The investigation aims to study the source and concentration of polycyclic aromatic hydrocarbon (PAHs) fractions in the surface sediments of selected estuaries of the southwest coast of Kerala India. The concentration of PAHs ranged from 0.47 to 126.64 ng/g. The estuarine sediments were enriched by HMW-PAHs and they are occupied nearly 93.76 % of the total concentration, followed by LMW-PAHs (LMW-PAH – 6.23%). The sum of surface sediment-associated PAH distribution was higher in the inner part of the estuary, especially at Anjuthengu and Kadinamkulam estuaries. The sediment grain size and distance of the sampling point from the coast are significantly playing an important role in the distribution of the PAHs. The ratio of LMW/HMW PAHs in this study indicating that the pyrolytic process is the chief source of PAHs in the estuarine sediments. The calculated total TEQ value ranged from 0.20 to 54.80 ng/g. A comparative study suggests that the obtained TEQ value was less than the other locations of India and worldwide.
Research Article
Distribution of Polycyclic Aromatic Hydrocarbons (PAHs) in Surface Sediments Collected From Selected Estuaries of Kerala, West Coast of India
https://doi.org/10.21203/rs.3.rs-632229/v1
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Low and high molecular weight PAHs
selected estuaries
surface sediments
Total toxic equivalent
Numerous studies have reported that polycyclic aromatic hydrocarbons (PAHs) are recognized as notable carcinogens mutagens and ubiquitous contaminants in a wide variety of mediums including air, food, sediments, and water. A wide variety of Solid-liquid extraction (SLE) methods was used to solve components of interest from solid samples such as soil or sediments using a suitable solvent. Various modes of SLE techniques such as maceration, ultrasonic-assisted extraction (UAE), microwave-assisted extraction (MAE), Soxhlet extraction (SE), and accelerated solvent extraction (ASE) were applied to extract this compound from chosen environmental samples (Ghassempour et al. 2008; Madej et al. 2018). The choice of the extraction procedure depended on several influential factors such as capital and operating cost, operation simplicity, required amount of organic solvent required, and the availability of a standardized method (Dean et al. 1997). The soxhlet extraction procedure was recommended by the US Environmental Protection Agency (US EPA) for extracting semi-volatile and non-volatile organics from solid matrices. However, they are arduous procedures, required a large amount of solvent, and not suitable for separating the thermally degradable compounds (De Castro et al. 1998).
The ultrasonic probe extraction procedure is an efficient method especially for their high extraction efficiency, lower equipment costs, ease of operation, little sample preparation, lower extraction temperatures, and suitability for trace level organic compounds in soil and sediments (Song et al. 2002; Banjoo et al. 2005). However, the efficiency of this method is depending on the solvent or solvent composition, extraction time, sample load, and water content (Berset et al. 1999). According to Sun et al. 1998, acetone was found to be the most efficient solvent for extracting the US EPA listed 16 priority pollutant PAHs in soils. The loss of hydrocarbon compounds by nearly 16% was observed during oven drying of samples at 45º C (Wong et al. 1980; Berset et al. 1999). The notable systematic study on dynamics of polycyclic aromatic hydrocarbons (PAHs) in surface sediments was reported at Cochin estuary by Ramzi et al. 2017. The present study aims to report the concentration of 16 USEPA listed PAHs in surface sediments of selected estuaries, west coast of Kerala, India
1.1 Study area
Kerala coastal area has been endowed with an expansive body of brackish waters including backwaters, lagoons, and estuaries including mangrove swamps. The chain of backwaters from south to north of the Kerala coast is interconnected by an extensive network of canals and they have played a significant role in the socio-economic status and cultural history of Kerala. Among the chain of backwaters, we selected four backwaters (Kayals means backwaters) namely Kadinamkulam, Anchuthengu, Kappil-Hariharapuram, Kayamkulam.
Kadinamkulam Kayal lying in between Lat 8° 35 to 8° 45 N and Long 76° 45 to 76° 56 E in the Thiruvananthapuram district. This is connected to the Veli Kayal on the southern side by the Parvathyputhanar canal and the Anchuthengu Kayal on the northern side through the lower reaches of the Vamanapuram River. Kadinamkulam backwater is connected with the sea only during the rainy season through the opening of the sand bar at Perumathura. Kappil-Hariharapuram Kayal is lying between 8°77' 75.90" to 8°78'88.13"N latitudes and 76°67'58.48" to 76°67'68.83"E longitudes. This backwater system receives freshwater input from the small river called Ayiroor Puzha. This Kayal is connected with Paravur Kayal through the Maniyamkulam canal. Kappil Kayal is widely used for fishing, retting, recreation, aquaculture, etc. Kayamkulam Kayal is a narrow stretch brackish water body, which is lying between 9° 2’and 9° 12’N latitude and 76°26’ and 76°32’E longitude. During flood season, this canal system was filled with fresh water from the Pampa and Achankoil River. Kayamkulam sand bar was developed parallel to the Kayal due to the tidal influence of the Arabian Sea. Ayirumthengu mangrove ecosystem was flourished in the southern low-lying areas of Kayamkulam Lake. This mangrove ecosystem was richly vegetated by Rhizophora sp., Avecenniasp. and Acanthus sp.
2.1 Sampling and Pre-treatment process
The surface sediments were collected from selected estuaries of the Kerala coast using a grid-based sampling method (Fig. 1). The sampling grid was created using the grid index features tool of Arc GIS 10.3. The pre-created grid plot was tracked by Locus Map Free (Version 3.50.1). The geographical coordinates of the sampling points were extracted from the KMZ extension file of the Arc GIS software package. Twenty surface sediments were collected from three selected estuaries of the Kerala coast (Kayamkulam, Anchuthengu, Kadinamkulam, and Varkala-Hariharapuram estuaries). The collected surface sediment was transferred to amber-colored glass jars using a pre-clean stainless steel spatula and kept in the icebox. The sediments were immediately transferred into the laboratory and kept under − 20°C in a deep freezer until analysis. The textural characteristics of the sediment (sand, silt, and clay) were determined by pipette analysis (Folk, 1980) in wet sediments. The surface sediments were freeze-dried, homogenized, and powdered using an agate mortar and pestle. The surface sediments were treated with 1N HCl and washed with double distilled water to remove salts and carbonates. The concentration of organic matter (OM) was estimated by exothermic heating followed by oxidation with potassium dichromate and concentrated H2SO4. An excess amount of dichromate was titrated against 0.5 N of ferrous ammonium sulfate (Gaudette et al., 1974).
2.2 Separation and analysis of PAHs
The sonication/ultrasonic agitation method was used to obtain higher extraction efficiencies during the extraction of the PAH fraction (Sun et al. 1998). Hence, the freeze-dried and homogenized sediment was used to extract the PAH with dichloromethane – methanol (2:1 ratio) solvent mixture in a sonication/ultrasonic agitation bath for 48 h and the obtained extract was treated with activate granular copper to remove the sulfur impurities. Finally, the extracted solution was evaporated using the rotary evaporation method and the extract was purified using the silica-alumina (2:1 ratio) column cleanup method. Later, the column was eluted with n-hexane to remove the aliphatic compounds followed by PAH compounds were eluted by n-hexane – dichloromethane mixture (3:7 ratio). The final extract was evaporated by a gentle nitrogen stream and the near-dryness extract was prepared for PAH determination using 500µl n-hexane. The USEPA listed sixteen PAHs were analyzed using a flame ionization detector on an Agilent 7890B Series Gas Chromatograph. The column temperature for analyses was initially programmed from 60°C (initial time, 2 min) at a rate of 10°C per min, 120–300°C at a rate of 3° C per min, and held at 310° C for 5 min. The injector and detector were kept at 280° C and 325° C respectively and the injection volume was 2 µL during both injection modes. The extraction efficiency was cross-checked based on the recovery output of the known amount of PAH standard mixture. The recovery of PAHs varied between 82% and 95%. All the chemical analyses were done in triplicates and output results are expressed on a dry weight basis. The sum of the PAH, high and low molecular weight rings, and potential toxic equivalent as shown in bar charts.
3.1 Concentration of LMW and HMW ring PAHs
The studied PAH fractions were classified as low molecular weight PAHs (2 and 3 rings) and high molecular weight PAHs (4 and above rings). The name of the studied PAH fractions, the number of rings, concentration range, mean, standard deviation, Toxic Effects-Range Low (ERL), Toxic Effects-Range Medium (ERM), Carcinogenic potency, and molecular weight of each PAHs were shown in Table 1. The surface sediments of the estuaries were dominated by fine-grained silt to clay grade fractions and few samples from the mouth of the estuaries were exhibiting sandy nature. The total PAH concentration ranges from 0.47 to 126.64 ng/g, with a mean value of 15.08 ng/g. In detail, the low molecular weight rings (LMW rings − 2 & 3 rings) in the sediments range from 0 to 5.42 ng/g, whereas heavy molecular weight rings (HMW rings − 4 & above rings) concentration ranges from 5.42 to 122.1 ng/g. The estuarine sediments were enriched by HMW-PAHs and they are occupied nearly 93.76 % of the total concentration, followed by LMW-PAHs (LMW-PAH – 6.23%). Among the LMW ring PAHs, Naphthalene, Acenaphthene, and Anthracene was detected as a high enriched compound, whereas HMW-PAHs was enriched by Benzo(b)fluoranthene, Benzo(k)fluoranthene, Benzo(a)pyrene, Indeno[1,2,3-cd]pyrene, and Benz[ghi]perylene (Table 1). The sediment-associated Ʃ16 PAHs distribution was higher in the inner part of the estuary, especially at Anjuthengu and Kadinamkulam estuaries. Similar studies on the Cochin estuary also supported that the distance of the sampling point from the estuary mouth and inundated seawater also act as a controlling factor of the distribution of PAHs. The enrichment of PAHs in the inner part of the estuarine system was indirectly affected by sediment characteristics, fluvial and tidal flow processes. According to Safe, 1998, benzo[a]pyrene is one of the most toxic of the parent PAH, and this compound is used as a surrogate chemical marker for genotoxic organic compounds. The possible source of the PAHs was due to the proximity of anthropogenic activities such as road run-off and/or combusted particulates from vehicles or possibly the railway tracks (Vane et al. 2020). According to the previous studies, the relationship between the organic carbon/natural organic matters including humic substance coasting in the mineral surface directly affected the distribution of PAHs (Stout and Emsbo-Mattingly, 2008; Ukalska Jaruga et al., 2018). Further, this investigation suggests that the relationship between TOC and PAHs showing a positive correlation in sediment cores. The negative correlation significance was shown in between grain size (sand-silt and clay ratio) from the Mersey estuary (Vane et al., 2007), whereas ƩPAHs in sediment and pore water of the Yellow river China showing a positive relationship with silt and fine grain fractions. The surface sediments of this study suggesting a similar observation especially in the inner part of the estuaries, where the sediment is enriched with fine fractions (Yu et al. 2009; Maruya et al. 1996; Maruya et al. 1997).
The PAHs reached the marine environment through both the high-temperature pyrolytic processes and the petrogenic source (Xu et al. 2007). The rapid increase of PAHs in the Cochin estuary was chiefly controlled by monsoonal changes, land/river runoff, and the combustion of pyrolytic source materials. Further, the reported total PAH concentration of the Cochin estuary was 100 times higher than in the present study. A comparative study of PAHs in sediments was compared with previously reported investigations of India and worldwide. The earlier studies on PAH distribution in aquatic ecosystems were significantly affected by sediment texture, organic content, and flow characteristics (He et al., 2014; Kumar et al., 2016; Vane et al. 2020). The concentration of PAHs in selected estuaries of the west coast was lower than in the other study region.
PAHs in sediments could cause liver neoplasm and other abnormalities in bottom-dwelling fish (Malins et al. 1988; Vethaak et al. 1992), and with delayed hatching, induction of deformities, disruption of larvae swimming activity, and DNA damage (Cousin and Cachot, 2014). The ratio between low molecular weight and high molecular weight PAH fractions can be used to identify the sources of PAH. The calculated ratio was > 1 indicates the petrogenic source of PAH, whereas ratio < 1 indicates the pyrolytic source. In this study, the ratio of LMW/HMW PAHs indicating that pyrolytic fractions dominate in these estuaries.
NOAA's sediment quality guideline was widely applied to determine the contamination level of PAHs in the aquatic system (NOAA, 1999). Long et al. 1995 suggested the two important tools such as Effect Range Low (ERL) and Effect Range Median (ERM) to determine the sediment quality level. Both indices (ERL and ERM) were helpful to enumerate the threshold value and rarely occurring adverse biological effects. The toxicological values with their effect ranges are used to assess the sediment quality, i.e. 10th percentile represented as an effect range low (ERL) and the 50th percentile ranked as effect range medium (ERM) (Long et al. 1995). The PAH distribution in the selected estuaries of Kerala indicates that the concentration of PAHs was less than the SQGs suggested ERL and ERM values. The analytical results of PAHs concluded that the surface sediments of the selected estuarine system falling under the low contamination and low-risk category.
The sediment's toxicity range was assessed from the sum of all potential carcinogenic PAH congers (TCPAH - BaA, Chr, BbF, BkF, BaP, DbA, and InP fractions; Chen and Chen, 2011). The TCPAH values of the surface sediments of the estuaries were ranged from 16 to 44.21 ng/g. The analytical value of the TCPAH was less than the SQGs reported ERL-ERM values (1373– 8410 ng/g; Long et al., 1995). The potential toxicity is the toxic equivalent (TEQ) of individual PAH was derived using the following equation (Nasher et al., 2013; Li et al., 2015).
Where, Ci is the concentration of an individual PAH fraction and TEFi is the toxicity factor of individual fractions. The TEF of BaA, Ch, BbF, BkF, BaP, IP and DbA are 0.1, 0.001, 0.1, 0.01, 1, 0.1 and 1 respectively (USEPA, 1993). The calculated total TEQ value ranged from 0.20 to 54.80 ng/g (Fig. 2). A comparative table of TEQ value with other study regions suggests that the obtained TEQ from this study was less than the other locations of India and worldwide (Table 4).
The outcome of the investigation suggests that the surface sediments of selected estuaries of the Kerala coast were less contaminated by other compared study areas around the world. Further, the present study area was less contaminated by polycyclic aromatic hydrocarbons (PAHs) and experiencing less ecological risk.
Ethics approval and consent to participate
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Consent for publication
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Availability of data and materials
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Competing interests
No Competing interests
Funding
No fundings received from funding agency to carry out the work
Authors' contributions
Krishnamoorthy Radhakrishnan & Shaik Mohammed. Hussain : Conceptualization, Visualization
Subbiah Krishnakumar, Kaliyaperumal Sanjai Gandhi & Dhanasekaran Pradhap : Conceptualization,Investigation, Writing - original draft
Nazeerkhan Akramkhan, Palanichamy Prakasheswar &: Fieldwork & Sample collection
Subbiah Maheswaran & Anandarao Rajkumar: Investigation & Data curation
Acknowledgements
The authors thank Dr.S.M Hussain, Professor and Head, Department of Geology, University of Madras, Guindy Campus, Chennai- 600 025 for providing the laboratory facilities to carry out the analysis.
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Table 1 concentration ranges, mean and standard deviation (S.D) of individual PAHs (ng/g) in the surface sediments, Kayals of West coast of Kerala, India
|
S.no |
Name of the PAH |
No of rings |
Sediment (n = 20) |
Carcinogenic potencya |
Molecular weight |
||||
|
Range (ng/g) |
Mean (ng/g) |
S.D. (ng/g) |
ERL |
ERM |
|||||
|
1 |
Naphthalene (Nap) |
2-Ring |
ND - 3.99 |
0.511 |
0.987 |
160 |
2100 |
D |
128.18 |
|
2 |
Acenaphthylene (Acy) |
3-Ring |
ND |
ND |
ND |
44 |
640 |
- |
152.2 |
|
3 |
Acenaphthene (Ace) |
3-Ring |
ND |
ND |
ND |
16 |
500 |
- |
154.2 |
|
4 |
Anthracene (Ant) |
3-Ring |
ND - 2.12 |
0.106 |
0.474 |
853 |
1100 |
D |
178.24 |
|
5 |
Phenanthrene (Phe) |
3-Ring |
ND - 2.15 |
0.250 |
0.579 |
240 |
1500 |
D |
178.24 |
|
6 |
Fluorene (Fl) |
3-Ring |
ND - 0.55 |
0.028 |
0.123 |
19 |
540 |
D |
166.23 |
|
7 |
Benzo(a)anthracene (BaA) |
4-Ring |
ND - 7.29 |
1.160 |
1.691 |
261 |
1600 |
B2 |
228.3 |
|
8 |
Chrysene (Chr) |
4-Ring |
ND - 6.88 |
0.800 |
1.559 |
384 |
2800 |
B2 |
228.3 |
|
9 |
Fluoranthene (Flu) |
4-Ring |
ND - 6.5 |
0.823 |
1.442 |
600 |
5100 |
D |
202.26 |
|
10 |
Pyrene (Pyr) |
4-Ring |
ND - 6.71 |
0.763 |
1.492 |
665 |
2600 |
D |
202.26 |
|
11 |
Benzo(b)fluoranthene (BbF) |
5-Ring |
ND - 12.19 |
1.727 |
2.692 |
320 |
1800 |
B2 |
252.32 |
|
12 |
Benzo(k)fluoranthene (BkF) |
5-Ring |
ND - 19.7 |
1.908 |
4.405 |
280 |
1620 |
B2 |
252.32 |
|
13 |
Benzo(a)pyrene (BaP) |
5-Ring |
ND - 21.28 |
2.211 |
4.645 |
430 |
1600 |
B2 |
252.32 |
|
14 |
Dibenzo(a,h)anthracene (DBA) |
5-Ring |
ND - 8.68 |
0.874 |
1.974 |
63.4 |
260 |
B2 |
278.35 |
|
15 |
Indeno [1,2,3-cd] pyrene (InP) |
6-Ring |
ND - 15.46 |
2.098 |
3.409 |
- |
- |
B2 |
276.34 |
|
16 |
Benz[ghi]perylene |
6-Ring |
ND - 17.41 |
1.074 |
3.951 |
430 |
1600 |
D |
276.34 |
B2 Probable carcinogen, D - not classifiable as to human carcinogenicity (USEPA carcinogenic classificationa), S.D – Standard Deviation, ND – Not detected, ERL - Toxic Effects-Range Low, ERM - Toxic Effects-Range Medium
Table 2 sample wise distribution of sand, silt and clay (in %), low molecular and high molecular weight rings (ng/g), Total PAH (ng/g) of surface sediments, Kayals of West coast of Kerala, India
|
Location |
1 |
2 |
3 |
4 |
5 |
6 |
7 |
8 |
9 |
10 |
11 |
12 |
13 |
14 |
15 |
16 |
17 |
18 |
19 |
20 |
|
Sand % |
73 |
18.2 |
73.8 |
23.6 |
96.6 |
69.6 |
86.2 |
29.4 |
83.4 |
75.2 |
13.8 |
4.2 |
85.8 |
4.6 |
2 |
42 |
2.2 |
0.8 |
44.4 |
94.4 |
|
Silt % |
26.2 |
80.8 |
25.4 |
76 |
3 |
25.4 |
13.4 |
70.4 |
16.4 |
24.8 |
85.8 |
95.4 |
14 |
95 |
97.6 |
57.6 |
97 |
98.8 |
55 |
5.2 |
|
Clay % |
0.8 |
1 |
0.8 |
0.4 |
0.4 |
5 |
0.4 |
0.2 |
0.2 |
0 |
0.4 |
0.4 |
0.2 |
0.4 |
0.4 |
0.4 |
0.8 |
0.4 |
0.6 |
0.4 |
|
LMW rings |
0 |
0.81 |
5.42 |
2.77 |
0 |
0 |
0 |
0 |
0 |
0.65 |
0 |
0 |
1.28 |
4.54 |
1.05 |
0 |
0 |
0 |
1.35 |
0 |
|
HMW rings |
1.38 |
10.16 |
11.14 |
7.56 |
0.47 |
0.8 |
1.94 |
12.68 |
3.34 |
5.68 |
19.73 |
3.33 |
27.68 |
122.1 |
8.12 |
0.51 |
3.06 |
0 |
13.83 |
15.18 |
|
Total PAH |
1.38 |
10.97 |
16.56 |
10.33 |
0.47 |
0.8 |
1.94 |
12.68 |
3.34 |
6.33 |
19.73 |
3.33 |
28.96 |
126.64 |
9.17 |
0.51 |
3.06 |
ND |
15.18 |
15.18 |
|
Total TEQ |
0.60 |
4.75 |
7.17 |
4.47 |
0.20 |
0.35 |
0.84 |
5.49 |
1.45 |
2.74 |
8.54 |
1.44 |
12.53 |
54.80 |
3.97 |
0.22 |
1.32 |
0.00 |
6.57 |
6.57 |
ND – Not detected, LMW rings - Low molecular weight rings (2 & 3 rings); HMW rings - High molecular weight rings (4 & above rings), TEQ – Toxic equivalent
Table 3 comparison table of polycyclic aromatic hydrocarbon (PAHs) in the present study and other worldwide estuarine and coastal systems report
|
S.no |
Details of the study region |
Concentration Sum of PAH |
References |
|
1 |
Mersey Estuary, UK |
626–3766 |
Vane et al. 2007 |
|
2 |
Norwegian harbors, Norway |
2100–31100 |
Cornelissen et al. 2006 |
|
3 |
San Francisco Bay, USA |
26.1–600 |
Maruya et al. 1996 |
|
4 |
Tokyo Bay, Japan |
534–292370 |
Zakaria et al. 2002 |
|
5 |
Xiamen Harbor, China |
247–480 |
Zhou et al. 2000 |
|
6 |
Minjiang River Estuary, China |
112–877 |
Zhang et al. 2004 |
|
7 |
Jiulong River Estuary and Western Xiamen Sea, China |
59–1177 |
Maskaoui et al. 2002 |
|
8 |
Yellow River, China |
464–2621 |
Yu et al. 2009 |
|
9 |
Himalayan lakes, Nepal |
67.9 ± 22.1 |
Guzzella et al. 2011 |
|
10 |
Seine River basin, France |
5000 - 90,000 |
Lorgeoux et al. 2016 |
|
11 |
Minnesota lakes, USA |
489.3 ± 980.5 |
Crane et al. 2017 |
|
12 |
Cochin estuary, India |
194–14149 |
Ramzi et al. 2017 |
|
13 |
Chitrapuzha River, India |
5046–33087 |
Kumar et al. 2016 |
|
14 |
Hugli river, India |
0–1839 |
Zuloaga et al. 2013 |
|
15 |
Iko River estuary mangrove system, Nigeria |
6100–35,270 |
Essein et al. 2011 |
|
16 |
Esterode Urias, estuary, Mexico |
27–418 |
Jaward et al. 2012 |
|
17 |
Patos Lagoon Estuary, Brazil |
89–10451 |
Garcia et al. 2010 |
|
18 |
Galician estuaries, NW Spain |
44–7901 |
Perez-Fernandez et al. 2015 |
|
19 |
Selangor River estuary, Malaysia |
203–964 |
Masood et al. 2016 |
|
20 |
Selected estuaries of west coast of Kerala |
Present study |
Table 4 Comparison of TEQ values of surface sediments of the selected estuaries of Kerala coast, Southwest coast of India with data from other areas worldwide
|
Study area |
TEQ (ng/g) |
References |
|
Naples Harbour, Italy |
2–4723 |
Sprovieri et al. 2007 |
|
Kaohsiung Harbor, Taiwan |
1404–1964 |
Chen and Chen, 2011 |
|
Bahia Blanca Estuary, Argentina |
0–1969 |
Oliva et al. 2015 |
|
Meiliang Bay in China |
94–856 |
Qiao et al. 2006 |
|
Xiamen Bay, China |
15–282 |
Li et al. 2010 |
|
Ría Arousa, Spain |
1.2–820 |
Perez-Fernandez et al. 2015 |
|
Sundarban mangrove wetland, Bangladesh |
13–1014 |
Zuloaga et al. 2013 |
|
Sundarban mangrove wetland, India |
1–2451 |
Zuloaga et al. 2013 |
|
West coastal of the Gulf of Tunis, Tunisia |
8–666.4 |
Mzoughi and Chouba, 2011 |
|
Cochin Estuary, India |
1–971 |
Ramzi et al. 2017 |
|
Selected estuaries of Kerala Southwest coast of India |
0.29 – 54.80 |
Present study |