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a
National Center for Coastal Research, Chennai 600100, India
b
Indira Gandhi Centre for Atomic Research,Tamil Nadu 603102, India
c
Central University Rajastan, Rajastan, 305817, India
Keywords: The objective of the present study was to conduct an ecological and health risk assessment of heavy metals in the
Heavy metals seawater of the southeast coast of India. The distribution profile of heavy metals in the surface seawater was Fe
Ecological risk (79.60 ± 21.57 μg/L) > Zn (9.31 ± 1.33 μg/L) > Cu (5.19 ± 2.00 μg/L) > Ni (2.45 ± 0.76 μg/
Seawater pollution index L) > Mn (1.20 ± 1.00 μg/L) > U (0.44 ± 0.23 μg/L) > Pb (0.36 ± 0.06 μg/L) > Cr (0.31 ± 0.57 μg/
Health risk assessment
L) > Cd (0.11 ± 0.05 μg/L) > Co (0.07 ± 0.20 μg/L). Cu level for most of the samples exceeded the USEPA
Dermal exposure
criteria for acute CMC (criterion maximum concentration) and chronic CCC (criterion continuous concentra
Uranium
tion). Other studied metals, Cd, Cr, Pb, and Ni, remained below the acute CMC and chronic CCC guidelines. The
seawater pollution index (Iwp) of Cr, Ni, Zn, Cd, and Pb complied with the category–I seawater (< 1, unpolluted).
The ERI values (0.46–3.99) of the seawater of the studied coast mostly fell under the ecologically low risk
category with respect to heavy metals. Dermal Hazard index values were orders of magnitude lower than one,
indicating no potential health concern due to dermal exposure.
Billions of pounds of trash containing a significant amount of me in seawater along the entire stretch of the ecologically diverse Tamil
tallic pollutants enter the sea each year due to human activities Nadu coastline. Moreover, studies on coastal metal pollution of Tamil
(Rochman et al. (2016); Daoji and Daler (2004)). In past decades, un Nadu coast have been primarily focused on sediment and biota (Kumar
controlled growth in industrialization along the southeast coast of India et al. (2019); Rameshkumar et al. (2018); Senthil Kumaar et al. (2014);
has led to rapid contamination of its coastal environment. In Particular, Kumar et al. (2017); Sivakumar et al. (2016); Kasilingam et al. (2016);
incessant input of heavy metals through domestic and industrial waste Ravisankar et al. (2019)). The complexity of heavy metal analysis in
from point and non-point sources has significantly deteriorated the seawater due to their low dissolved concentrations and high salt in
marine ecosystem of the coast (Tholkappian et al. (2018); Ganugapenta terference is probably the main hindrance for studies in seawater
et al. (2018); Jayaraju et al. (2009)). The steady increase in toxic heavy compared to in sediment and biota. The main objective of the present
metal concentration in the seawater raises significant concern about the investigation was to assess the distribution of heavy metals in the
ecological hazard to its habitat, and health risk to the dependent po seawater at selected locations along the major part of the southeast
pulation (Ananthan et al. (2006); Karthikeyan et al. (2007)). Assess coast of India and to evaluate the corresponding ecological and health
ment of heavy metal contamination in the seawater is one of the vital risk by employing the USEPA risk assessment paradigm.
steps toward ensuring seawater quality to perpetuate the wellbeing of Eight ecologically distinct locations (S1–S8) were selected along the
marine habitats and sustenance of marine resources and to minimize southeast coast of India, covering a 300 km stretch (Fig. 1). Details of
the possible health risk to humans. the ecological significance and discrete features of the sampling loca
Pollution of the marginal marine environment and related en tions are described in supplementary materials (S1). Seawater samples
vironmental problems along the southeast coast of India have been from the surface (< 0.5 m) and bottom (at 10–12 m depth) were col
recognized for more than four decades (Nammalwar et al. (1985)). lected using a niskin water sampler. pH, temperature, and dissolved
However, apart from the patchy reports of heavy metal contaminations oxygen (DO) were measured in situ. Suspended particulate matter
at some locations (Thomas and Mohaideen (2015); Padhi et al. (2013)), (SPM) was calculated as the difference between the initial and final
no study reported the spatial distribution of heavy metal contamination weight of the filter paper after drying at 105 °C overnight. Dissolved
⁎
Corresponding author.
E-mail address: ranjib@igcar.gov.in (R.K. Padhi).
https://doi.org/10.1016/j.marpolbul.2020.111712
Received 22 June 2020; Received in revised form 11 September 2020; Accepted 21 September 2020
Available online 13 October 2020
0025-326X/ © 2020 Elsevier Ltd. All rights reserved.
S.B. Kumar, et al. Marine Pollution Bulletin 161 (2020) 111712
INDIA
Arabian Bay of
Sea Bengal
Karnataka
Fig. 1. Geographical position and location of sampling sites along the south east coast of India.
heavy metals analysis in seawater was carried out following the salt Distribution of Cr, Mn, Fe, Co, Ni, Cu, Zn, Pb, Cd, and U in the
matrix elimination and heavy metal pre-concentration by chelex com surface and bottom seawater is presented in Fig. 2. The level of dis
plexation (Padhi et al. (2013)). Samples were analyzed for Cr, Mn, Fe, solved metals in the surface and bottom seawater showed wide spatial
Co, Ni, Cu, Zn, Pb, Cd, and U by high resolution inductively coupled variations along the studied coastline. The order of the heavy metal
plasma mass spectrometry (ICP-MS). The full procedure of sample level in the surface water was Fe (79.60 ± 21.57 μg/L) > Zn
preparation and analytical method for the metal analysis is given as (9.31 ± 1.33 μg/L) > Cu (5.19 ± 2.00 μg/L) > Ni
supplementary material (S2). (2.45 ± 0.76 μg/L) > Mn (1.20 ± 1.00 μg/L) > U
The observed values of physicochemical parameters were within the (0.44 ± 0.23 μg/L) > Pb (0.36 ± 0.06 μg/L) > Cr
expected range for the seawater of this coastline (Table S1). pH and (0.31 ± 0.57 μg/L) > Cd (0.11 ± 0.05 μg/L) > Co
salinity were observed to be lowest for location S3 (pH: surface-7.40, (0.57 ± 0.20 μg/L), whereas in the bottom seawater, the trend was
bottom-7.80; salinity: surface-31.36, bottom-31.46 PSU), which might Fe > Zn > Cu > Ni > Mn > Pb > U > Cr > Cd with their
be due to the influence of freshwater discharge to the sea from the average values being 109.45 ± 43.44, 12.87 ± 5.57, 6.35 ± 6.59,
nearby Mutthukadu backwaters. DO values (2.80 to 6.56 mg/L) were 2.73 ± 0.71, 1.78 ± 2.18, 0.55 ± 0.31, 0.35 ± 0.12, 2.01 ± 0.76,
always observed to be higher in surface seawater than bottom water. 0.11 ± 0.06 μg/L, respectively (Table S2a). Co concentration re
DO was recorded between 2.8 (bottom) to 3.6 mg/L (surface) in the mained below the detection limit (BDL) for all the bottom seawater
seawater at S2, which was lower than the minimum of 4 mg/L O2 samples. In general, the concentrations of all the studied dissolved
content required for the survival of aquatic organisms. In accordance metals in the bottom water were marginally higher than that in surface
with the criteria for DO in the Seawater Quality Standard of China water except U. Dissolved U primarily occurs as oxidized U(VI) which
(SEPA (1997)), the seawater along the coast was mostly between the forms soluble uranyl carbonate complexes in the oxygenated surface
relatively clean (category-II) to the slightly polluted categories (cate seawater. The soluble U(VI) form reduces to the insoluble U(IV) form
gory-III). The seawater at S2 was observed to be hypoxic and corre under oxygen-depleted conditions, which results in the removal of
sponds to category-IV (medium polluted) to category-V (heavily pol dissolved U from the water column (Rolison et al. (2017)). The lower U
luted) seawater with respect to DO content (SEPA (1997)). S2 is located concentration at the bottom compared to the surface seawater observed
between the Adayar River and Coovum River estuaries, which carry in our study was consistent with the negative DO gradient across the
untreated sewage from Chennai city to the sea (Jayaprakash et al. depth of the seawater.
(2012); Silambarasan et al. (2012)) and thus, DO gets depleted here due Among the ten heavy metals investigated, Fe, Zn, Mn, Co, and Cu
to its utilization for the decomposition of the sewage bound organic are known to be essential metallic elements required at a certain level
matter. for all aquatic life forms. A comparative account of heavy metal
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S.B. Kumar, et al. Marine Pollution Bulletin 161 (2020) 111712
Fig. 2. Distribution of ten heavy metals in the surface and bottom seawater of eight selected locations along the south east coast of India.
concentration observed in the present study with earlier reported stu input sources such as NieCd battery manufacturing. Cr (1.16–2.01 μg L-
dies in different coasts across world is given as supplementary material 1) remained undetected in most of the samples even though Cr content
(Table S2b). In the present study, Fe values recorded were comparable in the sediment of these locations was reported to be relatively high
with the values observed for South Australian and Egyptian (Kumar et al. (2017)). At the reduced level of O2 observed at the bottom
Mediterranean coastlines (Chakraborty and Owens (2014); Khaled et al. seawater, it is likely that the transformation of particle reactive in
(2017)). Previous studies in the Bay of Bengal and other coastal areas soluble Cr(III) to soluble Cr(VI) would be a minor process to contribute
(Srichandan et al. (2016); Rejomon et al. (2008); Al-Taani et al. (2014)) to dissolved Cr. Thus, higher Cr content in sediment might not be an
have reported a very low dissolved Fe concentration. Conversely, Fe indicator for its elevated level in seawater. Low concentrations of Pb
content as high as 1698 μg/L and 2368 μg/L were reported from Ennore (0.29–1.26 μg/L) and Cd (0.04–0.2 μg/L) were detected and remained
Creek and Bay of Bengal coast, Bangladesh, respectively (Jayaprakash well below the USEPA acute CMC and chronic CCC for aquatic life.
et al. (2015); Hasan et al. (2016)). In our present investigation, stations Compared with the seawater quality Standard of China (SEPA (1997)),
S1, S2, and S3 showed higher Fe values compared to other stations. This seawater quality of the studied coast can be regarded as clean to rela
indicated the profound influence of anthropogenic input from the tively clean water (category-I-II) with respect to Cr, Zn, Cd, Cu, and Pb,
neighboring metropolitan city of Chennai on the metal contamination (Table S4). It was identified that, compared to other stations, S2 seems
in the adjoining coast. Co generally occurs at low concentrations in to be more polluted with heavy metals. S2 station is located near the
seawater, and the mechanism that governs its distribution in seawater is Chennai harbor, and in between the Adyar and Cooum Rivers. Waste
not well elucidated (Saito and Moffett (2002)). In the present study, Co water from the Chennai metropolitan area along with toxic chemicals
concentration remained below the detecting limit expect in the surface released in the harbor, which contain a high amount of heavy metals,
water at location S1. However, previous studies carried out near loca might be the primary reason for its elevated level at S2 compared to
tion S1 have reported much higher values of dissolved Co (Jayaprakash other stations.
et al. (2015)). Bottom water of S1 and S2 showed the highest con Pearson correlation and principal component analysis (PCA) were
centrations (3.38 and 6.14 μg/L) of Mn with an average of conducted to investigate the association of physicochemical parameters
1.47 ± 1.63 μg L-1. Similarly, Cu concentration (average: 5.73 μg/L) with heavy metals. The Pearson correlation analysis (Table 1) showed
was also observed to be highest for the bottom water of S2 (20.89 μg/L). strong negative correlations of Zn and Pb with DO (R = −0.552,
As specified in the USEPA aquatic life criteria table, criterion maximum −0.574; p < 0.05), which indicated the likelihood of the transfor
concentration (CMC) for acute toxicity and criterion continuous con mation of Zn and Pb to soluble form in the aerobic environment and
centration (CCC) for chronic toxicity of Cu are 4.8 and 3.1 μg/L, re their reductive scavenging in anaerobic conditions. Moreover, strong
spectively (USEPA (n.d.)) (Table S3). Cu concentration in most of the associations such as Co–pH (R = −0.523; p < 0.05) and Cr, Mn, Zn,
samples exceeded the acute CMC and chronic CCC. However, con Cu, and Pb with temperature (R = −0.537, −0.583, −0.585, −0.516,
centrations observed in our study were relatively low compared to −0.625, respectively; p < 0.05), suggested strong influence of pH and
other coasts (Table S2b). The Zn level in the studied coastline, with an temperature on the distribution of dissolved heavy metals in seawater.
average value of 10.97 ± 4.19 μg/L, was much lower than the acute All heavy metals showed positive correlations among themselves except
CMC of 90 μg/L and chronic CCC of 81 μg/L and thus is not expected to U and Co (Table 1), and U was the only metal which exhibited a strong
pose toxicity risk to the aquatic organisms. Other studied metals, Cd, negative correlation with Fe, Ni, and Cd (−0.525 (p < 0.05), −0.656
Cr, Pb, and Ni, for which the USEPA aquatic life criteria exist, remained (p < 0.01), and −0.490 (p < 0.1), respectively). As seawater is the
below the acute CMC and chronic CCC values ((Table S3). Among all largest reservoir of U, its negative correlation with other metals further
the metals studied, Ni in particular showed a reasonably strong corre corroborated the fact that all other metals in the studied coast were
lation with the suspended particulate matter (R2=0.55, Fig. S1), in enriched through anthropogenic input. In PCA analysis, five principal
dicating the importance of the biogeochemical cycle involving parti components were extracted with eigenvalues > 1, which contributed
culate in maintaining Ni levels in the coastal water. Ni forms stable about 87.10% of the total variance (Fig. S2). The bi-plot of the first two
complexes with inorganics and organic ligands, leading to its accumu principal components (PCs) indicated that all the metals showed posi
lation in the suspended matter, which might be one of the leading tive loadings in PC1, except U and Co. U was negatively loaded,
reasons for its strong correlation with SPM (Moore and Ramamoorthy whereas the loading of Co was not significant (Fig. 3). Loading pattern
(2012)). The distribution profile of Ni was strikingly similar to that of of heavy metals indicated the common process or source of origin of all
Cd (R2 = 0. 77, Fig. S1). This suggested their association with common these metals along this coast. This further corroborated the earlier
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S.B. Kumar, et al. Marine Pollution Bulletin 161 (2020) 111712
Table 1
Pearson's correlation matrix for dissolved heavy metal and the physicochemical parameters in seawater.
DO pH Salinity Temp SPM Fe Cr Mn Co Ni Zn Cu Cd Pb U
DO 1
pH −0.203 1
Salinity −0.380 0.671⁎⁎⁎ 1
Temp 0.660⁎⁎⁎ 0.013 −0.173 1
SPM 0.134 −0.003 −0.009 0.114 1
Fe −0.396 −0.168 −0.223 −0.323 0.301 1
Cr −0.180 0.174 0.229 −0.537⁎⁎ 0.104 0.351 1
Mn −0.412 −0.231 −0.076 −0.583⁎⁎ −0.270 0.610⁎⁎ 0.491⁎ 1
Co −0.030 −0.523⁎⁎ 0.027 −0.010 −0.261 0.110 −0.129 0.144 1
Ni −0.005 0.025 0.064 −0.198 0.711⁎⁎⁎ 0.604⁎⁎ 0.433 0.143 0.058 1
Zn −0.552⁎⁎ 0.216 0.151 −0.585⁎⁎ 0.168 0.742⁎⁎⁎ 0.680⁎⁎⁎ 0.696⁎⁎⁎ −0.154 0.570⁎⁎ 1
Cu −0.411 −0.037 −0.038 −0.516⁎⁎ 0.079 0.779⁎⁎⁎ 0.775⁎⁎⁎ 0.781⁎⁎⁎ −0.044 0.463⁎ 0.858⁎⁎⁎ 1
Cd 0.076 0.099 −0.146 −0.367 0.062 0.390 0.769⁎⁎⁎ 0.297 −0.090 0.545⁎⁎ 0.574⁎⁎ 0.613⁎⁎ 1
Pb −0.574⁎⁎ 0.175 0.156 −0.625⁎⁎ −0.030 0.592⁎⁎ 0.728⁎⁎⁎ 0.766⁎⁎⁎ −0.179 0.297 0.923⁎⁎⁎ 0.824⁎⁎⁎ 0.488⁎ 1
U −0.232 0.122 0.252 0.137 −0.313 −0.525⁎⁎ −0.303 −0.421 −0.100 −0.656⁎⁎⁎ −0.416 −0.425 −0.490⁎ −0.259 1
⁎
Correlation is significant at the 0.1 level.
⁎⁎
Correlation is significant at the 0.05 level.
⁎⁎⁎
Correlation is significant at the 0.01 level.
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S.B. Kumar, et al. Marine Pollution Bulletin 161 (2020) 111712
respectively (for details, see Table S6 and its footnote). Estimated ERI
values exceeded one for the bottom seawater of S2 (3.99), S8 (1.34), and
S3 (1.06). The trend of ERI for the surface seawater at different loca
tions was S3 (1.63) > S6 (1.58) > S4 (1.23) > S2 (1.14) > S1
(1.10) > S7 (0.92) > S5 (0.76) > S8 (0.56) (Fig. 5). The ERI values
indicated that the seawater along the studied coast fell under the eco
logically low risk category with respect to heavy metals.
Human Health risk assessment (HRA) typically considers three ex
posure pathways, such as inhalation, ingestion, and dermal absorption.
For seawater metal contamination, health risk to those involved in
water contact activities such as fishermen, surfers, divers and swim
mers; dermal exposure is the dominant risk component compared to
ingestion or inhalation (Kim et al. (2004)). Unintentional ingestion of
seawater during recreational activities is only about 30–50 mL (per
event of 0.6 h/day) (WHO (2003)) and hence its contribution to HRA
can be neglected unless the seawater is heavily polluted. Dermal hazard
index (HIderm) as the sum of hazard quotients (HQdermi) represents the
cumulative non-carcinogenic risk calculated in accordance with Eqs.
(5), (6), and (7) (USEPA (1991, 2002)).
n
i
HIderm = HQderm
i (5)
i
HQderm = CDIderm/ Rfdderm (6)
Fig. 4. Seawater pollution index for the studied coast calculated for six metals
separately (Iwpi) and overall index Iwp (for combined metal). C i × SA × AF × ABSd × ET × EF × ED × CF
CDIderm =
BW × AT (7)
taken as 1 for Zn, 2 for Cr, 5 for Cu, Ni, and Pb, and 30 for Cd (Li et al. where, CDIderm is the chronic daily intake; C is the concentration of ith
i
(2012); Xu et al. (2008); Kang et al. (2020)) (Table S3)). The estimated metal in the water samples (mg/L), SA is exposed skin area (5700 cm2),
HQi of Cr, Zn, Cd, and Pb was less than one for both surface and bottom AF is adherence factor (0.07 mg/cm2), ABSd is dermal absorption
seawater of all the locations. Additionally, HQi values varied from 0.98 fraction (0.03), ET is the exposure time (0.6 h/day), EF is exposure
to 2.3 for Ni and 2.5 to 33.7 for Cu and it clearly showed that Cu and Ni frequency (365 days/year), ED is exposure duration (70 years for
are the metals of potential concern along the studied coast. Among all adults), BW is body weight (70 kg for adults), AT is the average time
the sampling locations, the seawater at S2 showed the highest HQi for (ED × 365 days) and CF is the conversion factor (10−6 Kg/mg). The
both Cu (33.7) and Ni (2.3). However, HQi calculation accounts for only Rfdderm (mg/day) for the heavy metal used in Eq. (6) is provided in
the ecological sensitivity criteria and concentration of metal and thus, Table S7. The average CDIderm values were in the range of 10−11 to
appropriate for a preliminary assessment of aquatic toxicity. In order to 10−9 mg/day with the highest value observed for Fe (9.6 × 10−9) and
determine the overall risk posed by the simultaneous presence of lowest value observed for Cd (1.09 × 10−11). The calculated average
multiple heavy metals and to account for their difference in the degree HQi values of metals were in the order: Cr > Cd > Ni > Fe > Pb >
of toxicity, the normalized toxicity response factor was introduced (Eq. Mn > Cu > Co > Zn. Among all the studied locations, S2 exhibited
(4)) into the calculation of overall ecological risk index (ERI). ERI less the maximum and S7 had the minimum dermal hazard index. However,
than 1, 1–5, 5–10, 10–15, and greater than fifteen can be classified as HQderm were orders of magnitude lower than 1 (ranged between
no risk, low risk, moderate risk, considerable risk, and high-risk classes, 7.4 × 10−6 - 2.2 × 10−7), which indicated that the seawater along the
studied coast does not pose any adverse health concern via dermal
exposure with regard to heavy metal.
In summary, the present study determined the distributional char
acteristics of ten heavy metals in the surface and bottom seawater of the
southeast coast of India. Among all the studied locations, bottom sea
water at S2 exhibited the highest ecological concern. Risk assessment
indices such as Iwp, ERI, and CDIderm evaluated in the present study
indicated that the coastal water poses no potential ecological or health
threat with regard to heavy metals. However, more studies on the
spatiotemporal heterogenity is necessary to conclusively establish the
ecological risk contour of the coast. Cu concentration exceeded the
acute CMC and chronic CCC for most of the samples and was identified
as the metal of potential concern.
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S.B. Kumar, et al. Marine Pollution Bulletin 161 (2020) 111712