Assessment of Heavy Metal Distribution in the Fishing

JNROnline Journal Journal of Natural Remedies ISSN: 2320-3358 (e) Vol. 21, No. 4(S2), (2020) ISSN: 0972-5547(p)

ASSESSMENT OF HEAVY METAL DISTRIBUTION IN THE FISHING HARBOURS OF SOUTHEAST COAST OF INDIA V.Adlin Asha1, Rexin Thusnavis2 1Research Scholar (Reg No: 18223162032018), Department of chemistry, Pioneer Kumaraswamy College, Nagercoil, Affiliated to Manonmanium University, Tirunelveli, Tamilnadu, India. 2Department of Chemistry, Pioneer Kumaraswamy College, Nagercoil, Tamil Nadu, India ABSTRACT In this present study, the parameters of water quality and the concentration of trace metals such as Cadmium(Cd), Copper(Cu), Zinc(Zn), Lead(Pb), Cobalt(Co), Iron(Fe)are analysed in the surface waters of Chinnamuttom, Colachel, and Muttom fishing harbours, in the south coast of India from October 2019 to May 2020. During the period of study the concentration of heavy metals like Cu and Zn has shown a higher concentration and variation in all the three stations. The correlation test (p<0.01) has showed a strong correlation between Fe-Pb (S1), Zn-Cr (S2), Total Hardness–Cu (S2), EC-Cu (S2), EC-TDS (S3) in the three stations chosen for study. Heavy metals are analysed using atomic absorption spectrometry. Keywords: Heavy metals, parameters, South coast, Fishing Harbour. 1. INTRODUCTION In the aquatic ecosystem there is an overwhelming of heavy metals which attract the global attention towards the persistence and environmental toxicity. (Mir Mohammad Ali & Mohammed Lokman Ali et al., 2016). The concentration of metals in the marine condition relies upon their physical, synthetic, and organic dispersal. The development, utilization, sinking and demineralization of natural issues control the biogeochemistry of minor components in the marine environment. (SuchismitaSrichandan et al., 2016). Incorporated watershed board should investigate the watershed management measures depending on the quality of water and analysis. Bioaccumulation of these metals in aquatic farms harms the food chain thereby, the aquatic ecosystem and the health of human beings will be under threat. The intake of these metals that are deposited in the adipose tissue and liver of human beings affect their nervous and immune systems. Chromium can cause cancer when human beings are exposed to it for significant stretches of time. (Yinan Zhang et al., 2017) Water is one of the most basic assets on earth. Involving about 70% of the earth's surface, it is without doubt the most valuable assets that exists on the planet. Although most countries perceive this reality, water bodies remain the most dirtied. Consequently, living life forms both in water and those dependent on nature resource are under threat due to environmental pollution. (Joseph, & R Fianko et al., 2013). The contamination of coasts has been increasing in the recent years and this has increased natural disasters in many developing countries. Consequently, in the biotic community it is very important to estimate the concentration of heavy metals. (Suresh Kumar, C et al., 2016). Heavy metals are components with a particular gravity that is at least four to five times the particular gravity of water at a similar temperature and pressure. They have a positive valance and arepresent in the group I to III in the periodic table. (JakirHussain et al., 2017) Further, the nature of seawater and the concentration of heavy metals are very important because many Gulf countries depend on desalinated seawater as an important wellspring for the industrial and domestic consumption. (Choudri, BS et al., 2015). These heavy metals are in mobile forms, so that they leach and spread out through different mediums and are bioavailable to be absorbed by living beings. Since the overwhelming metals are not degradable, bioaccumulation happens through all degrees causing various ailments and harming. (Joao Vareda, P et al. 2019). 2.MATERIALS AND METHOD The surface water samples from October 2019 to May 2020 were collected from Chinnamuttom S1, ColachelS2,Muttom S3 fishing harbours using 100 ml polyethylene

Journal of Natural Remedies Vol. 21, No. 4(s2),(2020) terephthalate (PET) bottles. All the PET bottles were rinsed with the surface waters of each location before sampling. These samples are taken at a distance of 100 meters, 200 meters, 300 meters away from the edge of each harbour. The bottles were immersed below the water level for about 10 cm to prevent contamination through air. So, totally nine samples are taken from three harbours for each month. The samples were properly labelled for the identification of sources on the site and immediately transported to the laboratoryfor preservation and analysis. The sampling of water covered two season monsoons and a post monsoon. 2.1 Metal analysis: The physicochemical parameters and concentration of the selected trace metals like Cr, Cu, Zn, Pb, Cd, Fe in all surface water samples were analysed by Atomic Absorption Spectrometry (AAS).It is a technic used mostly for measuring quantities of chemical elements present in samples by measuring the absorbed radiation by the chemical elements of interest. The minimum, maximum, mean, SD SE, values of heavy metals are statistically shown in table 2. 2.2 Study Area: Kanyakumari district is at the juncture of the Western coastal plains and Eastern coastal plains(Figure-1). Chinnamuttom S1 is the only coastal area that lies near the Eastern coastal plains. The nearest town is Kanyakumari, an international tourist spot nearly 1.5 km away from the harbour. It was constructed in 1984 at the cost of 684.70 lakhs. The colachel S2 harbour is a natural harbour which 20 meters deep. It is located near the Western coastal plains. Muttom S3harbour is situated 16 km away from Nagercoil. It is a private fishing harbour for which TN government has offered 40 acres of land. It is constructed in the year 2008. In this study Chinnamuttom is considered as S1, Colachel S2, Muttom S3 and the latitude and longitude of the fishing harbours are given in Table -1. Table -1 STATION LATITUDE LONGITUDE S1 8.0943450N 77.5614450E S2 8.17190N 77.25510E S3 8.12620N 77.31960E

Figure-1

3. RESULT AND DISCUSSION 3.1. Water Quality Parameters The physico– chemical parameters of water such as pH, Total Dissolved Solids (TDS), Electrical conductivity (EC), Total Hardness, Temperature, Turbidity of water samples, their minimum and maximum values are stated in Table-2. The results show a considerable variation in the parameters. pH is one of the most common analyses in water testing, and it reports whether 28

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the water is acidic or alkaline in nature. Fluctuations in the acidity or basicity of seawater can have intense effects on the biological growth, activity of marine organisms and on the chemical reactions in the seawater column. The pH range of 7.5 to 8.5 is acceptable. (Hossam A. Zaqoot et al., 2018). In this study, pH ranges from 6.38 to7.83 in all the locations, and it indicates that they are within the acceptable limit. (Table-2) Total dissolved solids is the total amount of the mobile charged ions, including minerals, salts and metals dissolved in a given volume of water in mg/L (Sagar, SS et al., 2015). The TDS value varied between 458.3 mg/L to 2563 mg/L in S1, 809 mg/L to 3453 mg/L in S2, 694 mg/L to 3418mg/L S3 as shown in Table-2. Electrical conductivity will give the capacity of a substance in solution to conduct electric current. The electrical conductivity shows seasonal variation with respect to varying stations. The EC depends on the amount of dissolved solids in water. (Sreenivasulu1.G et al.)In study the EC value varied between 774 µmho/cm to 3625 µmho/cm in S1, 851 µmho/cm to 4827 µmho/cm in S2, 860 µmho/cm to 4433 µmho/cm in S3. Table-2 Statistical analysis for physicochemical parameters

Chinnamuttom Colachel Muttom

Para meters Min Max Mean SD SE Min Max Mean SD SE Min Max Mean SD SE

pH 6.39 6.83 6.61 0.31 0.22 6.71 7.52 7.12 0.57 0.405 7 7.13 7.07 0.09 0.06 TDS mg/l 458 2563 1511 1488.25 1052 809 3453 2131 1869.59 1322 694 3418 2056 1926.16 1362

EC µmho/cm 774 3625 2200 2015.96 1426 851 4827 2839 2811.46 1988 860 4433 2647 2526.49 1787 Total Hardness mg/l 102 598 350 350.72 248 244 561 403 224.15 158.5 155 433 294 196.58 139

Temp ºC 24.1 28.6 26.4 3.18 2.25 24 28.8 26.4 3.39 2.4 23.9 28 26 2.90 2.05

Turbidity NTU 1.46 3.63 2.55 1.53 1.09 1.8 3.43 2.62 1.15 0.815 1.5 3.97 2.74 1.75 1.24

The total hardness (Ca2+, Mg2+) of seawater shows the minimum of 102 mg/l to maximum 598 mg/l in S1, minimum 244mg/l to maximum 561 mg/l in S2 and minimum155 mg/l to maximum 433 mg/l in S3 of three study sites shown in Table-2. The lowest value 102 mg/l is noted in the month of March. It may due to upwelling currents of high mineral content which is responsible for regulating the ions in total hardness. (Suresh Kumar et al., 2013). The water temperature controls the rate of all chemical reactions, and affects, their reproduction and immunity. It is an important biological factor responsible for so many metabolic activities (Abbassi1, M et.al 2017).The surface water temperature of all the stations are in the range of minimum 24.1ºC in the season monsoon and maximum 28.6ºC in the post monsoon. This may due to urban or sewage runoff. In turbidity there is a slight variation based upon the season, it is found to be high in the season monsoon than in the post monsoon. In all the three stations S1, S2, S3 a minimum value of 1.46 NTU and a maximum value of 3.97 NTU are noted. In all the stations the highest value occurs during the post monsoon period. 3.2 .Metal Analysis: The surface water samples were collected from Chinnamuttom (S1), Colachel (S2), Muttom (S3) fishing harbours to analyse the concentration of Cr, Cu, Zn, Pb, Cd, Fe. The

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minimum and maximum values during the study is given in Table-3. Based upon the concentration of heavy metals separate graph is plotted (Figure-2). In the station S1, Cr shows a higher concentration of 77.6 µg/l in the month of November and a lower value of 43 µg/l in February (Fig 1). The concentration of copper in station S1 has a mean value of 50.3 µg/l .This value is lower when compared with the concentration of Cu obtained in Gaza fishing harbour of Palestine (Hossam, A Zaqoot et., al., 2018). The Zn concentration in station S1 noted a maximum value of 865 µg/l in November and minimum concentration 547 µg/l in March, that falls under post monsoon season. Figure-3 Chinnamuttom (S1) 1000

100

1 Cr Cu Zn Pb Cd Fe Monsoon Post Mosoon

The concentration of Zn is lower in this study when compared with the Mediterranean coastal waters in Eastern Nile Delta (198 mg/l) by MassoudSaad, AH &Ehsan Hassan, M (2002). The lower value recorded is due to the high precipitation of Zn salts from column to sediment,and the high temperature in the post monsoon. The mean concentration of Pb and Cd are 5.72 µg/l and 1.81 µg/l which is nearer to the Israeli standard 5 µg/l and 0.5 µg/l respectively. (HossamZaqoot, A et al., 2018). But it is still lower than the acceptable concentration 100 µg/l according to the guidelines of WHO on the value of heavy metals (Ahmed, A Melegy et al., 2019). The concentration of Fe shows the higher value of 719.3 µg/l when comparing with other stations. Table-3 Comparison of metals in sea water with different guidelines and other studies in the world

Metal Cr µg/l Cu µg/l Zn µg/l Pb µg/l Cd µg/l Fe µg/l Reference

Sample S1 S2 S3 S1 S2 S3 S1 S2 S3 S1 S2 S3 S1 S2 S3 S1 S2 S3 This Min 38 71.3 61.8 32.5 33.7 35 547 241 322 4.33 1.5 3.1 1.33 1.5 3.1 206 140 109 study Max 77.6 228 113 68 76.6 64.6 865 632 573 9 2.5 19.4 2.8 7.9 19.4 719 325 161

Mean 56.8 150 87.4 50.3 55.2 49.8 706 437 448 6.7 2 11 2.1 4.6 11.3 463 233 135

EPA Std. nd 45µg/l 1180µg/l 28µg/l 71µg/l nd [6] USEPA2000

Marine water quality nd 50µg/l 100µg/l 50µg/l 10µg/l nd [20] standards for harbours

WHO2004 nd 50µg/l nd 100µg/l nd 3000µg/l [2]

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EU Habour basin water 0.50mg/l 0.50mg/l 50.00mg/l 0.50mg/l 5µg/l 3.00mg/l ]13[ std.

"nd" is no data

In the station S2, the concentration of Cr is minimum in the month of May 71.3 µg/l and maximum in November 228.1 µg/l .When comparing the other stations the concentration of Cr is higher in the station S2.The concentration of Cr is high when compared with the values recorded in Ennore Creek of India (Suresh Kumar, C et al., 2013) that range between 11.60 µg/l to 15.75 µg/l. The concentration of Cu and Zn in the water sample ranged from 33.73 µg/l to 76.63 µg/l and 240.6 µg/l to 631.6 µg/l respectively. The concentration Pb in the water sample in S2 shows the range of 1.5 µg/l to 2.5 µg/l with a mean value of 2.07 µg/l. The mean concentration of Cd and Fe are 3.11 µg/l and 234.2 µg/l in station S2. The increasing concentration of Fe in the coast increases the susceptibility of fishes to infectious disease (Joseph R. Fianko et al., 2013).(Figure-3) Figure-3 Colachel (S2) 1000

100

1 Cr Cu Zn Pb Cd Fe Monsoon Postmonsoon

In station S3, the concentration of Cr has a minimum of 61.8 µg/l and maximum 113 µg/l. The Cu values in S3 is 50.3 µg/l which is higher in concentration as compared with the mean value of Yellow river estuary and its adjacent sea with 2.65 µg/l( Aikun TANG et al., 2010).This is due to the supply of copper in fertilizers and surface run-off that enters into the water (Ahmed, A Melegy et al.,2019).The concentration of Zn and Pb shows the range of 322 µg/l to 573.3 µg/l and 3.1 µg/l to 19.36 µg/l with a mean of 540.5 µg/l and 7.99 µg/l respectively. The higher values may due to the discharges from agricultural areas containing fertilizers and pesticides. Zn has a higher concentration than the ISI limits 5 µg/l Cd and Fe shows a mean value of 1.89 µg/l and 161 µg/l. The concentration of Cd is closely matched with the natural concentration of sea water 0.1 µg/l (Senthilnathan, S et al., 1999). (Figure-5) Figure-4 Muttom (S3) 1000

100

1 Cr Cu Zn Pb Cd Fe Monsoon Postmonsoon

3.3 Pearson correlation coefficient

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Pearson’s correlation is used to detect the correlation between heavy metals(Cr, Cu, Zn, Pd, Cd, Fe and the physical chemical parameters like TDS, EC, total hardness, temperature and turbidity of Chinnamuttom (S1), Colachel (S2), Muttom (S3) fishing harbours (Table-4). A strong correlation is found between Fe-Pb (S1), Zn-Cr (S2), Total Hardness–Cu (S2), EC-Cu (S2), EC- TDS (S3).This strong correlation may due to the similar levels of contamination or release from same pollution point or identical behaviour during their transport. (Mir Mohammed Ali et al., 2016). A moderate correlation is between Cu-Cr (S1), Zn-Cu (S1), Zn-Cu (S2), total hardness-Zn, Cr, EC (S2), total hardness-TDS (S3), turbidity-Zn, Temperature (S3). This correlation suggests that the heavy metals are from same chemical environment or from same sources.(Wei Hsiang Tan et al., 2016).A weak correlation is found between Zn-Cr (S1), Pb-Cr (S1), Pb-Cu (S1), turbidity-Fe (S1), Cd-Cr, Cu (S2), TDS-Fe (S3), Pb-Cr, Cu (S3).This weak correlation suggests that the trace elements are not specifically associated with each other and they are insignificant in distribution.(Joseph,RFianko et al., 2013). Table-4

Chinnamuttom (S1)

Cr Cu Zn Pb Cd Fe pH TDS EC Tot. Hard Temp Turbidity Cr 1.00

Cu 0.52 1.00 Zn 0.26 0.56 1.00 Pb -0.27 0.29 0.33 1.00 Cd -0.59 -0.40 -0.46 -0.49 1.00 Fe -0.09 0.14 0.43 0.90 -0.66 1.00 pH -0.21 -0.37 -0.56 -0.71 0.76 -0.71 1.00 TDS 0.04 0.47 0.47 0.87 -0.56 0.89 -0.57 1.00 EC 0.48 0.20 0.55 0.01 -0.44 0.36 -0.05 0.43 1.00 Tot.Hard -0.03 0.14 0.77 0.58 -0.44 0.75 -0.66 0.66 0.53 1.00 Temp -0.70 -0.73 -0.36 0.01 0.27 0.04 0.32 -0.27 -0.23 -0.17 1.00 Turbidity 0.81 0.80 0.63 0.19 -0.74 0.23 -0.64 0.36 0.34 0.31 -0.76 1.00

Colachel (S2) Cr 1.00 Cu 0.74 1.00 Zn 0.96 0.86 1.00 Pb 0.31 0.44 0.33 1.00 Cd -0.12 -0.18 0.00 0.07 1.00 Fe 0.63 0.66 0.70 0.53 0.10 1.00 Ph -0.23 -0.70 -0.39 -0.26 0.16 0.01 1.00 TDS 0.41 -0.23 0.17 0.09 -0.01 -0.15 0.36 1.00 EC 0.62 0.98 0.78 0.33 -0.20 0.61 -0.74 -0.40 1.00 Tot.Hard 0.83 0.94 0.87 0.40 -0.35 0.49 -0.69 0.03 0.88 1.00 Temp -0.67 -0.29 -0.63 0.27 -0.11 -0.44 -0.26 -0.36 -0.23 -0.28 1.00 Turbidity 0.34 -0.21 0.26 -0.32 0.50 0.22 0.63 0.50 -0.29 -0.22 -0.79 1.00 Muttom (S3) Cr 1.00 Cu 0.43 1.00 Zn 0.65 0.30 1.00 Pb 0.18 0.17 0.09 1.00 Cd 0.17 0.72 0.04 0.47 1.00 Fe -0.43 -0.40 -0.70 -0.35 -0.03 1.00 Ph -0.12 0.67 0.18 0.50 0.60 -0.50 1.00 TDS -0.46 0.25 -0.36 0.61 0.38 -0.11 0.78 1.00 EC -0.60 0.23 -0.62 0.32 0.33 0.19 0.62 0.92 1.00 Tot.Hard -0.62 0.09 -0.62 0.52 0.51 0.20 0.54 0.84 0.84 1.00 Temp 0.00 -0.11 -0.63 -0.08 -0.13 0.22 -0.39 -0.09 0.09 0.16 1.00 Turbidity 0.38 0.09 0.77 0.12 0.09 -0.21 0.13 -0.19 -0.39 -0.43 -0.90 1.00 32

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4. CONCLUSION This study is carried out to analyse the quality of water andconcentration of heavy metals in the three fishery harbours of Kanyakumari district. The levels of heavy metals in all the three stations are within the range of acceptance limit of EU Harbour water standard, but according to Marine water quality standards for harbours Indonesia & EPA standard, Cu and Zn show a higher value in all the three stations. .The distribution of heavy metals in fishing harbour may due to the fishing harbour activity and the mixing of anthropogenic effluents in the fishing Harbour. Further research and periodical monitoring of concentration of heavy metals in seawater along the fishery harbour and its surrounding are recommended. REFERENCE 1. Abbassi1,M, Banaoui1,A, Charioui1,I, Kaaya,A, Elkhou1,A 2017,’ Physico-chemical characterization of the coastal waters of the city of Sidi Ifni (Morocco), Journal of Materials and Environmental Sciences. JMES, 2017 Vol. 8, Issue 9, Page 3112-3120. 2. Ahmed Melegy,A, Mohamed El-Bady,S and HuseinMetwally,I, 2019,’ Monitoring of the changes in potential environmental risk of some heavy metals in water and sediments of Burullus Lake, Egypt,Bulletin of the National Research Centre 43:143. 3. Aikun TANG, Ruhai LIU, Min LING, Liaoqi XU, Jinyu WANG 2010,’Distribution Characteristics and Controlling Factors of Soluble Heavy Metals in the Yellow River Estuary and Adjacent Sea’, Procedia Environmental Sciences 2, 1193–1198. 4. Choudri,BS,MahadBaawain,&Mushtaque Ahmed 2015,’Review of water quality and pollution in coastal areas of Oman, Poll Res. 34 (2) : 229-239 . 5. Decree of the State Minister of the Environment Number, 2004,’Regarding Standard Quality of Seawater State Minister of the Environment’, Republic of Indonesia,Unofficial Translation by Water Environmental Partnership in Asia Number 51, Article 1. 6. Hasan,MR, Khan, MZH, Khan,M, Aktar,S, Rahman,M, Hossain,F, and Hasan ASMM 2016, ‘Heavy metals distribution and contamination in surface water of the Bay of Bengal ’,coast Cogent Environmental Science, 2: 1140001 7. HossamZaqoot,A, Adnan Aish,M, HishamWafi,M, 2018,’ Study on heavy metal pollution in Gaza fishing harbour along the Mediterranean Sea-Gaza beach, Palestine, Journal of Aquatic Science and Marine Biology Vol.1, Issue 1, PP 24-34 8. JakirHussain,Ikbal Husain, Mohammed Arif,Nidhi Gupta 2017,’Studies on heavy metal contamination in Godavari river basin’,Appl Water Sci 7;4539-4548. 9. Joao Vareda,P, ArturValente,JM,Valente,LuisaDuraes 2019,’Assessement of Heavy metal pollution from Anthropogenic activities and remediation strategies :review’,Journal of Environmental Management246,101-118. 10. Joseph,RFianko, Cynthia Laar,JuiletOsei, Alfred,KAnim,AbassGibrilla Dickson Adomako 2013, ‘Evaluation of some heavy metal loading in the Kpeshilagoon,Ghana, Appl Water Sci 3:311–319. 11. MassoudSaad,AH&EhsanHassan,M, 2002,’ Heavy metals in the Rosetta estuary of the Nile and the adjoining Mediterranean waters: evidence of removal of dissolved heavy metals from waters as a result of possible binding to suspended matter’, Hydrobiologia 469: 131–147, 2002. 12. Ali, MdSaifulislam, MdZillurRahman 2016, ‘Preliminary assessment of heavy metals in water and sediment of Karnaphuli River, Bangladesh’, Environmental nanotechnology, Monitoring & Management 5 27-35. 13. Sagar, SS, Chavan, RP, Patil, CL, Shinde, DN, Kekane, SS, 2015,’ Physico-chemical parameters for testing of water-A review’, International Journal of Chemical Studies 2015; 3(4): 24-28. 14. Sciortino, JA, Ravikumar, R 1999, Fishery Harbour Manual on the Prevention of Pollution - Bay of Bengal Programme, BOBP For Fisheries Management,22,Madras, India . 15. Senthilnathan,S,Azeez,PA 1999,’Water quality effluents from dyeing and Bleaching Industries in Tirupur, Tamilnadu, India’, Jr of Industrial pollution control Vol.15 (1), Pg 79-88.

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