“4 Research Report”
Occurrence, spatial distribution, and health status risk of emerging Contaminants inmarine water, sediment and biota samples in Bay of Bengal, India
Arun Elaiyaraja, Research Scholar, Department of Environmental Biotechnology, School ofEnvironmental
Sciences, Bharathidasan University, Tiruchirappalli, Tamil Nadu, India
1.
Introduction
Synthetic musks are organic compounds produced in large quantities and extensively used in various
consumer products, especially cosmetics and personal care products (PCPs) (Mottaleb et al., 2012;
Nakata, 2005). Polycyclic musks (PCMs - galaxolide and tonalide) are widely applied in various PCPs
and additives in cigarettes and fish baits (Homem et al., 2015). They can cause oestrogenic/antioestrogenic effects in humans and other organism (Huang et al., 2016; Hu et al., 2011). Synthetic musks
are currently found in most surface aquatic systems and atmosphere (Lange et al., 2015; Nakata et al.,2012; Lee et al., 2014). They enter the aquatic environment through direct means like swimming andbathing in rivers and beaches, and indirect discharges, like effluents from wastewater treatment plants(WWTPs) (Homem et al., 2015; Groz et al., 2014). Synthetic musks are lipophilic, persistent and highly
bio accumulative. They easily adsorb onto organic matter and accumulate in the soil, sediments andmarine organisms (Huang et al., 2016; Wang et al., 2013; Chen et al., 2014). Galaxolide and tonalide were
frequently observed in the effluents of domestic WWTPs and fish tissues from aquatic environments close
to urban centres of Germany and China (Lange et al., 2015; Zhang et al., 2013; Klaschka et al., 2013;
Reiner and Kannan, 2011). Nakata et al. (2012) found synthetic musks contamination in mussels fromcoastal areas in Asian countries. Contamination studies on freshwater fish by emerging contaminants were
scarcely reported. Nevertheless, monitoring of synthetic musks in marine samples (Water, Sediment andBiota) was not investigated in India. Hence, the current study was carried out to explore the fate ofsynthetic musks (Galaxolide, tonalide and Musk Ketone) in marine water, sediment and biota samples.
1.1.

Objective To collect the samples with background data and determine the quantification of Galaxolide,tonalide and MK in Marine samples which was already collected by the PI in Bay of Bengal,
southern India.
 To determine the levels of synthetic musks (Galaxolide, tonalide and MK) in the appropriate
samples from marine water, sediment and biota, and their bioaccumulation factors in biota
samples will be measured and human and environmental risk assessment will be calculate basedon this RQ = MEC/PNEC. (RQ- Risk Quotient, MEC-Measured Environmental Concentration,
PNEC-Predicted No Environmental Concentration).

INDIA

M2

M1

M4

M3

M6

M5

Bay of Bengal

LEGEND
Sampling Sites
M1 - Ennore Beach
M2 - Marina Beach
M3 - Pattinapakkam
M4 - Besant Nagar
M5 - Golden Beach
M6 - ECR Beach
M7 - Devipattinam
M8 - Mandapam
M9 - Pamban
M10 - Rameswaram
M11 - Dhanushkodi
M12 - Thoothukudi

Tamil Nadu

M7

M8
M9

12
M11
M10

Indian Ocean

https://bhuvan.nrsc.gov.in/

Fig. 1 Map of the study area with all sampling locations marked.

Fig.2 shows the extraction and analysis of Synthetic Musk

2. Extraction procedure for Synthetic Musk in Marine Samples
Number samples were collected Marine water (12), Sediment (12), Biota (8) in Chennai metro pollutants area and Gulf of Mannar Bioreserve (GMB).
3.
Result and discussion
3.1 Occurrence of Synthetic musks in Marine water
The concentration (mean and median) and detection frequency of synthetic musks (Galaxolide, Tonalide and MK) in marine water were summarised in Table 1. The
concentrations of galaxolide, tonalide and MK in marine water from the Bay of Bengal in southern, India, were ND - 3.08 (ng/L), ND-0.84 (ng/g), and ND - 5.58
(ng/g), respectively (Fig. 3). The detection frequency of synthetic musks are observed in the order of Musk Ketone > Galaxolide > Tonalide). Musk Ketone wasfound high in Gulf of Mannar region and compare with that metro pollutant area is very lowest concertation detected at M1 and M3. The municipal sewage,
industrial wastewater, and hospital wastewaters were directly or indirectly discharged into the Gulf of Mannar region, which leads to a higher concentration of SMs
in the marine water. The major source of SMs Contamination in these Gulf of Mannar may be due to the leak of sewage treatment systems and the Human activities
had been the predominant source for SMs in the Gulf of Mannar region, specifically M8, M9, M10, M11 and M12 (fig.2).

Galaxolide

TonalideMusk Ketone

7.00
6.00

4.00
3.00
2.00
1.00

M12

M11

M10

M9

M8

M7

M6

M5

M4

M3

M2

0.00

M1

Concentration (ng/L)

5.00(Locations ID)

Fig. 3 Concentrations (ng/L) of Synthetic Musk in seawater from the Bay of Bengal, India
Similarly, of from M8 to M10 sampling sites were human activities (bathing, washing etc.) were high.
These reasons would imply higher SMs concentration in the Mannar regions. Chemical transformation(i.e., oxidation) mechanism may play a significant role in eliminating SMs from sewage (Lv et al., 2010).
The present observation of SMs corroborates with our earlier studies on pharmaceutical and personal careproducts (Triclosan, Triclocarban, Benzotriazole UV Stabilizers, Parabens, NSAIDS and Carbamazepine)
and plasticisers (phthalates and phenolics) as found higher levels in the riverine system reported(Ramaswamy et al., 2011; Selvaraj et al., 2015; Vimalkumar et al., 2018; Shanmugam et al., 2014). The
concentration of galaxolide and tonalide in Haihe River in China ranged from 3.5 to 32 ng/L and 2.3 to26.7 ng/L, respectively. However, synthetic musk levels observed in this study were 1–2 orders ofmagnitude lower than reported in the Arctic, the North Sea and Northern Germany (galaxolide 0.012–2.03
ng/L and tonalide 0.003–0.965 ng/L) (Xie et al., 2007). Lee et al. (2014) investigated the contamination of
SMs in the Nakdong River in Korea, and total SMs were two to three orders of magnitude (150–16,720
ng/L) greater than the present study. Further, it indicates that the consumption of fragrances containing
SMs in Korea was high.
3.2 Occurrence of Synthetic musks in Marine sedimentPhthalate concentration (mean and range) and their prevalence in sediment from southern Indian Bay of
Bengal are given in Table 1. The concentrations of galaxolide and MK in marine sediment from the Bayof Bengal were ND - 3.61 (ng/g) and ND - 10.53 (ng/g), respectively (Fig. 4). In sediment samples, thegalaxolide and Musk Ketone detection rates were 67 % and 42 % and tonalide not detected at in any
sediment samples. Galaxolide and MK were also dominated SMs in sediments of the Pearl River Delta(China) (Zeng et al., 2008), Macao coastal region (China) (Wang et al., 2014) and Lake Michigan (USA)(Peck and Hornbuckle, 2004) respectively. The lipophilic properties of galaxolide and tonalide lead totheir absorption onto particles during seawater and sediment partitioning (Lange et al., 2015). In thepresent study, SMs concentration in sediment was higher than the water samples from the bay of Bengal
regions. This could be due to the surface runoff of synthetic musk from its potential sources, i.e. leachingfrom land, and treated/non-treated domestic wastewater. Vimalkumar et al. (2020) reported higher
concentrations of synthetics musks in the particulate phase than in the dissolved phase of wastewater fromSavannah, Georgia, USA reported PPCPs and Musks. In water, PPCPs and suspended particulate matter(SPM) relate with each other and accumulate in the sediment and this could elevate the concentration of
PPCPs in water and sediment (Zhao et al., 2013). Higgins et al. (2011) and Wang et al. (2014) stated that
personal care products (PCPs) persist in the sediment because of their high affinity towards organiccarbon. Moreover, PPCPs has a low solubility and high no octanol-water partition coefficient; this could
be a possible reason for its accumulation in matrices like sediment (Lv et al., 2014). Synthetic Musks has
high affinity to organic carbon (Guna et al., 2014) and this could be used as a reliable indicator fororganic contamination in the aquatic ecosystem.

Galaxolide

Tonalide

Galaxolide

Musk Ketone
Concentration (ng/g)

Concentration (ng/g)

14.0
12.0
10.0
8.0
6.0
4.0

TonalideMusk Ketone

1000.0
100.0
10.0
1.0
0.1

2.0
M12

M11

M10

M9

M8

M7

M6

M5

M4

M3

M2

M1

0.0

(Locations ID)

Fish Speaice Name

Fig. 4 and 5 Concentrations (ng/g(dw & ww)) of Synthetic Musk in sea sediment and Fish from the
Bay of Bengal, India
3.3 Occurrence of Synthetic musks in Marine Biota samples
The levels of synthetic musks in eight species fish samples collected Bay of Bengal are shown in Fig. 1.
Galaxolide, tonalide and MK in fish ranged as ND - 178, ND - 134 and ND - 2.5 ng/g (ww). Whereas as
the highest concertation at detected at Galaxolide and Tonalide in Escualosa thoracata (spic) respectively(Fig.5). The higher octanol – water partition coefficients (LogKow) for galaxolide (5.9), tonalide (5.7) andMK (4.3) (Chen et al., 2015) reflecting their residual burden in biota. A clear seasonal distribution patternof SMs was noticed in this study. Kannan et al. (2005) USA reported lower concentrations of galaxolide
and tonalide in the Atlantic salmon (1–3.2 ng/g ww; 1–1.6 ng/g (ww), Atlantic sharpnose shark (4.6–5.2
ng/g (ww); 1.4–1.7 ng/g (ww) and smallmouth bass (4.3–5.4 ng/g (ww); 1.6–1.9 ng/g (ww) However, theconcentration of in present study higher concertation of Galaxolide in the species of Escualosa
thoracata, . Galaxolide concentration in the liver of marine hammerhead shark (Sphyrnidae) in Japanese
coastal waters was ranged from 16 to 48 ng/g (ww), which is lower than the fish in the Gulf of Mannar
region.
4. Human health risk assessment
The human Hazard Quotient (HQhuman) was calculated from Adult Exposure (AE) rates through fish andthe acceptable daily intake (ADI) for SMs.
1. AE= (Cf * FC)/BW) 2. (HQhuman = AE/ADI)
A human exposure risk assessment by fish consumption was assessed as per Yao et al. (2018). The
acceptable daily intake for SMs galaxolide, tonalide and MK are 150, 5 and 15 mg/kg BW, respectively(Block, 2003; P. Prevention, 2014; Worth and Patlewicz, 2007). Yao et al. (2018) and Boonsaner and
Hawker (2013) assessed human exposure of PCPs and found no risks. The present investigation
concludes that human exposure of SMs by fish consumption is negligible, and there are no human healthrisks in GFM
regions (Fig.7).

Fig.6. Human health risk assessment

Table. 1 Synthetic musk concentration (range, mean ± SD, and detection frequency) in seawater, sediment and fishsamples from Tamil Nadu Coastal
Marine Environment
Water (12)Synthetic

Range

Musks

Sediment (12)Mean ±

Df

SD

(%)

Range

Mean ±

Df

SD

(%)

Biota (8)Range

Mean ±

Df

SD

(%)

Galaxolidend-3.00.6 ± 1.2

25

nd-3.61.0 ± 1.08

67

nd-17822.3 ± 62.9

25

Tonalidend-0.80.08 ± 0.2

17

nd-0.50.04 ± 0.15

8

nd-13416.9 ± 47.5

37

Musk Ketonend-5.51.5 ± 2.1

42

nd-10.5

2.4 ± 3.7

42

nd-2.50.3 ± 0.9

12

Past achievement related to this project or meeting (article, conference presentation, award, patent,
etc. by PI and members)

Articles (Joint research publication):
1. BabuRajendran, R.,J.W. Kim,T. Isobe,K.H. Chang, A. Amano, T.W. Miller,
F.P.Siringan, S. Tanabe (2011). Determination of preservative and antimicrobial
compounds in fish from Manila Bay, Philippines using ultra high performanceliquid chromatography tandem mass spectrometry, and assessment of humandietary exposure. Journal Hazardous Materials 192: 1739-1745 (IF 4.114).
2. Kim, J.W., T. Isobe, R. BabuRajendran, K.H. Chang, A. Amano, T.W. Miller,
F.P.Siringan, S. Tanabe (2011). Contamination and bioaccumulation of
benzotriazole ultraviolet stabilizers in fish from Manila Bay, the Philippines using
an ultra-fast liquid chromatography-tandem mass spectrometry. Chemosphere 85:751-758 (IF 3.253).
3. Kim, J.W., R. BabuRajendran, K.H. Chang, T. Isobe, S. Tanabe(2011).
Multiresidueanalytical method for the determination of antimicrobials,
preservatives, benzotriazole UV stabilizers, flame retardants and plasticizers in fishusing ultra high performance liquid chromatography coupled with tandem mass
spectrometry. Journal of Chromatography A 1218:3511-3520 (IF 4.101).
4. Minh, N.H., T.B.Minh, N.Kajiwara, T.Kunisue, A.Subramanian, H.Iwata,
T.S.Tana, R.BabuRajendran, S.Karuppiah, P.H.Viet, B.C.Tuyen, S.Tanabe(2006). Contamination by Persistent Organic Pollutants in dumping sites of Asiandeveloping countries: implication of emerging pollution sources. Archives ofEnvironmental Contamination and Toxicology 50 (4): 474-481 (IF 1.864).
5. Kunisue, T., M. Watanabe, H. Iwata, A. Subramanian, I. Monirith, T.B. Minh, R.
BabuRajendran, T.S. Tana, P.H. Viet, M. Prudente, S. Tanabe (2004). Dioxins andrelated compounds in human breast milk collected around open dumping sites in
Asian developing countries: Bovine milk as a potential source. Archives ofEnvironmental Contamination and Toxicology 47: 414-426 (IF 1.864).
A.N. Subramanian
1. Annamalai Subramanian, Tatsuya Kunisue, Shinsuke Tanabe. 2015.Recent
Status of Organohalogens, Heavy Metals and PAHs Pollution in Specific
Locations in India. Chemosphere, 137:122-134.
2.

Lee HuuTuyen, Nguyen Minh Tue, Shin Takahashi, Go Suzuki, Pham Hung Viet,Annamalai Subramanian, Kesav A. Bulbule, PeethambaramParthasarathy,
AlagappanRamanathan, Shinsuke Tanabe. 2014. Methylated and unsubstitutedpolyaromatic hydrocarbons in street dust from Vietnam and India: Occurrence,distribution and in vivo toxicity evaluation. Enviro.Pollu., 194: 272-280.
3.

HazukiMizukawa, Kei Nomiyama, Tatsuya Kunisue, Michi X. Watanabe,
Annamalai Subramanian, Hisato Iwata, Mayumi Ishizuak, Shinsuke Tanabe.
2015. Organohalogens and their hydroxylated metabolites in the blood of pigs
from an open waste dumping site in south India: Association with hepatic
cytochrome P450. Environ. Res., 138: 255-263.

 Book Chapters:
1. Patil, N. N., Arun. E., Vimalkumar, K., & Ramaswamy, B. R. (2022). Phthalate
Esters and Their Ecotoxicological Risks from the Rivers of India. In Organic
Pollutants (pp. 153-176). Springer, Cham.
2. Nikhil NishikantPatil, S. Krishna Kumar, K. Vimalkumar, Arun. E,
BabuRajendran, R. Organochlorine pesticide contamination in the Kaveri(Cauvery) river, India: Water Challenges and Solutions on a Global Scale (Ed.
Satinder Ahuja), ACS Books, Washington, DC, 2015: 447p.
 Conference Presentation:
1. K. Vimalkumar, S. Govindaraj, Nikhil Nishikant Patil, E. Arun and R.
BabuRajendran. Non steroidalanti inflammatory drugs (NSAIDs) in major riversof Tamilnadu, India. International Conference on “Recent Trends in Bioscience”.
(07th – 09th February, 2016) at Alagappa University, Karaikudi, Tamilnadu, India.
2. Vimalkumar K, Bhuvaneswari R, Govindraj S, Arun E and BabuRajendran R.
Human and Environmental Risk Assessment of Organochlorine pesticides in Water
and Fish from River Cauvery, Tamilnadu. Two days workshop on “ Micropollutants
in water and their hazards” (12th – 13th January, 2015) at IIT, Madras, Tamil Nadu,
India.