87 ug/g, Zn – 165 – 200 ug/g, Cu – 77 - 113 ug/g and Fe – 5.3 – 5.95 ug/g. (Singare, et al. 2013; Tiwari et al. 2013; Maity et al, 2014, 2015, 2016;

Pandit et al 2014 and Sahu et al 2014) The results we have obtained for the metals analysed are given below.

Cadmium (Cd) Cadmium is produced mainly as a by-product of mining, smelting and refining of zinc and, to a lesser degree, as a by-product of lead and copper manufacturing. Most of cadmium produced is used in the production of nickel-cadmium batteries. Other major uses of refined cadmium are: pigments for plastics, ceramics and enamels; stabilizers for plastics; plating on iron and steel; and as an element of some lead, copper and tin alloys.

Cadmium is a toxic element that has no reported essential role in human body or biological systems in higher species; it mainly affects kidneys and bones, and also a carcinogen by inhalation. Cadmium can accumulate in liver, kidneys and bones, which may serve as sources of exposure later in life. In the environment, cadmium is toxic to plants, animals and micro- organisms. Being a chemical element, cadmium is persistent and cannot be broken down into less toxic substances in the environment.

During the present study Cd was mostly below the detection levels of 0.0001mg/L. It was not recorded from the water, sediment, mangroves and plankton samples. However, Cd was recorded from invertebrates such as a polycheate species (0.0012 to 0.00412 mg/gm) from the riverine end as wells within the sanctuary near the Airoli region, the muscle of gastropod Melampus ceylonicus (0.0035 mg/gm) and Melampus sp (0.0017 mg/gm) as well as the flesh of edible bivalve Arca sp. (0.0032 mg/gm). Among vertebrates, Cd was recorded from the liver of fish Mystus gulio (0.0026 mg/gm), and in trace amounts from the feather samples of Flamingo (0.0006 mg/gm) and Gull (0.0005mg/gm). Cadmium has in fact been shown to play a metabolic role in carbonic anhydrase in certain oceanic diatoms (Cullen et al., 1999). Nevertheless, it is still considered non-essential for other organisms including aquatic invertebrates. As per the Indian Environment (Protection) Rules, 1986 Cd should not exceed 2.0 mg/l along the marine waters. The values during the present study were well within the limits, however,the documentation of Cd in different faunal groups indicates its concern in the food web including humans.

Cobalt (Co) The occurrence of cobalt in the earth's surface varies greatly. This element does not exist in its native form and is encountered in elemental form only in meteorites. Cobalt is most often found in the form of arsenides and sulphides. The major source of cobalt pollution (apart from industrial waste) is the burning of cobalt. Industrial exposure to Co was observed to cause an increase in the accumulation and concentration of this metal in humans, eliciting associated adverse effects on neuromuscular transmission (Kim et al, 2006) and neurological status (Matés, 2010).

Humans may ingest up to several milligrams of cobalt per day in their diet and can even tolerate higher doses of Co during clinical treatment for anaemia without adverse effects to the heart. However, the ingestion of relatively high levels of Co from inorganic Co salts with large amounts of alcohol has been reported to pose health risk to humans.

During the present study the Co was recorded from some components of the ecosystem. In water it was found only along the east bank near Airoli to Digha region. It was marginally (varying between 0.0008 to 0.0053 mg/gm) present in plankton (Fig. 3). However, in the sediments Co was present throughout the creek and it varied between 0.0103 and 0.0545 mg/gm (Fig. 4). The macrobenthos (Fig.5 to 7) showed varying levels of Co concentration (0.0011 to 0.00427 mg/gm) in different taxa except crustaceans and bivalves. In the mangrove species, Avicennia marina acutisima, it was observed in high concentration in Vashi samples along the east bank while the west bank had low concentrations (Fig. 8). In the fish species Co was recorded in varying levels in the scales, liver and muscle tissue (Fig. 9) and the concentrations varied between 0.005 mg/gm and 0.0135 mg/gm, with high concentration of muscle of fish Mystus gulio, Mugil cephalus, Therapon jarbua and Arius sp. Cobalt was present in the feathers (varying between 0.0008 to 0.0017 mg/gm) of all the three species of birds (Fig. 10). Indian does not have any set standard value for Cobalt, however as per the US limits the standard value to 0.0025g/l.

0.25 Fig. 3: Comparison of different metals in the plankton Fig. 4: Concentration of Cobalt along the from Thane creek 0.06 different tidal levels in the sediment from the creek 0.2 Phytoplankton Low tide mark Zooplankton 0.05 Mid tide mark 0.15 0.04 High tide mark

0.03 mg/gm 0.1

Co mg/gmCo 0.02 0.05 0.01

0 0 Cd Co Cr Cu Ni Pb Zn As Hg West - 1 3 5 7 East -2 4 6 8 Heavy Metals Sampling locations Fig.5: Concentration of Cobalt in the Gastropods along 0.0050 Fig. 6: Concentration of Cobalt in the Barnacles the West Bank (WB) and East Bank (EB) of Thane creek 0.0045 of Thane creek 0.0040 0.0035 0.0040 0.0030 0.0025 0.0020 0.0030

mg/gm 0.0015 0.0010

0.0005 mg/gm 0.0020 0.0000 0.0010

0.0000 West bank East Bank Mangroves Sampling locations Sampling locations Fig. 7: Concentration of Cobalt in the Polychaetes along Fig.8 : Concentration of Cobalt in Avicennia marina 0.004 the West Bank (WB) and East Bank (EB) of Thane creek 0.10 acutisima along Thane creek 0.0035

0.003 0.08

0.0025 0.06 0.002

0.0015 mg/gm 0.04 mg/gm 0.001 0.02 0.0005 0 0.00 WB -1L WB-3H WB-3M WB-7H WB-7M EB-2L EB-4M EB-6H EB-8L Godrej Kanjurmarg Vashi Koparkhairane Sampling stations Sampling locations

0.016 Fig. 9: Concentration of cobalt in different species of fish. 0.014 Scales Muscle 0.012 Liver 0.01 0.008 0.006 Cobalt mg/gm Cobalt 0.004 0.002 0 Therapon jarbua Lates calcarifer Megalops Mugil sp. Arius sp. Mystus gulio Acetes prawn Arca mussel Scylla scerata cyprinoides Fish species 0.25 Fig.10: Concentration of different metals in the bird feathers collected from Thane creek Black Kite 0.2 Flamingo Gull 0.15

mg/gm 0.1

0.05

0 Cd Co Cr Cu Ni Pb Zn As Hg Heavy metals

Chromium (Cr) Chromium is a heavy metal with toxic potential in marine environment. Chromium alloy and metal producing industry, cooling towers, industrial discharges into the water (electroplating and metal finishing industries being the major sources) and runoff from urban areas are the principal sources. Bioaccumulation occurs mostly in marine biota that utilize gill. Chromium, however, does not appear to be accumulated at higher trophic level in the marine food web. Of all the metals, Cr has truly unique toxicological characteristics. In human, Chromium damages liver, kidney and blood cells causing liver, renal failure or haemolysis. Contact with chromium plating can cause skin ulcers (Chrome ulcers). Chromium toxic in higher levels, its trivalent form is required in trace amount for sugar and lipid metabolism. Complete removal from diet causes deficiency. High quantity is toxic and carcinogenic (especially the hexavalent Cr). Cr+6 is mutagenic especially when inhaled. Cr+6 in solution form can cause contact dermatitis. Oral +3 +6 toxicity of Cr ranges from 1.5 to 3.3 mg/kg, while for Cr is 50 to 150 mg/kg. While for total chromium the value up to 2 .0 mg/l is the standard as per the Environment (Protection) Rules of 1986.

During the present study Cr concentration in the waters varied between 0.54 and 10.38 mg/L (Fig. 11). The values were higher along the east bank compared to the west bank. Similarly, in the sediment (Fig. 12) Cr concentration varied between 0.0031 and 0.1841 mg/gm. The concentration among the benthic organisms varied between 0.0006 and 0.4172 mg/gm (Fig. 13 to18). Of the faunal group examined, the barnacles had the highest concentration followed by Polychaets, Gastropods, Bivalves and crabs.. The fish species analysed also had high concentration of chromium ranging between 0.003 and 3.74 mg/gm. (Fig. 19) with maximum concentrations seen in the fish muscle. Chromium was also recorded in low concentration in the

tissues of bivalves, crabs and shrimp. The concentration in the mangrove Avicennia marina acutisima varied between 0.046 and 0.223 mg/gm. The values were high at Vashi location followed by Godrej and Kanjurmarg (Fig. 20). The feathers of all the three species of birds have Cr ranging between 0.007 and 0.094 mg/gm (Fig. 10). Comparison of the values obtained at different levels of food chain indicates bioaccumulation and with that of the standards (2.0 mg/l Total Cr) suggests caution at consumption of some of the fish species.

Fig 11: Concentration of Chromium in the water Fig.12 : Concentration of Chromium in the sediment 12 along the West Bank (WB) and East Bank (EB) of along the west and east bank of Thane creek 0.2 Thane creek 10 Low tide mark Mid tide mark 8 0.15 High tide mark

mg/L 0.1 4 mg/gm 2 0.05 0 0 West -1 3 5 7 East -2 4 6 8 Sampling stations Sampling stations

Fig. 13: Concentration of Chromium in the Barnacles Fig.14 : Concentration of Chromium in the along Thane creek 0.05 Gastropods along (west Bank (WB) and East Bank 0.025 (EB) Thane creek 0.04 0.02 0.03 0.015 0.02 mg/gm

mg/gm 0.01 0.01 0 0.005

0 Sampling locations West bank East Bank Mangroves Sampling stations

Fig. 15: Concentration of Chromium in the Fig. 16: Concentration of Chromium in the crab 0.02 polychaetes along the West Bank (WB) and East Illyoplax gangetica along West Bank (WB) and East Bank (EB) along Thane creek 0.012 Bank (EB) of Thane creek

0.015 0.01

0.008 0.01 0.006 mg/gm mg/gm 0.005 0.004 0.002

0 0 WB -1L WB-3H WB-3M WB-7H WB-7M EB-2L EB-4M EB-6H EB-8L WB-1H WB-5H EB-2H EB-4H EB-6H Sampling locations Sampling stations

Fig. 17: Concentration of Chromium in Bivalves 0.14 Fig. 18: Concentration of heavy metals in the along the West bank(WB) and East Bank (EB) from coelentrates from Thane creek 0.015 0.12 Thane creek Seaanemone-West bank 0.1 Seaanemone-East Bank 0.01 0.08 0.06 mg/gm mg/gm 0.005 0.04 0.02 0 0 Cd Co Cr Cu Ni Pb Zn As Hg WB-5L WB-7H EB-4L EB-8H Sampling stations Heavy Metals

Fig.19 : Concentration of Chromium in different 4.00 Fig. 20: Concentration of Chromium in Avicennia species of fish. 3.50 Scales marina acutisima along Thane creek Muscle 0.2500 3.00 Liver 2.50 0.2000 2.00

mg/gm 1.50 0.1500 1.00 0.50 mg/gm 0.1000 0.00 0.0500

0.0000 Godrej Kanjurmarg Vashi Koparkhairane Sampling stations Sampling locations

Copper (Cu)

Copper is an essential trace nutrient that is required in small amounts (5-20 micrograms per gram (µg/g)) by humans, other mammals, fish and shellfish for carbohydrate metabolism and functioning of more than 30 enzymes. It is also needed for formation of haemoglobin and haemocyanin, the oxygen-transporting pigments in the blood of vertebrates and shellfish respectively. Though toxic at higher levels, Cu deficiency can cause anaemia like symptoms, bone abnormalities, hypo-pigmentation, impaired growth, and increased incidence of infections, abnormalities in glucose and cholesterol metabolisms. Cu concentrations that exceed 20 µg/g can be toxic as explained by Heike Bradl (2005) and Wright and Welbourn (2002). Accumulation of Cu causes Wilson’s disease. Cu has antimicrobial property and can kill Pseudomonas, E. coli and other bacteria. Ingestion of too much Cu due to food cooked in copper-cookware can cause health problems, such as vomiting, jaundice, cirrhosis, Wilson’s disease, Alzheimer’s disease (30 mg / kg dose is toxic when consumed).

Copper is moderately soluble in water and binds easily to sediments and organic matter. In the present study the values in water ranged from 0.34 to 46.69 mg/gm. The values were higher along the east bank compared to the west bank. However the sediments showed higher concentration along the west bank, ranging from 0.0505 to 0.3152 mg/gm. The zooplankton showed high accumulation as compared to phytoplankton. In the macrobenthic organisms the concentration of Cu varied between 0.0181 and 1.79325 mg/gm and had high concentration along the east bank except for the sea anemones that had high values along the west bank (Fig. 18, 21-27). Among the fish species Cu was recorded in the scales, liver and muscle of all species as well as the exoskeleton of crab Scylla serrata with highest concentration in the fish Mystus gulio

(Fig. 28). The concentration was also exceptionally high in the mangrove at Vashi (Fig. 29). The bird feathers also showed high concentration with the maximum recorded from the Gull followed by Flamingo and Black Kite (Fig. 10.) The Environment (Protection) Rules, 1986 states values of Cu up to 3 mg/l as tolerable in marine ecosystems. In the present study the values were all within the limit in the faunal component although there is a pattern of bioaccumulation.

100 Fig. 22: Concentration of Copper in the sediments Fig.21: Concentration of Copper in the water of along the different tidal levels of Thane creek Thane creek 0.35 Low tide mark 80 0.3 Mid tide mark 60 0.25 High tide mark 0.2 mg/L 40 0.15 mg/gm 20 0.1 0.05 0 0 West - 1 3 5 7 East -2 4 6 8 Sampling locations sampling locations

Fig.23 : Concentration of Copper in The Barnacles Fig.24: Concentration of Copper in the gastropods along the Thane creek 0.4 found along the West Bank (WB) and East Bank 0.35 (EB) of Thane creek 0.35 0.3 0.3 0.25 0.25 0.2 0.2

mg/gm 0.15 0.15 mg/gm 0.1 0.1 0.05 0.05 0 0 West bank East Bank Mangroves Sampling locations Sampling locations

2 Fig.25: Concentration of Copper in the Polychaetes Fig.26 : Concentration of Copper in the crab Illyoplax found along the West Bank(WB) and East Bank (EB) gangetica found along the West Bank (WB) and East of Thane creek 0.05 Bank (EB) of Thane creek 1.5 0.04

1 0.03 mg/gm

mg/gm 0.02 0.5 0.01

0 0 WB -1L WB-3H WB-3M WB-7H WB-7M EB-2L EB-4M EB-6H EB-8L WB-1H WB-5H EB-2H EB-4H EB-6H Sampling stations Sampling Locations

Fig.27 : Concentration of Copper in the Bivalves Fig.28 : Concentration of Copper in Avicennia marina found along the West Bank (WB) and East Bank 10.0000 acutisima along Thane creek 0.06 (EB) of Thane Creek 8.0000 0.05 6.0000 4.0000 0.04 mg/gm 2.0000 0.03

mg/gm 0.0000 0.02 0.01 0.00 WB-5L WB-7H EB-4L EB-8H Sampling Locations Sampling locations

12 Fig.29: Concentration of Copper in the fish from Thane creek Scales 10 Muscle Liver 8

6 mg/gm 4

0 Therapon jarbua Lates calcarifer Megalops cyprinoides Mugil sp. Arius sp. Mystus gulio Acetes prawn Arca mussel Scylla scerata Fish species

Iron (Fe) Iron is naturally released into the environment from weathering. However, it may also be released into the aquatic environment through human activities, such as burning coke and coal, acid mine drainage, mineral processing, sewage, iron related industries and the corrosion of iron and steel (CCREM 1987). In animals, plants and fungi, Fe is often the metal ion incorporated into the heme complex, an essential component of cytochrome proteins that mediate redox reactions, and of oxygen carrier proteins such as Haemoglobin, Myoglobin and Leghaemoglobin. Iron is an important component of many other important enzymes.

The dietary sources of Fe include red meat, beans, poultry, fish, leafy vegetables, and molasses. Iron in meat is better absorbed. The dietary supplement of iron is usually in the form of iron fumarate, iron glycinate (iron chelated with amino acid glycine because it gets better absorbed). The iron requirement varies with age. Iron should not be taken unless there is iron deficiency. If there is defect in regulation of uptake of iron, the individual may absorb more iron than needed leading to accumulation of iron. This cause, iron overload disorders such as hemochromatosis, damage to heart, liver etc. The effects include coma, liver failure, respiratory distress syndrome, metabolic acidosis etc.

Marine organisms accumulate iron; but they also rapidly excrete it in clean water conditions. Normally, tissue concentrations of iron are related to the water and sediment concentrations, but there is considerable variability. Tissue concentrations vary seasonally, being lower in winter and spring than in summer and autumn, and furthermore tissue and shell concentrations increase

with increasing salinity (Mance and Campbell 1988). The bioaccumulation of iron by marine organisms does not appear to pose a hazard to higher trophic levels.

During the present study the concentration of Fe was recorded in every component of Thane creek. In the water it varied between 2.04 and 485.04 mg/gm across the creek and was in higher concentrations along the East bank as compared to the west bank (Fig. 30). The sediments also reported Fe concentration; however it was very patchily distributed and was observed around the Bhandup to Ghatkopar and Koparkhairne to Vashi varying between 32.41 and 49.85 mg/gm. Among the plankton the zooplankton had high concentration of Fe (i.e. 13.74 mg/gm) while the phytoplankton had 1.43 mg/gm indicating bioaccumulation. The benthic organisms also showed concentrations ranging between 0.34 to 11.55 mg/gm (Fig.31 to 36). The concentration was high in crabs, bivalves and sea anemones found along the west bank, whereas the polychaetes and gastropods had higher values on the east bank. The fish showed varying levels of concentration in the muscle, liver and scales/ exoskeleton of the species examined. The Fe concentration ranged between 0.29 and 36.1 mg/gm and was found maximum in the muscle of Mystus gulio fish followed by Mugil sp. and Therapon jarbua (Fig. 37). The concentration of the metal in the mangrove species Avicennia marina acutisima at Vashi was five times higher than that recorded from Godrej mangrove area (Fig. 38). Accumulation of the metal was also seen in the feathers of Gull, Flamingo and Black Kite in descending order (Fig. 39). The Schedule IV of Environment (Protection) Rules, 1986 states values of Fe up to 3 mg/l as tolerable in marine ecosystems. The present study has several values above the accepted limit indicating detrimental status.

Fig.30: Concentration of Ferrous in the water from 600 Thane creek. Fig. 31: Concentration of Ferrous in Barnacles found in Thane creek. 500 400 15 300 10 mg/L 200 5 100 mg/gm 0 0 West bank East Bank Mangroves EBS2 EBS4 EBS6 EBS8 WBS1 WBS3 WBS5 WBS7

EBS2a EBS4a EBS6a EBS8a Sampling stations WBS1a WBS3a WBS5a WBS7a Sampling stations Fig.32: Concentration of Ferrous in the Gastropods Fig.33: Concentration of ferrous in the Polycheate found along West bank (WB) and East Bank (EB) found along West Bank (WB) and East Bank (EB) 12 12 of Thane creek of Thane creek 10 10 8 8 6 6 mg/gm mg/gm 4 4 2 2 0 0

Sampling Stations Sampling stations

Fig.34: Concentration of Ferrous in the crab Fig.35: Concentration of Ferrous in the bivalves Illyoplax gangetica found along the West Bank (WB) found along the West Bank (WB) and East Bank 1.2 and East Bank (EB) of Thane creek 4 (EB) of Thane creek. 1 0.8 3 0.6 2 mg/gm 0.4 mg/gm 0.2 1 0 0 WB-1H WB-5H EB-2H EB-4H EB-6H WB-5L WB-7H EB-4L EB-8H Sampling Stations Sampling Locations Fig. 36: Concentration of Ferrous in the Fig. 37: Concentration of Ferrous in the fish found seaanemones found along the West Bank and East 40 in Thane Creek. 4.0 Bank of the Thane creek Scales 30 Muscle 3.0 Liver 20 mg/gm 2.0 10 mg/gm

1.0 0

0.0 Seaanemone-West bank Seaanemone-East Bank Sampling Stations Fish Species Fig.38 : Concentration of Ferrous in Avicennia Fig.39: Concentration of Ferrous in the feathers of marina acutisma along Thane creek birds found in Thane Creek 300.0 3.5 250.0 3 200.0 2.5 150.0 2 mg/gm 100.0

50.0 mg/gm 1.5 0.0 1 0.5 0 Black Kite Flamingo Gull Sampling locations bird species

Nickel Nickel is a metal of widespread distribution in the environment: there are almost 100 minerals of which it is an essential constituent and which have many industrial and commercial uses. Nickel and its compounds belong to the classic noxious agents encountered in industry but are also known to affect non-occupationally exposed individuals. The general population may be exposed to nickel in the air, water and food. Inhalation is an important route of occupational exposure to nickel in relation to health risks.

Nickel is a ubiquitous trace-metal and occurs in soil, water, air, and in the biosphere. The average content in the Earth's crust is about 0.008%. Most nickel is used for the production of stainless steel and other nickel alloys with high corrosion and temperature resistance. Nickel alloys and nickel plating are used in vehicles, processing machinery, armaments, tools, electrical equipment, household appliances, and coinage. Nickel compounds are also used as catalysts, pigments, and in batteries. The primary sources of nickel emissions into the ambient air are the combustion of coal and oil for heat or power generation, the incineration of waste and sewage sludge, nickel mining and primary production, steel manufacture, electroplating, and miscellaneous sources,

such as cement manufacturing. Nickel from various industrial processes and other sources finally reach waste water. Residues from waste-water treatment are disposed of by deep well injection, ocean dumping, land treatment, and incineration (WHO 1991).

Nickel toxicity in aquatic invertebrates varies considerably according to species and abiotic factors. However, accumulation factors in different trophic levels of aquatic food chains suggest that bio-magnification of nickel along the food chain, at least in aquatic ecosystems, does not occur (WHO 1991). Nickel is a nutritionally essential trace metal for several animal species, micro-organisms and plants, and therefore either deficiency or toxicity symptoms can occur when, respectively, too little or too much Ni is taken up.

During the present study Ni was present in all components of Thane creek. Ni in water ranged between 0.20 and 0.83 mg/L (Fig. 40); the concentration showed an increasing trend towards the sea and was comparatively higher on the east bank. The sediments showed higher concentration on the west bank as compared to the east bank (Fig. 41), the values varying between 0.026 and 0.112 mg/gm. The benthic organisms followed a trend similar to the water with higher values along the east bank and increasing trend to the sea (Fig. 42 to 46). Nickel concentration, higher concentration along the east bank, was the highest in the crab Illyoplax gangetica. Fish also had Ni in the scales, liver and muscle with the highest content being in the muscle of Mugil sp. followed by Mystus gulio and Therapon jarbua (Fig 47). As was seen with the other metals the mangrove had higher content at Vashi (Fig. 48). The bird feathers too showed a Ni concentration with high values in the Gull followed by flamingo and the Black kite (Fig. 10). The level of Nickel was very low as compared to the standard limit of 5.0 mg/l suggested by the Environment (Protection) Rules of 1986.

1 Fig.40 : Concenteration of Nickel in the waters of Fig.41 : Concentration of Nickel in the sediment Thane creek along the West Bank (WB) and East Bank (EB) of 0.8 0.12 Thane creek 0.1 Low tide mark 0.6 Mid tide mark 0.08 High tide mark 0.4mg/L 0.06 mg/gm 0.2 0.04 0.02 0 0 West - 1 3 5 7 East -2 4 6 8 Sampling Stations Sampling Stations Fig.42: Concnetration of Nickel in the Barnacles Fig. 43: Concentration of Nickel inthe Gastropods found along Thane creek along the West bank (WB) and East Bank (EB) of 0.015 Thane creek. 0.01 0.01 0.005 mg/gm mg/gm 0 0.005 West bank East Bank Mangroves 0 Sampling locations 1 2 3 4 5 6 7 8 9 10 11 Sampling stations

Fig.44: Concentration of Nickel inthe Polychaetes Fig.45: Concentration of Nickel in the Crab found along the West Bank (WB) and East Bank Illyoplan gangetica found along the West Bank (WB) (EB) of Thane creek. 0.0015 and East Bank (EB) of Thane creek 0.015

0.01 0.001 mg/gm 0.005 mg/gm 0.0005

0 0 WB-1H WB-5H EB-2H EB-4H EB-6H Sampling Locations Sampling Locations Fig. 46: Concnetration of Nickel in the bivalves Fig.47 : Concentration of Nickel in Avicennia marina acutisima along Thane creek reported from Thane creek 0.2500 0.005 0.2000 0.004 0.1500 0.003 0.1000 0.002 mg/gm mg/gm 0.001 0.0500 0 0.0000 WB-5L WB-7H EB-4L EB-8H Godrej Kanjurmarg Vashi Koparkhairane Sampling Stations Sampling locations Fig.48: Concentration of Nickel in the fish found in Thane creek 0.07 0.06 Scales Muscle Liver 0.05 0.04 0.03 mg/gm 0.02 0.01 0 Therapon jarbua Lates calcarifer Megalops Mugil sp. Arius sp. Mystus gulio Acetes prawn Arca mussel Scylla scerata cyprinoides Sampling Locations

Lead (Pb) Lead is a poisonous metal that can damage nervous connections and cause blood and brain disorder. Long term exposure to lead can cause nephropathy, plumbism and colic-like abdominal pain. Lead enters body through breathing or swallowing. High lead levels in body can cause increase in B.P., damage to kidney and brain. It can cause miscarriage in pregnant women. Lead affects reproduction ability of women. Lead is emitted in atmosphere through various means, including fossil fuel burning, and may be inhaled or ingested after it settles down on edibles. This lead quickly gets in the blood stream and causes damage to CNS, Kidney, immune system and cardiovascular system.

In aquatic ecosystems, uptake by primary producers and consumers seems to be determined by the bioavailability of the lead. The uptake and accumulation of lead by aquatic organisms from water and sediment are influenced by various environmental factors, such as temperature, salinity, and pH, as well as humic and alginic acid content. In many organisms, it is unclear whether lead is adsorbed onto the organism or actually taken up. Consumers take up lead from their contaminated food, often to high concentrations, but without bio-magnification (WHO 1995).

For marine waters, according to the Environment (Protection) rules, 1986 2 mg/l of lead is considered as the maximum permisible limit.In Thane creek Pb was reported in water, in concentrations varying between 0.19 and 3.13 mg/L (Fig. 49). However, it was below the detection level (0.0001 mg/gm) in the sediments of the creek. Pb was not detected in the phytoplankton, while the zooplankton had a concentration of 0.007mg/gm (Fig. 3). In other components such as macrobenthos, Pb was notdetected from the crab Illyoplax gangetica but was present in the other organisms like Barnacles, Gastropods, Bivalves, Polychaetes and Sea anemones(range - 0.0007 to 0.1113 mg/gm,Fig. 50 to 53). In both water and the benthic organisms the lead showed an increasing trend towards the sea with higher values on the east bank. The mangrove species studied also had high lead concentration along the east bank compared to the west bank (Fig. 54), varying between 0.0260 and 0.263 mg/gm. All the fish species studied from Thane creek had Pb residues in its scales, liver and muscle; but the fish Mystus gulio had exceptional accumulation reaching a value of 0.504 mg/gm compared to the levels in others where the values varied between 0.0008 and 0.015 mg/gm (Fig.55).

3.5 Fig.49: Concentration of Lead in the water from Fig.50 : Concentration of Lead in the barnacles Thane creek found along Thane creek 3 0.008 2.5 0.007 2 0.006 0.005

1.5mg/L 0.004 1 mg/gm 0.003 0.5 0.002 0 0.001 0 West bank East Bank Mangroves Sampling Locations Sampling locations

Fig.51: Concentration of Lead in the Gastropods Fig.52: Concentration of Lead in the polychaetes found along the West (WB) and East (EB) banks found along the West (WB) and East (EB) banks of 0.07 of Thane creek Thane creek. 0.012 0.06 0.01 0.008 0.05 0.006 0.04

mg/gm 0.004 0.03 0.002 mg/gm 0 0.02 0.01 0 WB -1L WB-3H WB-3M WB-7H WB-7M EB-2L EB-4M EB-6H EB-8L sampling stations Sampling locations

Fig.53: Concentration of Lead in the bivalves Fig.54: Concentration of Lead in Avicennia marina acutisima along Thane creek found along the West (WB) and East (EB) banks 0.3000 of thane creek 0.2500 0.006 0.2000 0.005 0.004 0.1500 0.003 mg/gm 0.1000

0.002mg/gm 0.0500 0.001 0 0.0000 Godrej Kanjurmarg Vashi Koparkhairane WB-5L WB-7H EB-4L EB-8H Sampling locations Sampling locations 0.6 Fig. 55: Concentration of Lead in the Fish found from Thane creek Scales 0.5 Muscle Liver 0.4

0.3 mg/gm 0.2

0.1

0 Therapon Lates calcarifer Megalops Mugil sp. Arius sp. Mystus gulio Acetes prawn Arca mussel Scylla scerata jarbua cyprinoides Sampling locations

Zinc (Zn) Zinc is an essential trace element necessary for plants and animals and micro organisms. It is involved in about 100 to 300 enzymes. In proteins, Zn ions are often coordinated to amino acid side chains of aspartic acid, glutamic acid, cysteine, and histidine. About 2 - 4 gm of Zn is distributed throughout the body. Most Zn is in brain, muscles, bones Kidneys and liver, the highest concentration being in prostate and parts of the eye. Zn, rich in semen, is an important factor for development of reproductive organs. Zn plays important role in central nervous system function. It modulates brain excitability. It plays important role in synaptic vesicles (of glutamatergic neurons). Zn has an import role in learning. But it is a dark horse as it also acts as neurotoxic. Zn deficiency causes mal-absorption, chronic liver disease, chronic renal disease, sickle cell disease, diabetes and malignancy. Low Zn also causes depressed growth, Alopecia, impaired appetite, impaired host defence, reproductive and teratogenic effect.

Zinc is used in coating to protect iron and steel, in alloys for die casting, in brass, in strips for dry batteries, in roofing and in some print processes. Zinc is one of the most ubiquitous and mobile of the heavy metals and is transported in natural waters in both dissolved forms and associated with suspended particles (Mance and Yates 1984). It may enter the aquatic environment through natural or anthropogenic sources, including sewage and industrial discharges. Zinc is an essential element for many marine organisms and, as such, is readily bio-accumulated and can pose a threat to fish and birds. Hunt and Hedgecott (1992) reported the toxicity and bioaccumulation of zinc to be greater at lower salinity.

In Thane creek Zinc was recorded in higher concentrations along the west bank with values ranging between 0.35 to 48.34 mg/L (Fig. 56). A similar trend was observed in the sediments with the concentration of Zn varying between 0.045 to 0.219 mg/gm (Fig. 57). Similarly Zn showed higher concentration in Zooplankton (0.202 mg/gm) compared to Phytoplankton (0.0217 mg/gm) (Fig. 3). Among the benthic organisms Zn was not recorded from Bivalves, while in the other organisms the concentration ranged from 0.0051 to 1.3382 mg/gm (Fig. 58 to 61). Except for barnacles and sea anemones the Zn was higher along the east bank of the creek, as was observed in the Mangrove Avicennia marina acutisima (Fig. 62). The fish also showed accumulation of Zn in the scales, liver and muscles varying from 0.0488 to 0.218 mg/gm (Fig. 63); the maximum concentration was reported from the muscle of Mystus gulio fish. The bird feathers showed concentrations varying between 0.112 and 0.2102 mg/gm (Fig 10). For marine waters, according to the Environment (Protection) rules, 1986 15 mg/l of Zinc is considered as the maximum permissible limit, however in Thane creek the values are much higher indicating detrimental status.

Fig.56: Concentration of Zinc in the waters of Fig.57: Concentration of Zinc in the sediments of 100 Thane creek Thane creek 0.25 Low tide mark 80 0.2 Mid tide mark High tide mark 60 0.15

mg/L 40

mg/gm 0.1

20 0.05

0 0 West - 3 5 7 East -2 4 6 8 1 Sampling locations Sampling locations Fig.58: Concentration of Zinc in the Barnacles Fig.59: Concentration of Zinc found in Gastropods found along Thane creek 0.3 0.4 found along West (WB) and East (EB) bank of 0.35 Thane creek 0.25 0.3 0.2 0.25 0.2 0.15

mg/gm 0.15

mg/gm 0.1 0.1 0.05 0.05 0 0 West bank East Bank Mangroves Sampling stations Sampling Locations Fig.60: Concentration of Zinc in the Polychaetes Fig.61: Concentration of Zinc found in Crabs found along West (WB) and East (EB) bank of 0.06 Illyoplax gangetica along the West (WB) and East (EB) 1.6 Thane creek. banks of Thane creek 1.4 0.05 1.2 0.04 1 0.8 0.03 mg/gm

0.6 mg/gm 0.4 0.02 0.2 0.01 0 0 WB-1H WB-5H EB-2H EB-4H EB-6H Sampling Locations Sampling Locations

Fig. 62: Concentration of Zinc in Avicennia marina Fig.63: Concentration of Zinc in the fish obtained acutisima along Thane creek 10 from Thane creek 8.0000 Scales 7.0000 8 Muscle 6.0000 Liver 5.0000 6 4.0000

mg/gm 4 mg/gm 3.0000 2.0000 2 1.0000 0.0000 0

Sampling locations Sampling Locations

Arsenic (As)

Arsenic in nature is widely distributed in a number of minerals, mainly as arsenides of copper, nickel, and iron, or as arsenic sulfide or oxide. In water, As is usually found in the form of arsenate or arsenite. Methylated arsenic compounds occur naturally in the environment as a result of biological activity. The most important commercial compound, As (III) oxide, is a by- product in the smelting of copper and lead ores. Arsenic compounds are also used in wood preservatives.

Arsenic enters the marine environment from natural diffuse sources and from anthropogenic point and diffuse sources. Arsenic has been of interest as its compounds are toxic but as well they have been shown to be of therapeutic value. Because of the chemical similarity of As and phosphorus, arsenate (AsO-) may follow the same metabolic pathways in organisms as phosphorus, and interfere in phosphorus metabolism.

A range of marine organisms have been found to accumulate As from sediments and the water column, including the bivalve molluscs, the flatworm Planaria and the algae were considered to take up sorbed arsenic from suspended or surficial sediments and from dissolved arsenic from the water column. While these species appear to accumulate As to quite high levels, a large proportion may be present as arsenobetaine which is a water soluble compound that poses little hazard to the organism or its consumer (Smith and Edwards 1992). Arsenic is bio-concentrated in organisms, but is not biomagnified in food chains and so bioaccumulation is unlikely to be a problem in marine organisms.

In Thane creek, Arsenic was present in varying concentrations in water between 0.11 and 0.34 mg/L (Fig. 64). The concentration in the sediment varied between 0.0011 and 0.012 mg/gm (Fig. 65), the values were higher along the west bank. Arsenic was present only in Zooplankton (Fig. 10) and absent in phytoplankton as well as the bivalves and crabs. Among the benthic organisms it was observed only in polychaetes, gastropods and barnacles with higher concentration along the west bank (Fig. 66 to 68). The concentration was high in the liver of all the fish studied as compared to the other metals investigated. The muscles of all the fish species showed accumulation with highest values in Mystus gulio. Among the birds (Fig. 10) Arsenic was reported only in the Flamingo feathers. Although the biomagnifications was not very significant

the values obtained for water were above the permissible limits as prescribed by Environment (Protection) Rules 1986 of 0.2 mg/L

0.4 Fig.64 : Concentration of Arsenic in the waters of Fig. 65: Concentration of Arsenic found in the Thane creek 0.014 0.35 sediments of Thane creek 0.3 0.012 Low tide mark Mid tide mark 0.25 0.01 High tide mark 0.2 0.008 0.15mg/L 0.006 0.1 mg/gm 0.05 0.004 0 0.002

0 EBS2 EBS4 EBS6 EBS8 WBS1 WBS3 WBS5 WBS7 EBS2a EBS4a EBS6a EBS8a WBS1a WBS3a WBS5a WBS7a West - 1 3 5 7 East -2 4 6 8 Sampling Locations Sampling locations Fig.66: Concentration of Arsenic in the Barnacles Fig.67: Concentration of Arsenic in the Gastropods 0.003 along Thane creek found along the West (WB) and East (EB) banks of Thane creek 0.0025 0.008

0.002 0.006

0.0015 0.004 mg/gm mg/gm 0.001 0.002

0.0005 0 0 West bank East Bank Mangroves Sampling Locations Sampling locations Fig.68: Concentration of Arsenic in the Polychaetes Fig.69: Concentration of Arsenic in the fish found in 0.005 0.025 found along the West (WB) and East (EB) banks of Thane creek Thane creek Scales 0.004 0.02 Muscle 0.003 0.015

mg/gm 0.01

mg/gm 0.002 0.005 0.001 0 0

Sampling Locations Fish Species

Mercury (Hg) Mercury is a metal which is liquid at normal temperatures and pressures. It forms salts in two ionic states, mercury (I) and mercury (II). Mercury (II), or mercuric salts are very much more common than mercury (I) or mercurous salts. Mercury also forms organometallic compounds, some of which are of industrial and agricultural use. These organometallic compounds are stable, although some are readily broken down by living organisms, while others are not. Atmospheric pollution from industrial production is probably low, but pollution of water by mine tailings is significant. The burning of fossil fuels is a source of Hg. The chloralkali industry and, previously, the wood pulping industry, also released significant amounts of mercury. Although the use of mercury is decreasing, high concentrations of the metal are still present in sediments associated with the industrial applications of mercury. Some mercury compounds have been used in agriculture, principally as fungicides.

Mercury is now known to be a neurotoxin that causes structural damage to the brain and inhibits the activity of enzymes that are needed for normal neurotransmission. This impact occurs at lower concentrations than previously thought (10 ppm, instead of 50 ppm). Children and foetuses are at highest risk from exposure because their brains are still developing.

In Thane creek Mercury was recorded from all components of the ecosystem. In the water it varied between 0.21 and 0.39 mg/L and was observed only from the mid of the creek up to the northern end joining the Ulhas river (Fig. 10). In the sediment mercury was present throughout the creek with higher values along the east bank varying between 0.0086 and 0.0114 mg/gm. Among the benthic organisms Hg was recorded only from the Gastropods and Polychaetes while in other organisms there were stray records. Overall the concentration varied between 0.0007 and 0.116 mg/gm (Fig.10, 72 & 73). Among the fish species, Hg was recorded in the scales, liver and muscle of Mystus gulio and Mugil sp. while the other species showed accumulation in only one of the tissues (Fig. 74). However what was interesting was accumulation of Hg among the birds feathers of all the three species (Fig. 10) and was seen maximum in Black kite followed by gull and flamingo. The presence of mercury in the waters and the different faunal components indicates alarming conditions as the levels in the water were much higher than the permissible limits of 0.01 mg/L prescribed by the Environment (Protection) rules of 1986. Fig.70: Concentration of Mercury in the Waters of Fig.71: Concentration of Mercury in the sediments Low tide mark 0.5 Thane creek 0.012 from Thane creek Mid tide mark 0.4 0.01 0.3 0.008 0.2 0.006 mg/gm 0.1 0.004mg/gm 0 0.002 0 West - 1 3 5 7 East -2 4 6 8 Sampling Locations Sampling locations Fig. 73: Concentration of Mercury in the Polychaetes 0.14 Fig.72: Concentration Fig. : Concentration of Mercury in the Gastropods found along the West (WB) and found along the West (WB) and East (EB) of Thane 0.12 East (EB) banks of Thane creek 0.006 creek

0.1 0.005 0.08 0.004 0.06 mg/gm 0.003 0.04 mg/gm 0.002 0.02 0 0.001 0 WB -1L WB-3H WB-3M WB-7H WB-7M EB-2L EB-4M EB-6H EB-8L Sampling locations Sampling locations

0.02 Fig. 74: Concentration of Mercury in the fish found in Thane creek 0.018 0.016 Scales Muscle Liver 0.014 0.012 0.01

mg/gm 0.008 0.006 0.004 0.002 0 Therapon jarbua Lates calcarifer Megalops Mugil sp. Arius sp. Mystus gulio Acetes prawn Arca mussel Scylla scerata cyprinoides Fish Species

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