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Polycyclic aromatic hydrocarbons (PAHs) at the Gulf of Kutch, Gujarat, India: Occurrence, source apportionment, and toxicity of PAHs as an emerging issue
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Polycyclic aromatic hydrocarbons (PAHs) at the Gulf of Kutch, Gujarat, India: Occurrence, source apportionment, and toxicity of PAHs as an emerging issue Rahul K. Rajpara, Dushyant R. Dudhagara, Jwalant K. Bhatt, Haren B. Gosai, Bharti P. Dave⁎ Department of Life Sciences, Maharaja Krishnakumarsinhji Bhavnagar University, Sardar Vallabhbhai Patel Campus, Bhavnagar 364001, Gujarat, India
A R T I C L E I N F O
A B S T R A C T
Keywords: Polycyclic aromatic hydrocarbons (PAHs) Source apportionment Sediment quality guidelines (SQGs) Risk assessment Toxic equivalent quotient (TEQ)
The present study extrapolates the assessment and characterization of a barely studied region, the Gulf of Kutch, (near Jamnagar), Gujarat, India, in terms of PAH exposure, adverse effects caused by them, and various toxicological indices showing the catastrophic effects of their elevated concentrations. ΣPAH concentration in the site ranged from 118,280 to 1,099,410 ng g− 1 dw, with a predominance of 2–3-ring PAHs (79.09%) as compared to 4–5- and 6-ring PAHs (20.91%). The concentrations of carcinogenic PAHs were found to be between 8120 and 160,000 ng g− 1 dw, with a mean of 63,810 ng g− 1 dw, which is much higher than normal acceptable values. The toxic equivalent quotient for 6CPAHs ranged from 150.47 to 26,330 ng g− 1 BaPeq, encompassing 50.63% of ΣPAH toxicity. This toxicological profile of the present study site would be of paramount importance as it offers fresh information regarding the load of legacy pollutants such as PAHs and the inputs and methods to cope with their extremely high concentrations in less explored marine habitats.
Rapid economic development and the increasing consumption of petroleum and coal in developing countries such as India are among the prime reasons for the growing concern for developing methods to treat an array of pollutants, which otherwise could cause severe ailments and threaten environmental health globally. Polycyclic aromatic hydrocarbons (PAHs) are found in almost every ecological matrix because of extensive anthropogenic intrusion. They possess an ecological risk as some of them have been reported to be carcinogenic, mutagenic, and/or teratogenic in nature (Kim et al., 2013; Huang et al., 2012; Pietzsch et al., 2010). The composition of PAH assemblage in marine sediment mainly depends on the sources of PAHs and the extent of innate processes they undergo since their discharge into marine environments (Neff et al., 2005). PAHs are exposed to various components of the ecosystem because of vehicle exhaust and other anthropogenic activities, such as industrialization, and can be accumulated in terrestrial and marine ecosystems as a result of dry and wet deposition of PAH fine particles, direct riverine and petroleum inputs, and urban runoffs. These factors contribute to elevate PAH concentrations in marine sediments, thereby making marine sediments the ultimate sinks of these refractile compounds (Bhatt et al., 2014; Pietzsch et al., 2010). Sources of PAHs in marine sediments are classified into pyrogenic (pyrolytic), petrogenic, and diagenic sources. Pyrolytic sources include
⁎
the combustion processes of fossil fuels, incomplete combustion of organic materials such as wood, coal, and oil, and anthropogenic activities characterized by HMW PAHs. Petrogenic input is attributed to petroleum products, off shore exploitations, urban runoffs, and oil seeps due to natural activities. Diagenic PAHs such as perylene are formed because of biological processes and are found in both marine and freshwater sediments (Dudhagara et al., 2016a, 2016b; Barakat et al., 2011; Jiang et al., 2009). PAHs have always been associated with an increased risk of developing cancer in various human tissues including skin, lung, bladder, and stomach. The severity of the cancer developed depends on the mode of exposure and the form of PAHs (Kim et al., 2013). PAHs are also known as endocrine disrupting compounds because of their ability to bind endogenous receptors (Wattiau, 2002). Recently, the surrounding areas of the Gulf of Kutch (near Jamnagar), Gujarat, India, have been experiencing a great deal of economic development as special economic zones (SEZs); this often results in the risk of environment pollution due to the release of toxic organic compounds and oil spills from petrochemical plants, ship transport, ship breaking–recycling activities, and other anthropogenic activities in marine ecosystem. However, data on the sources, mechanism, and distribution of PAHs and their potential risks to environment health is scarce. This knowledge gap needs to be filled by determining
Corresponding author at: Department of Life Sciences, Maharaja Krishnakumarsinhji Bhavnagar University, Sardar Vallabhbhai Patel Campus, Bhavnagar 364001, Gujarat, India. E-mail address: [email protected] (B.P. Dave).
http://dx.doi.org/10.1016/j.marpolbul.2017.04.039 Received 13 November 2016; Received in revised form 16 April 2017; Accepted 22 April 2017 0025-326X/ © 2017 Elsevier Ltd. All rights reserved.
Please cite this article as: Rajpara, R.K., Marine Pollution Bulletin (2017), http://dx.doi.org/10.1016/j.marpolbul.2017.04.039
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Fig. 1. (A) Geographic location of the study site and (B) various sampling points.
they pose in marine sediments. Contaminated surface sediment samples were collected from the Gulf of Kutch (Fig. 1). The study area included the upstream part of the gulf. It was divided into 12 points along the coastline of the Gulf of Kutch, as shown in Fig. 1(A, B), with a distance of 200 m between two consecutive sampling points. Sampling was performed from January 2012 to December 2013. From each sampling point, samples of surface sediments were collected in triplicates and immediately transferred to amber glass bottles and stored at − 20 °C until further analysis. In total, 36 (12 × 3) samples were collected, and the results of the analyses were expressed as the mean of triplicate samples.
the distribution of priority PAHs present in oil-contaminated sediments of the Gulf of Kutch. As described earlier, the apportionment of PAH sources was performed on the basis of the isomeric ratios of the PAHs to (i) evaluate the ecological risks caused by each PAH according to sediment quality guidelines (SQGs) and sediment quality criteria (SQCs) and (ii) evaluate the combined ecological risk and the toxicity levels of PAHs by using mean effects range median quotient (M-ERM-Q) and toxic equivalent quotient (TEQ) analyses, respectively. Thus, the results of this study can be a meaningful reference by providing baseline information on the sources of PAHs, toxicity levels of individual PAH, and ecological risk
2
3
39,060 ± 0.02 42,240 ± 0.01 5330 ± 0.03 ND 20,170 ± 0.01 65,060 ± 0.03 3050 ± 0.02 5070 ± 0.01 1250 ± 0.02 5260 ± 0.02 ND 4440 ± 0.01 ND ND 5250 ± 0.020 ND 29,070 ± 0.03 15,330 ± 0.111 9080 ± 0.020 ND 63,860 ± 0.02 31,050 ± 0.02 25,080 ± 0.02 ND ND ND ND 6730 ± 0.02 ND ND 5300 ± 0.11 ND Where Values in ng g− 1 dw of sediment 1 Nap, 2 Ace, 3 Acel, 4 Flu, 5 Phe, 6 Ant, 7 Flt, 8 Pyr, 9 Chr, 10 BaA, 11 BbF, 12 BkF, 13 BaP, 14 DahA,1 5 BghiP, 16 IP. ND = not detected or below the detection limit (< DL).
39,060 ± 0.01 ND 5260 ± 0.05 ND 20,160 ± 0.05 66,030 ± 0.11 3060 ± 0.01 13,430 ± 0.01 1560 ± 0.02 545 ± 0.01 ND ND ND 1140 ± 0.01 ND ND 9060 ± 0.01 23,530 ± 0.025 ND 5570 ± 0.01 59,210 ± 0.30 22,050 ± 0.01 ND 36,070 ± 0.02 38,740 ± 0.56 12,340 ± 0.02 ND 3180 ± 0.07 ND 2040 ± 0.01 ND ND 11,070 ± 0.01 ND ND ND 67,660 ± 0.12 5060 + 0.030 11,320 ± 0.01 13,600 ± 0.02 ND ND ND ND ND ND 9570 ± 0.01 ND 8030 ± 0.01 ND 13,050 ± 0.01 ND 31,470 ± 0.01 62,050 ± 0.010 23,600 ± 0.005 ND ND ND ND ND 6040 ± 0.01 ND 12,330 ± 0.010 ND 11,930 ± 0.02 ND 16,170 ± 0.05 2040 ± 0.01 25,060 ± 0.02 30,480 ± 0.05 ND 12,050 ± 0.01 22,290 ± 0.03 ND ND ND 12,510 ± 0.01 ND 6680 ± 0.010 ND ND ND ND ND 29,400 ± 0.10 58,050 ± 0.01 10,060 ± 0.01 8030 ± 0.01 ND ND ND 9560 ± 0.01 ND 2350 ± 0.01 11,150 ± 0.020 ND 31,750 ± 0.00 56,240 ± 0.01 ND ND 91,130 ± 0.05 106,050 ± 0.01 45,660 ± 0.02 48,720 ± 0.005 ND 20,050 ± 0.030 ND ND ND ND ND 9220 ± 0.005 173,320 ± 0.68 ND 413,860 ± 0.20 ND 260,330 ± 0.1 28,890 ± 0.58 16,560 ± 0.05 28,320 ± 0.40 57,550 ± 0.31 116,730 ± 0.41 ND ND ND 2590 ± 0.21 1260 ± 0.03 ND 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
119,530 ± 0.40 ND 430,260 ± 0.20 ND 230,550 ± 0.50 50,500 ± 0.33 9720 ± 0.18 16,040 ± 0.48 23,450 ± 0.35 ND ND ND 5530 ± 0.02 ND 3550 ± 0.015 ND
S4 S3 S2 S1 PAHs
Table 1 Distribution of the 16 priority PAHs listed by the USEPA in sediment samples S1–S12.
S5
S6
S7
S8
S9
S10
S11
S12
Prior to the extraction of 16 priority PAHs listed by the United States Environmental Protection Agency (USEPA, 1993), sediment samples were dried using sodium sulfate and sieved through a 10-mm stainless-steel mesh (> 2 mm) (Pietzsch et al., 2010). For the extraction of PAHs, a 10-g sample was added to 50 mL of dichloromethane:acetone mixture (1:1 v/v). This mixture was then placed in an ultrasonicator bath (Fisher Scientific, Mumbai, India) for 5 min, with 1 min of rest. This procedure was repeated twice, and each time, the supernatant (solvent phase) was pooled. The extract was combined and concentrated to 2–4 dichloromethane:acetone mixture using rotary vacuum evaporator (Büchi R215, Switzerland) (Dave et al., 2014). The extract was then cleaned using a chromatography column prepared with aluminum oxide (Al2O3) prior to the removal of elemental sulfur and humic materials, as suggested by Oros and Ross (2004) and Pietzsch et al. (2010). The final extract was further concentrated to 1 mL for GC–MS analysis, as described by Dudhagara et al. (2016a, 2016b) (Shimadzu QP2010 +, Japan). All analytical procedures and the obtained data were subjected to quality control. A standard PAH mixture containing the 16 USEPA priority PAHs, procured from Supelco, Bellefonte, USA, was subjected to the QA/QC procedure. The standard PAH mixture consisted of naphthalene (Nap), acenaphthene (Ace), acenaphthylene (Acel), fluorene (Flu), phenanthrene (Phe), anthracene (Ant), fluoranthene (Flt), pyrene (Pyr), benzo(a)anthracene (BaA), chrysene (Chr), benzo(b) fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene (BaP), dibenzo(a,h)anthracene (DahA), indeno(1,2,3-cd)pyrene (IP), and benzo(g,h,i)-perylene (BghiP). In addition to analyzing field samples, method blank (solvent), spiked blank (standard spiked with solvent), and matrix spiked blank (soil spiked with PAHs) samples were also analyzed simultaneously. The analysis of procedural blanks showed that the analysis system and the glassware used in this study were free of contamination. The relative standard deviations were < 15% on PAH measurements of recovery protocol, with an average ranging between 53.25 ± 14% and 111.73 ± 21%. From the signal-to-noise ratio of 3:1 in the blank samples, the method detection limit (MDL) of PAHs was estimated to be 50 ng g− 1 dw for individual PAHs (Dudhagara et al., 2016a, 2016b). The USEPA 16 priority PAHs were frequently detected in sediment samples, and their mean concentrations are presented in Table 1. The results indicate that majority of priority PAHs were present in all sediment samples. The concentration ranges (in ng g− 1 dw) of predominant PAHs were as follows: Nap 1260–173,320; Ace 3550–11,930; Acel 9220–106,050; Phe 2040–30,480; Ant 6040–62,050; Flt 5060–13,600; and Pyr 3180–59,210. The sequence of the 15 PAH congeners ordered according to their mean concentration was Acel > Phe > Ant > Nap > Pyr > Flt > BaA > Chr > Ace > DahA > BkF > BaP > BghiP > IP > Flu. The above results suggest that the contamination at the Gulf of Kutch was dominated by LMW PAHs. The pattern of distribution in sediment samples was found to vary, which could be attributed to the flux of the various coastal activities (De Luca et al., 2004). The level of PAH contamination in sediments was categorized into four levels: (i) low (0–100 ng g− 1), (ii) moderate (100–1000 ng g− 1), (iii) high (1000–5000 ng g− 1), and (iv) very high (> 5000 ng g− 1) (Baumard et al., 1998). According to this classification, the Gulf of Kutch, with a PAH concentration of 118,280–1,099,410 ng g− 1 dw, could be considered a very highly polluted site. Table 2 shows a comparison of ΣPAH concentrations (ng g− 1 dw) in surface sediments of different estuaries around the world and their adjacent coastal regions, as reported in previous studies, and those found in the present study. ΣPAH concentrations in sediments ranged from 118,280 to 1,099,410 ng g− 1 dw, with a mean value of 3.21 × 105 ng g− 1 dw. The results of the present study indicated that 96.29% of the ΣPAHs were LMW PAHs, while 3.71% were HMW PAHs. To the best of our knowledge, this study has reported the third highest ΣPAH concentration along the coastal regions around the world.
80,350 ± 0.05 7040 ± 0.01 23,260 ± 0.03 ND 8050 ± 0.03 53,060 ± 0.01 22,170 ± 0.02 870 ± 0.01 5630 ± 0.03 6050 ± 0.03 ND 3940 ± 0.020 2150 ± 0.030 ND 16,130 ± 0.020 ND
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Table 2 ΣPAHs detected at various international coastal areas including that at the present site.
1 2 3 4 5 6 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Location
Range (ng g− 1)
Mean (ng g− 1)
References
Izmit Bay, Marmara Sea, Turkey Hsin-ta Harbour, Taiwan Santander Bay, Spain Barcelona harbor, Spain Dalian Bay, China Liaodong Bay, China Biscay Bay, France Porto Torres, Sardinia, Italy Meizhou Bay, China Minjiang River Estuary Pearl River Estuary, China Northwest Mediterranean Sea Leizhou Bay, China Zhanjiang Bay, China Boston Harbour, USA Narragansett Bay, USA West Mediterranean Sea Black Sea coast, Turkey Alang-sosiya, India Gulf of Kutch, India
3.0 × 104–1.67 × 106 156–3382 1620–344,600 16,300–10,320 32.70–3558.88 276.26–1606.89 20–5159 70–1210 196.7–299.7 174.96–817.40 323–2372 86.5–48,090 21.72–319.61 41.96–933.90 7266–358,092 569–216,000 1.5–20,440 10–530 5020–981,000 118,280–1,099,410
6.01 × 105 – –
Telli-Karakoc et al., 2002 Fang et al., 2003 Viguri et al., 2002 Martínez-Lladó et al., 2007 Liu et al., 2001 Men et al., 2009 Tronczynsky et al., 2004 De Luca et al., 2004 Lin et al., 2003 Yuan et al., 2001 Mai et al., 2001 Benlahcen et al., 1997 Huang et al., 2012 Huang et al., 2012 Wang et al., 2001 Hartmann et al., 2004 Baumard et al., 1998 Readman et al., 2002 Dudhagara et al., 2016a, 2016b Present study
1152.08 743.03 – – 256.1 437.21 1587 – 103.91 315.98 – 21,100 – – 345,000 321,635
Fig. 2. Abundance of PAHs in the surface sediments of the Gulf of Kutch.
The majority of the PAHs in marine sediments originate from pyrogenic and petrogenic sources. Pyrolytic PAHs are produced from incomplete combustion of carbon and wood fossil fuels, and they are characterized by compounds with 4–6 aromatic rings, while petrogenic PAHs are generally of LMW. The ratio LMW/HMW PAHs differentiates petrogenic (> 1) and pyrogenic (< 1) sources. LMW/HMW PAH ratio of the 12 sediment samples (S1–S12) in this study ranged from 1.29 to 14.45, which suggests that the contamination was due to petrogenic sources [Fig. 3(A)] (Liu et al., 2008; Soclo et al., 2000). Phe has two thermodynamically stable structural isomers. Therefore, a higher Phe/ Ant ratio (> 10) was observed in petrogenic sources and a lower ratio (< 10) in pyrolytic sources (De Luca et al., 2004; Soclo et al., 1986). Fig. 3(B) shows that Phe/Ant ratio ranged from 0.151 to 13.37, suggesting that the PAHs in surface sediments could have originated from mixed sources. Fig. 3(B) also shows that the ratios of Ant/Ant + Phe in S1 and S7 were 0.09 and 0.06 (< 0.1), respectively, whereas the rest of the samples had a value > 0.1, suggesting the dominance of pyrogenic over petrogenic contamination (Rahmanpoor et al., 2014; Yunker et al., 2002). The ratio Flt/Pyr in most sediment samples was < 1, indicative of contamination by petrogenic sources (Magi et al., 2002). When Flt/(Flt
Fig. 2 shows the group profile of the 16 PAHs. The PAHs detected were categorized into four groups depending on the number of aromatic rings (Essien et al., 2012): group i: 2–3-ring PAHs accounting for 79.09% of the total PAHs, group ii: 4-ring PAHs accounting for 17.20% of the total PAHs, group iii: 5-ring PAHs contributing the least, only 1.61%, to the total PAHs, and group iv: 6-ring PAHs representing 2.09% of the total PAHs. This profile suggested that petrogenic PAHs such as 2–3-ring PAHs have contributed the most to the total PAHs. A remarkable observation was that the presence and concentration of 6ring PAHs (group iv) were slightly higher than those of 5-ring PAHs (group iii). The findings suggest that the persistence of 6-ring PAHs in sediments may be because they are resistant to microbial attack or cannot be used as carbon and energy sources. The characteristics of PAH pattern in marine sediments are subjected to different emission sources. It is necessary to determine the PAH sources for controlling their input and allocating responsibility for bioremediation activity (Zhang et al., 2016). To recognize the sources of PAHs, we compared the characteristic isomeric PAH ratios of LMW/ HMW, Ant/Ant + Phe, Phe/Ant, Flt/Pyr, and Flt/(Flt + Pyr) found in the present study with those reported in previous studies (Eguvbe et al., 2015; He et al., 2014; Yunker et al., 2002). 4
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Fig. 3. Cross-plots for the isomeric ratios (A) Flu/Flu + pyr vs. LMW/HMW, (B) Ant/Ant + Phe vs. Phe/Ant, and (C) Flu/Flu + pyr vs. Flu + Pyr.
These ratios revealed that surface sediments were contaminated because of petroleum-based inputs and combustion of fossil fuels, while the contribution of pyrogenic sources was less significant (Oros and Ross, 2004). SQG is an imperative tool for the assessment of contamination in sediment core and freshwater, marine, and estuarine sediments (MacDonald et al., 2000; Long et al., 2006). PAH concentrations less than the ERL indicate little or no harmful effects on organisms, with 15% incidence value. PAH concentrations between the ERL and ERM,
+ Pyr) ratios were < 0.4, 0.4–0.5, and > 0.5, the contamination was due to petrogenic sources, petroleum combustion, and wood or coal combustion, respectively. Flt/(Flt + Pyr) ratios in samples S1, S2, S9, and S11 were < 0.4, which indicates that the contamination was due to petroleum-based inputs, whereas that in S3 and S7 was between 0.4 and 0.5, which indicates that the contamination was due to combustion of fossil fuels, crude oil, and gasoline. Flt/(Flt + Pyr) ratio in samples S4 and S12 was > 0.5, suggesting that the contamination was possibly due to coal and wood combustion [Fig. 3(C)] (Rahmanpoor et al., 2014). 5
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Table 3 Sediment quality analysis of the present study site based on SQGs (Long et al., 1995; MacDonald et al., 1996). SQG (ng g− 1)
PAHs
Concentration range (ng g− 1)
< ERL
ERL-ERM
> ERM
ERL
ERM
LMW Ace Acel Ant Flu Phe ΣLMW PAHs
16 44 85.5 19 160 240
500 640 1100 540 2100 1500
5330–430,000 7040–56,240 5060–103,050 2040–5570 8050–260,330 83,790–876,400
– – – – – –
– – – – – –
S1–S12 S1–S12 S1–S12 S1–S12 S1–S12 S1–S12
HMW BaA BaP Chr DahA Flt Pyr ΣHMW ΣLMW + ΣHMW PAHs
552 261 340 384 63.4 600 1700 4022
3100 1600 1600 2800 260 5100 9600 44,792
545–116,730 2150–12,510 1250–57,550 1140–2590 3060–45,600 870–48,720 25,030–233,010 118,280–1,099,410
– – – – – – – –
S9 – S9, S11 S1–S12 – S11, S12 – –
S1–S8, 10–12 S1–S12 S1–S8, S10,12 – S1–S12 S1–S10 S1–S12 S1–S12
concentration of seven potential carcinogenic PAHs listed by the International Agency for Research on Cancer (IARC, 1987): BaA, Chr, BbF, BkF, BaP, DahA, and IP (Li et al., 2015; Orecchio et al., 2010). The potential toxicity based on the total concentration of the six detected carcinogenic PAHs (ΣCPAH6) in the study area ranged from 8120 to 160,000 ng g− 1 dw, with a mean concentration of 63,810 ng g− 1 dw. The values are much higher than those specified in the SQGs of CPAHs, in which the ERL is set as 1373 and the ERM is set as 8410 ng g− 1 (Long et al., 1995). The results of this study indicate that the site is contaminated with an alarmingly high amount of CPAH6, thus posing threat to the entire marine ecosystem in the Gulf of Kutch. The potential toxicity of the contaminated marine sediment samples was assessed using the total BaP equivalent quotient (TEQ) for seven carcinogenic PAH components (Pérez-Fernández et al., 2015; BorteySam et al., 2014; Nasher et al., 2013; Chen and Chen, 2011), which was calculated using the following equation:
with 30% to 50% incidence, indicate occasional harmful effects. When the concentration exceeds the ERM, the incidence ranges from 75% to 100%, indicating acute, adverse biological effects (Burton, 2002; Long et al., 1998, 1995; MacDonald et al., 1996). SQGs for PAHs in the marine sediments of the Gulf of Kutch are presented in Table 3. The data obtained from the present study indicate that the concentrations of most of the individual PAHs in the 12 sediment samples exceeded the ERM. The concentrations of LMW, HMW, and total PAHs were 83,790–876,000, 25,030–233,010, and 118,280–1,099,410 ng g− 1, respectively, which were also significantly higher than the ERM, suggesting adverse ecological risk on marine and coastal human life. However, concentrations of BaA in sample S9 (545 ng g− 1), Chr in samples S9 (1560 ng g− 1) and S11 (1250 ng g− 1), Pyr in samples S11 (5070 ng g− 1) and S12 (870 ng g− 1), and DahA in all sediment samples were between the ERL and ERM (Table 3). This is suggestive of occasional adverse effects, with an incidence value of 30–50%. In the present study, the biological effects of these PAHs in 12 sediment samples were also evaluated according to SQCs applied in Canada (ECM, 2007). The concentrations of 12 PAHs were higher than the FEL, indicative of more frequent adverse biological effects to the ecosystem (Table S2) (He et al., 2014). M-ERM-Q analysis is also a useful method to evaluate the ecological risk caused by multiple toxic compounds in sediments whose concentrations exceed the ERM values (Long and MacDonald, 1998). M-ERMQ can be calculated using the following equation:
MERMQ =
Total TEQcarc =
∑ Ci × TEF carc i
where Ci is the concentration of an individual CPAH (ng g− 1) and TEFicarc (toxic equivalence factor) is the toxic factor of this CPAH relative to BaP. TEFs for BaP, BaA, Chr, BbF, BkF, IP, and DahA were 1, 0.1, 0.001, 0.1, 0.01, 0.1, and 1, respectively. The total TEQ6carc relative to BaP in sediment samples ranged from 150.47 to 26,330 ng g− 1 BaPeq, with a mean concentration of 8633 ng g− 1 BaPeq. TEQ6carc in the present investigation was found to be higher than the cited data (Table 4). The contribution of carcinogenic PAHs to the total TEQ6carc is in the following order: BaP (50.63%) > DahA (31.07%) > BaA (15.27%) > IP (1.77%) > BkF (0.53%) > Chr
∑ C i ERM i n
where Ci is the concentration of compound i in a sediment sample, ERMi is the ERM for compound i, and n is the number of compounds. M-ERM-Q values were classified into four classes, < 0.1, 0.11–0.5, 0.51–1.5, and > 1.5, indicating low, medium-low, medium-high, and high priority sites, with equivalence to ≤ 11%, 25–30%, 46–53%, and ≥ 75% incidence of acute toxicity, respectively (Li et al., 2015). M-ERM-Q values for samples S1, S2, and S3 were 2.45, 2.2, and 1.14, respectively, indicating a high incidence (> 75%) of acute toxicity, whereas those for samples S4–S12 were 0.41, 0.34, 0.5, 0.44, 0.47, 0.34, 0.51, 0.42, and 0.43, respectively, indicating the incidence of acute toxicity at a medium-high (25–30%) level. Variations in M-ERL-Q may be because of temporal shifts in horizontal PAH concentrations along the shoreline, probably attributed to the release of industrial effluents, petrochemical transport, and accidental spills (Olawoyin et al., 2012; Neff et al., 2005). The toxicity of sediment samples was assessed according to the total
Table 4 Toxicity of BaPeq at various coastal areas. Sr. no
Sites
TEQCarc
Range (ng g− 1 BaPeq)
Reference
1
Napals Harbor, Italy
TEQ5carc
2–4723
2
Barents Sea, Russia
TEQ7carc
18–300
carc
94–856
Sprovieri et al., 2007 Savinov et al., 2003 Qiao et al., 2006
carc
TEQ7
76.3–174.6
TEQ7carc
3.9–1970
TEQ6carc
150.47–26,330
3 4 5 6
6
Meilianag Bay, China Langkawi Island, Malaysia Kaohsiung Harbor, Tiawan Gulf of Kutch, Gujarat, India
TEQ7
Nasher et al., 2013 Chen et al., 2013 Present study
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Environment Canada and Ministère du développement durable, de I'Environment et des Parcs du Québec, 2007. Criteria for the Assessment of Sediment Quality in Quebec and Application Frameworks: Prevention, Dredging and Remediation. Library and Archives Canada Cataloguing in Publication, Québec, pp. 1–39. Essien, J.P., Ebong, G.A., Asuquo, J.E., Olajire, A.A., 2012. Hydrocarbons contamination and microbial degradation in mangrove sediments of the Niger Delta region (Nigeria). Chem. Ecol. 28 (5), 421–434. Fang, M.D., Lee, C.L., Yu, C.S., 2003. Distribution and source recognition of polycyclic aromatic hydrocarbons in the sediments of Hsin-ta Harbour and adjacent coastal areas, Taiwan. Mar. Pollut. Bull. 46, 941–953. Hartmann, P.C., Quinn, J.G., Cairns, R.W., King, J.W., 2004. The distribution and sources of polycyclic aromatic hydrocarbons in Narragansett Bay surface sediments. Mar. Pollut. Bull. 48 (3), 351–358. He, X., Pang, Y., Song, X., Chen, B., Feng, Z., Ma, Y., 2014. Distribution, sources and ecological risk assessment of PAHs in surface sediments from Guan River Estuary, China. Mar. Pollut. Bull. 80 (1), 52–58. Huang, W., Wang, Z., Yan, W., 2012. Distribution and sources of polycyclic aromatic hydrocarbons (PAHs) in sediments from Zhanjiang Bay and Leizhou Bay, South China. Mar. Pollut. Bull. 64 (9), 1962–1969. International Agency for Research on Cancer (IARC), 1987. Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to Humans, IARC, Lyons. (Suppl. 7). Jiang, Y.F., Wang, X.T., Wang, F., Jia, Y., Wu, M.H., Sheng, G.Y., Fu, J.M., 2009. Levels, composition profiles and sources of polycyclic aromatic hydrocarbons in urban soil of Shanghai, China. Chemosphere 75 (8), 1112–1118. Kim, K.H., Jahan, S.A., Kabir, E., Brown, R.J., 2013. A review of airborne polycyclic aromatic hydrocarbons (PAHs) and their human health effects. Environ. Int. 60, 71–80. Li, J., Dong, H., Zhang, D., Han, B., Zhu, C., Liu, S., Liu, X., Ma, Q., Li, X., 2015. Sources and ecological risk assessment of PAHs in surface sediments from Bohai Sea and northern part of the Yellow Sea, China. Mar. Pollut. Bull. 96 (1), 485–490. Lin, J.Q., Wang, X.H., Hong, H.S., Chen, W.Q., Liu, R.X., Huang, Z.Q., 2003. PAHs' distribution and source analysis in surface sediments of the Meizhou Bay. J. Xiamen Univ. (Nat. Sci.) 42, 633–638. Liu, X.M., Xu, X.R., Zhang, X.T., Zhou, C.G., Li, H., 2001. A preliminary study on PAHs in the surface sediment samples from Dalian Bay. Acta Sci. Circumst. 21, 507–509. Liu, Y., Chen, L., Jianfu, Z., Qinghui, H., Zhiliang, Z., Hongwen, G., 2008. Distribution and sources of polycyclic aromatic hydrocarbons in surface sediments of rivers and an estuary in Shanghai, China. Environ. Pollut. 154 (2), 298–305. Long, E.R., MacDonald, D.D., 1998. Recommended uses of empirically derived, sediment quality guidelines for marine and estuarine ecosystems. Hum. Ecol. Risk. Assess. 4 (5), 1019–1039. Long, E.R., MacDonald, D.D., Smith, S.L., Calder, F.D., 1995. Incidence of adverse biological effects within ranges of chemical concentrations in marine and estuarine sediments. Environ. Manag. 19 (1), 81–97. Long, E.R., Field, L.J., MacDonald, D.D., 1998. Predicting toxicity in marine sediments with numerical sediment quality guidelines. Environ. Toxicol. Chem. 17, 714–727. Long, E.R., Ingersoll, C.G., MacDonald, D.D., 2006. Calculation and uses of mean sediment quality guideline quotient: a critical review. Environ. Sci. Technol. 40, 1726–1736. MacDonald, D.D., Carr, R.S., Calder, F.D., Long, E.R., Ingersoll, C.G., 1996. Development and evaluation of sediment quality guidelines for Florida coastal waters. Ecotoxicology 5 (4), 253–278. MacDonald, D.D., Ingersoll, C.G., Berger, T.A., 2000. Development and evaluation of consensus-based sediment quality guidelines for freshwater ecosystems. Arch. Environ. Contam. Toxicol. 39, 20–31. Magi, E., Bianco, R., Ianni, C., Di Carro, M., 2002. Distribution of polycyclic aromatic hydrocarbons in the sediments of the Adriatic Sea. Environ. Pollut. 119 (1), 91–98. Mai, B.X., Fu, J.M., Zhang, G., Lin, Z., Min, Y.S., Sheng, G.Y., Wang, X.M., 2001. Polycyclic aromatic hydrocarbons in sediments from the Pearl river and estuary, China: spatial and temporal distribution and sources. Appl. Geochem. 16, 1429–1445. Martínez-Lladó, X., Gibert, O., Martí, V., Díez, S., Romo, J., Bayona, J.M., de Pablo, J., 2007. Distribution of polycyclic aromatic hydrocarbons (PAHs) and tributyltin (TBT) in Barcelona harbour sediments and their impact on benthic communities. Environ. Pollut. 149 (1), 104–113. Men, B., He, M.C., Tan, L., Lin, C.Y., Quan, X.C., 2009. Distribution of polycyclic aromatic hydrocarbons in the Daliao River Estuary of Liaodong Bay, Bohai Sea (China). Mar. Pollut. Bull. 58, 818–826. Nasher, E., Heng, L.Y., Zakaria, Z., Surif, S., 2013. Assessing the ecological risk of polycyclic aromatic hydrocarbons in sediments at Langkawi Island, Malaysia. Sci. World J. 2013. Neff, J.M., Stout, S.A., Gunster, D.G., 2005. Ecological risk assessment of polycyclic aromatic hydrocarbons in sediments: identifying sources and ecological hazard. Integr. Environ. Assess. Manag. 1 (1), 22–33. Olawoyin, R., Grayson, R.L., Okareh, O.T., 2012. Eco-toxicological and epidemiological assessment of human exposure to polycyclic aromatic hydrocarbons in the Niger Delta, Nigeria. Toxicol. Environ. Heal. Sci. 4 (3), 173–185. Orecchio, S., Cannata, S., Culotta, L., 2010. How building an underwater pipeline connecting Libya to Sicilian coast is affecting environment: polycyclic aromatic hydrocarbons (PAHs) in sediments; monitoring the evolution of the shore approach area of the Gulf of Gela (Italy). J. Hazard. Mater. 181 (1), 647–658. Oros, D.R., Ross, J.R., 2004. Polycyclic aromatic hydrocarbons in San Francisco Estuary sediments. Mar. Chem. 86 (3), 169–184. Pérez-Fernández, B., Viñas, L., Franco, M.Á., Bargiela, J., 2015. PAHs in the Ría de Arousa (NW Spain): a consideration of PAHs sources and abundance. Mar. Pollut. Bull. 95
(0.29%). Hence, BaP has been proved to be the most potential human carcinogen prevalent at the contaminated site contributing to maximum toxicity. In conclusion, the present study extensively portrays the lessexplored coastline of Gujarat in terms of thorough assessment, occurrence, and exposure to legacy pollutants, i.e., PAHs. The site has been meticulously studied and has been highlighted on a global scale as the site possesses elevated levels of LMW and HMW PAHs. The ecological risk and potential toxicity assessments of PAHs indicated high probability of adverse effects on marine sediments of the Gulf of Kutch. The study revealed that the Gulf of Kutch bears a great risk and can be considered a historically contaminated site when compared to the existing data at other sites globally. The present study would be incontestably valuable to the global database by providing fresh information for regulatory agencies to improve the environmental quality. Acknowledgment The authors are thankful to the Gujarat State Biotechnology Mission (GSBTM) (Grant no. GSBTM/MD/PROJECT/SSA/3392/2012-13) and the Earth System Sciences Organization (ESSO), Ministry of Earth Sciences, Government of India, New Delhi (Grant no. MoES/16/06/ 2013-RDEAS), for their financial assistance to conduct this research. Appendix A. Supplementary data Supplementary data to this article can be found online at http://dx. doi.org/10.1016/j.marpolbul.2017.04.039. References Barakat, A.O., Mostafa, A., Wade, T.L., Sweet, S.T., El Sayed, N.B., 2011. Distribution and characteristics of PAHs in sediments from the Mediterranean coastal environment of Egypt. Mar. Pollut. Bull. 62 (9), 1969–1978. Baumard, P., Budzinski, H., Garrigues, P., 1998. Polycyclic aromatic hydrocarbons in sediments and mussels of the Western Mediterranean Sea. Environ. Toxicol. Chem. 17, 765–776. Benlahcen, K., Chaoui, A., Budzinski, H., Bellocq, J., Garrigues, P., 1997. Distribution and sources of polycyclic aromatic hydrocarbons in some Mediterranean coastal sediments. Mar. Pollut. Bull. 34, 98–305. Bhatt, J.K., Ghevariya, C.M., Dudhagara, D.R., Rajpara, R.K., Dave, B.P., 2014. Application of response surface methodology for rapid chrysene biodegradation by newly isolated marine-derived fungus Cochliobolus lunatus strain CHR4D. J. Microbiol. 52, 908–917. Bortey-Sam, N., Ikenaka, Y., Nakayama, S.M., Akoto, O., Yohannes, Y.B., Baidoo, E., Mizukawa, H., Ishizuka, M., 2014. Occurrence, distribution, sources and toxic potential of polycyclic aromatic hydrocarbons (PAHs) in surface soils from the Kumasi Metropolis, Ghana. Sci. Total Environ. 496, 471–478. Burton Jr., G.A., 2002. Sediment quality criteria in use around the world. Limnology 3 (2), 65–76. Chen, C.W., Chen, C.F., 2011. Distribution, origin, and potential toxicological significance of polycyclic aromatic hydrocarbons (PAHs) in sediments of Kaohsiung Harbor, Taiwan. Mar. Pollut. Bull. 63, 417–423. Chen, C.F., Chen, C.W., Dong, C.D., Kao, C.M., 2013. Assessment of toxicity of polycyclic aromatic hydrocarbons in sediments of Kaohsiung Harbor, Taiwan. Sci. Total Environ. 463, 1174–1181. Dave, B.P., Ghevariya, C.G., Bhatt, J.K., Dudhagara, D.R., Rajpara, R.K., 2014. Enhanced biodegradation of total polycyclic aromatic hydrocarbons (TPAHs) by marine halotolerant Achromobacter xylosoxidans using Triton X-100 and b-cyclodextrine a microcosm approach. Mar. Pollut. Bull. 79, 123–129. De Luca, G., Furesi, A., Leardi, R., Micera, G., Panzanelli, A., Piu, P.C., Sanna, G., 2004. Polycyclic aromatic hydrocarbons assessment in the sediments of the Porto Torres Harbor (Northern Sardinia, Italy). Mar. Chem. 86 (1), 15–32. Dudhagara, D.R., Rajpara, R.K., Bhatt, J.K., Gosai, H.B., Sachaniya, B.K., Dave, B.P., 2016a. Distribution, sources and ecological risk assessment of PAHs in historically contaminated surface sediments at Bhavnagar coast, Gujarat, India. Environ. Pollut. 213, 338–346. Dudhagara, D.R., Rajpara, R.K., Bhatt, J.K., Gosai, H.B., Dave, B.P., 2016b. Bioengineering for polycyclic aromatic hydrocarbon degradation by Mycobacterium litorale: statistical and artificial neural network (ANN) approach. Chemometr. Intell. Lab. 159, 155–163. Eguvbe, P.M., Iwegbue, C.M., Egboh, S.H., Ogala, J.E., Nwajei, G.E., 2015. Source apportionment and identification of polycyclic aromatic hydrocarbons (PAHs) in sediment cores of selected Creeks in Delta State, Nigeria. Environ. Forensic 16 (1), 51–75.
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Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) distributions in the Bay of Marmara sea: Izmit Bay. Environ. Pollut. 119, 383–397. Tronczynsky, J., Munschy, C., Héas-Moisan, K., Guiot, N., Truquet, I., Olivier, N., Men, S., Furaut, A., 2004. Contamination of the Bay of Biscay by polycyclic aromatic hydrocarbons (PAHs) following the T/V “Erika” oil spill. Aquat. Living Resour. 17, 243–259. USEPA, 1993. Provisional Guidance for Quantitative Risk Assessment of Polycyclic Aromatic Hydrocarbons. (Washington, DC). Viguri, J., Verde, J., Irabien, A., 2002. Environmental assessment of polycyclic aromatic hydrocarbons (PAHs) in surface sediments of the Santander Bay, Northern Spain. Chemosphere 48, 44–60. Wang, X.C., Zhang, Y.X., Chen, R.F., 2001. Distribution and partitioning of polycyclic aromatic hydrocarbons (PAHs) in different size fractions in sediments from Boston Harbor, United States. Mar. Pollut. Bull. 42 (11), 1139–1149. Wattiau, P., 2002. Microbial aspects in bioremediation of soils polluted by polyaromatic hydrocarbons. In: Biotechnology for the Environment: Strategy and Fundamentals. Springer, Netherlands, pp. 69–89. Yuan, D.X., Yang, D.N., Wade, T.L., Qian, Y.R., 2001. Status of persistent organic pollutants in the sediment from several estuaries in China. Environ. Pollut. 114, 101–111. Yunker, M.B., MacDonald, R.W., Vingarzan, R., Mitchell, R.H., Goyette, D., Sylvestre, S., 2002. PAHs in the Fraser River basin: a critical appraisal of PAH ratios as indicators of PAH source and composition. Org. Geochem. 33 (4), 489–515. Zhang, D., Liu, J., Jiang, X., Cao, K., Yin, P., Zhang, X., 2016. Distribution, sources and ecological risk assessment of PAHs in surface sediments from the Luan River Estuary, China. Mar. Pollut. Bull. 102, 223–229.
(1), 155–165. Pietzsch, R., Patchineelam, S.R., Torres, J.P., 2010. Polycyclic aromatic hydrocarbons in recent sediments from a subtropical estuary in Brazil. Mar. Chem. 118 (1), 56–66. Qiao, M., Wang, C., Huang, S., Wang, D., Wang, Z., 2006. Composition, sources, and potential toxicological significance of PAHs in the surface sediments of the Meiliang Bay, Taihu Lake, China. Environ. Int. 32, 28–33. Rahmanpoor, S., Ghafourian, H., Hashtroudi, S.M., Bastami, K.D., 2014. Distribution and sources of polycyclic aromatic hydrocarbons in surface sediments of the Hormuz strait, Persian Gulf. Mar. Pollut. Bull. 78 (1), 224–229. Readman, J.W., Fillmann, G., Tolosa, I., Bartocci, J., Villeneuve, J.P., Catinni, C., Mee, L.D., 2002. Petroleum and PAH contamination of the Black Sea. Mar. Pollut. Bull. 44, 48–62. Savinov, V.M., Savinova, T.N., Matishov, G.G., Dahle, S., Næs, K., 2003. Polycyclic aromatic hydrocarbons (PAHs) and organochlorines (OCs) in bottom sediments of the Guba Pechenga, Barents Sea, Russia. Sci. Total Environ. 306, 39–56. Soclo, H.H., Garrigues, P., Ewald, M., 1986. Analyse quantitative deshydrocarbures aromatiques polycycliques dans les se'diments re'centspar chromatographie en phase liquid et de'tection spectrofluorime'trique. Analusis 14 (7), 344–350. Soclo, H.H., Garrigues, P.H., Ewald, M., 2000. Origin of polycyclic aromatic hydrocarbons (PAHs) in coastal marine sediments: case studies in Cotonou (Benin) and Aquitaine (France) areas. Mar. Pollut. Bull. 40 (5), 387–396. Sprovieri, M., Feo, M.L., Prevedello, L., Manta, D.S., Sammartino, S., Tamburrino, S., Marsella, E., 2007. Heavy metals, polycyclic aromatic hydrocarbons and polychlorinated biphenyls in surface sediments of the Naples harbor (southern Italy). Chemosphere 67, 998–1009. Telli-Karakoc, F., Tolun, L., Henkelmann, B., Klimm, C., Okay, O., Schramm, K., 2002.
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Baseline
Polycyclic aromatic hydrocarbons (PAHs) at the Gulf of Kutch, Gujarat, India: Occurrence, source apportionment, and toxicity of PAHs as an emerging issue Rahul K. Rajpara, Dushyant R. Dudhagara, Jwalant K. Bhatt, Haren B. Gosai, Bharti P. Dave⁎ Department of Life Sciences, Maharaja Krishnakumarsinhji Bhavnagar University, Sardar Vallabhbhai Patel Campus, Bhavnagar 364001, Gujarat, India
A R T I C L E I N F O
A B S T R A C T
Keywords: Polycyclic aromatic hydrocarbons (PAHs) Source apportionment Sediment quality guidelines (SQGs) Risk assessment Toxic equivalent quotient (TEQ)
The present study extrapolates the assessment and characterization of a barely studied region, the Gulf of Kutch, (near Jamnagar), Gujarat, India, in terms of PAH exposure, adverse effects caused by them, and various toxicological indices showing the catastrophic effects of their elevated concentrations. ΣPAH concentration in the site ranged from 118,280 to 1,099,410 ng g− 1 dw, with a predominance of 2–3-ring PAHs (79.09%) as compared to 4–5- and 6-ring PAHs (20.91%). The concentrations of carcinogenic PAHs were found to be between 8120 and 160,000 ng g− 1 dw, with a mean of 63,810 ng g− 1 dw, which is much higher than normal acceptable values. The toxic equivalent quotient for 6CPAHs ranged from 150.47 to 26,330 ng g− 1 BaPeq, encompassing 50.63% of ΣPAH toxicity. This toxicological profile of the present study site would be of paramount importance as it offers fresh information regarding the load of legacy pollutants such as PAHs and the inputs and methods to cope with their extremely high concentrations in less explored marine habitats.
Rapid economic development and the increasing consumption of petroleum and coal in developing countries such as India are among the prime reasons for the growing concern for developing methods to treat an array of pollutants, which otherwise could cause severe ailments and threaten environmental health globally. Polycyclic aromatic hydrocarbons (PAHs) are found in almost every ecological matrix because of extensive anthropogenic intrusion. They possess an ecological risk as some of them have been reported to be carcinogenic, mutagenic, and/or teratogenic in nature (Kim et al., 2013; Huang et al., 2012; Pietzsch et al., 2010). The composition of PAH assemblage in marine sediment mainly depends on the sources of PAHs and the extent of innate processes they undergo since their discharge into marine environments (Neff et al., 2005). PAHs are exposed to various components of the ecosystem because of vehicle exhaust and other anthropogenic activities, such as industrialization, and can be accumulated in terrestrial and marine ecosystems as a result of dry and wet deposition of PAH fine particles, direct riverine and petroleum inputs, and urban runoffs. These factors contribute to elevate PAH concentrations in marine sediments, thereby making marine sediments the ultimate sinks of these refractile compounds (Bhatt et al., 2014; Pietzsch et al., 2010). Sources of PAHs in marine sediments are classified into pyrogenic (pyrolytic), petrogenic, and diagenic sources. Pyrolytic sources include
⁎
the combustion processes of fossil fuels, incomplete combustion of organic materials such as wood, coal, and oil, and anthropogenic activities characterized by HMW PAHs. Petrogenic input is attributed to petroleum products, off shore exploitations, urban runoffs, and oil seeps due to natural activities. Diagenic PAHs such as perylene are formed because of biological processes and are found in both marine and freshwater sediments (Dudhagara et al., 2016a, 2016b; Barakat et al., 2011; Jiang et al., 2009). PAHs have always been associated with an increased risk of developing cancer in various human tissues including skin, lung, bladder, and stomach. The severity of the cancer developed depends on the mode of exposure and the form of PAHs (Kim et al., 2013). PAHs are also known as endocrine disrupting compounds because of their ability to bind endogenous receptors (Wattiau, 2002). Recently, the surrounding areas of the Gulf of Kutch (near Jamnagar), Gujarat, India, have been experiencing a great deal of economic development as special economic zones (SEZs); this often results in the risk of environment pollution due to the release of toxic organic compounds and oil spills from petrochemical plants, ship transport, ship breaking–recycling activities, and other anthropogenic activities in marine ecosystem. However, data on the sources, mechanism, and distribution of PAHs and their potential risks to environment health is scarce. This knowledge gap needs to be filled by determining
Corresponding author at: Department of Life Sciences, Maharaja Krishnakumarsinhji Bhavnagar University, Sardar Vallabhbhai Patel Campus, Bhavnagar 364001, Gujarat, India. E-mail address: [email protected] (B.P. Dave).
http://dx.doi.org/10.1016/j.marpolbul.2017.04.039 Received 13 November 2016; Received in revised form 16 April 2017; Accepted 22 April 2017 0025-326X/ © 2017 Elsevier Ltd. All rights reserved.
Please cite this article as: Rajpara, R.K., Marine Pollution Bulletin (2017), http://dx.doi.org/10.1016/j.marpolbul.2017.04.039
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Fig. 1. (A) Geographic location of the study site and (B) various sampling points.
they pose in marine sediments. Contaminated surface sediment samples were collected from the Gulf of Kutch (Fig. 1). The study area included the upstream part of the gulf. It was divided into 12 points along the coastline of the Gulf of Kutch, as shown in Fig. 1(A, B), with a distance of 200 m between two consecutive sampling points. Sampling was performed from January 2012 to December 2013. From each sampling point, samples of surface sediments were collected in triplicates and immediately transferred to amber glass bottles and stored at − 20 °C until further analysis. In total, 36 (12 × 3) samples were collected, and the results of the analyses were expressed as the mean of triplicate samples.
the distribution of priority PAHs present in oil-contaminated sediments of the Gulf of Kutch. As described earlier, the apportionment of PAH sources was performed on the basis of the isomeric ratios of the PAHs to (i) evaluate the ecological risks caused by each PAH according to sediment quality guidelines (SQGs) and sediment quality criteria (SQCs) and (ii) evaluate the combined ecological risk and the toxicity levels of PAHs by using mean effects range median quotient (M-ERM-Q) and toxic equivalent quotient (TEQ) analyses, respectively. Thus, the results of this study can be a meaningful reference by providing baseline information on the sources of PAHs, toxicity levels of individual PAH, and ecological risk
2
3
39,060 ± 0.02 42,240 ± 0.01 5330 ± 0.03 ND 20,170 ± 0.01 65,060 ± 0.03 3050 ± 0.02 5070 ± 0.01 1250 ± 0.02 5260 ± 0.02 ND 4440 ± 0.01 ND ND 5250 ± 0.020 ND 29,070 ± 0.03 15,330 ± 0.111 9080 ± 0.020 ND 63,860 ± 0.02 31,050 ± 0.02 25,080 ± 0.02 ND ND ND ND 6730 ± 0.02 ND ND 5300 ± 0.11 ND Where Values in ng g− 1 dw of sediment 1 Nap, 2 Ace, 3 Acel, 4 Flu, 5 Phe, 6 Ant, 7 Flt, 8 Pyr, 9 Chr, 10 BaA, 11 BbF, 12 BkF, 13 BaP, 14 DahA,1 5 BghiP, 16 IP. ND = not detected or below the detection limit (< DL).
39,060 ± 0.01 ND 5260 ± 0.05 ND 20,160 ± 0.05 66,030 ± 0.11 3060 ± 0.01 13,430 ± 0.01 1560 ± 0.02 545 ± 0.01 ND ND ND 1140 ± 0.01 ND ND 9060 ± 0.01 23,530 ± 0.025 ND 5570 ± 0.01 59,210 ± 0.30 22,050 ± 0.01 ND 36,070 ± 0.02 38,740 ± 0.56 12,340 ± 0.02 ND 3180 ± 0.07 ND 2040 ± 0.01 ND ND 11,070 ± 0.01 ND ND ND 67,660 ± 0.12 5060 + 0.030 11,320 ± 0.01 13,600 ± 0.02 ND ND ND ND ND ND 9570 ± 0.01 ND 8030 ± 0.01 ND 13,050 ± 0.01 ND 31,470 ± 0.01 62,050 ± 0.010 23,600 ± 0.005 ND ND ND ND ND 6040 ± 0.01 ND 12,330 ± 0.010 ND 11,930 ± 0.02 ND 16,170 ± 0.05 2040 ± 0.01 25,060 ± 0.02 30,480 ± 0.05 ND 12,050 ± 0.01 22,290 ± 0.03 ND ND ND 12,510 ± 0.01 ND 6680 ± 0.010 ND ND ND ND ND 29,400 ± 0.10 58,050 ± 0.01 10,060 ± 0.01 8030 ± 0.01 ND ND ND 9560 ± 0.01 ND 2350 ± 0.01 11,150 ± 0.020 ND 31,750 ± 0.00 56,240 ± 0.01 ND ND 91,130 ± 0.05 106,050 ± 0.01 45,660 ± 0.02 48,720 ± 0.005 ND 20,050 ± 0.030 ND ND ND ND ND 9220 ± 0.005 173,320 ± 0.68 ND 413,860 ± 0.20 ND 260,330 ± 0.1 28,890 ± 0.58 16,560 ± 0.05 28,320 ± 0.40 57,550 ± 0.31 116,730 ± 0.41 ND ND ND 2590 ± 0.21 1260 ± 0.03 ND 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
119,530 ± 0.40 ND 430,260 ± 0.20 ND 230,550 ± 0.50 50,500 ± 0.33 9720 ± 0.18 16,040 ± 0.48 23,450 ± 0.35 ND ND ND 5530 ± 0.02 ND 3550 ± 0.015 ND
S4 S3 S2 S1 PAHs
Table 1 Distribution of the 16 priority PAHs listed by the USEPA in sediment samples S1–S12.
S5
S6
S7
S8
S9
S10
S11
S12
Prior to the extraction of 16 priority PAHs listed by the United States Environmental Protection Agency (USEPA, 1993), sediment samples were dried using sodium sulfate and sieved through a 10-mm stainless-steel mesh (> 2 mm) (Pietzsch et al., 2010). For the extraction of PAHs, a 10-g sample was added to 50 mL of dichloromethane:acetone mixture (1:1 v/v). This mixture was then placed in an ultrasonicator bath (Fisher Scientific, Mumbai, India) for 5 min, with 1 min of rest. This procedure was repeated twice, and each time, the supernatant (solvent phase) was pooled. The extract was combined and concentrated to 2–4 dichloromethane:acetone mixture using rotary vacuum evaporator (Büchi R215, Switzerland) (Dave et al., 2014). The extract was then cleaned using a chromatography column prepared with aluminum oxide (Al2O3) prior to the removal of elemental sulfur and humic materials, as suggested by Oros and Ross (2004) and Pietzsch et al. (2010). The final extract was further concentrated to 1 mL for GC–MS analysis, as described by Dudhagara et al. (2016a, 2016b) (Shimadzu QP2010 +, Japan). All analytical procedures and the obtained data were subjected to quality control. A standard PAH mixture containing the 16 USEPA priority PAHs, procured from Supelco, Bellefonte, USA, was subjected to the QA/QC procedure. The standard PAH mixture consisted of naphthalene (Nap), acenaphthene (Ace), acenaphthylene (Acel), fluorene (Flu), phenanthrene (Phe), anthracene (Ant), fluoranthene (Flt), pyrene (Pyr), benzo(a)anthracene (BaA), chrysene (Chr), benzo(b) fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene (BaP), dibenzo(a,h)anthracene (DahA), indeno(1,2,3-cd)pyrene (IP), and benzo(g,h,i)-perylene (BghiP). In addition to analyzing field samples, method blank (solvent), spiked blank (standard spiked with solvent), and matrix spiked blank (soil spiked with PAHs) samples were also analyzed simultaneously. The analysis of procedural blanks showed that the analysis system and the glassware used in this study were free of contamination. The relative standard deviations were < 15% on PAH measurements of recovery protocol, with an average ranging between 53.25 ± 14% and 111.73 ± 21%. From the signal-to-noise ratio of 3:1 in the blank samples, the method detection limit (MDL) of PAHs was estimated to be 50 ng g− 1 dw for individual PAHs (Dudhagara et al., 2016a, 2016b). The USEPA 16 priority PAHs were frequently detected in sediment samples, and their mean concentrations are presented in Table 1. The results indicate that majority of priority PAHs were present in all sediment samples. The concentration ranges (in ng g− 1 dw) of predominant PAHs were as follows: Nap 1260–173,320; Ace 3550–11,930; Acel 9220–106,050; Phe 2040–30,480; Ant 6040–62,050; Flt 5060–13,600; and Pyr 3180–59,210. The sequence of the 15 PAH congeners ordered according to their mean concentration was Acel > Phe > Ant > Nap > Pyr > Flt > BaA > Chr > Ace > DahA > BkF > BaP > BghiP > IP > Flu. The above results suggest that the contamination at the Gulf of Kutch was dominated by LMW PAHs. The pattern of distribution in sediment samples was found to vary, which could be attributed to the flux of the various coastal activities (De Luca et al., 2004). The level of PAH contamination in sediments was categorized into four levels: (i) low (0–100 ng g− 1), (ii) moderate (100–1000 ng g− 1), (iii) high (1000–5000 ng g− 1), and (iv) very high (> 5000 ng g− 1) (Baumard et al., 1998). According to this classification, the Gulf of Kutch, with a PAH concentration of 118,280–1,099,410 ng g− 1 dw, could be considered a very highly polluted site. Table 2 shows a comparison of ΣPAH concentrations (ng g− 1 dw) in surface sediments of different estuaries around the world and their adjacent coastal regions, as reported in previous studies, and those found in the present study. ΣPAH concentrations in sediments ranged from 118,280 to 1,099,410 ng g− 1 dw, with a mean value of 3.21 × 105 ng g− 1 dw. The results of the present study indicated that 96.29% of the ΣPAHs were LMW PAHs, while 3.71% were HMW PAHs. To the best of our knowledge, this study has reported the third highest ΣPAH concentration along the coastal regions around the world.
80,350 ± 0.05 7040 ± 0.01 23,260 ± 0.03 ND 8050 ± 0.03 53,060 ± 0.01 22,170 ± 0.02 870 ± 0.01 5630 ± 0.03 6050 ± 0.03 ND 3940 ± 0.020 2150 ± 0.030 ND 16,130 ± 0.020 ND
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Table 2 ΣPAHs detected at various international coastal areas including that at the present site.
1 2 3 4 5 6 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Location
Range (ng g− 1)
Mean (ng g− 1)
References
Izmit Bay, Marmara Sea, Turkey Hsin-ta Harbour, Taiwan Santander Bay, Spain Barcelona harbor, Spain Dalian Bay, China Liaodong Bay, China Biscay Bay, France Porto Torres, Sardinia, Italy Meizhou Bay, China Minjiang River Estuary Pearl River Estuary, China Northwest Mediterranean Sea Leizhou Bay, China Zhanjiang Bay, China Boston Harbour, USA Narragansett Bay, USA West Mediterranean Sea Black Sea coast, Turkey Alang-sosiya, India Gulf of Kutch, India
3.0 × 104–1.67 × 106 156–3382 1620–344,600 16,300–10,320 32.70–3558.88 276.26–1606.89 20–5159 70–1210 196.7–299.7 174.96–817.40 323–2372 86.5–48,090 21.72–319.61 41.96–933.90 7266–358,092 569–216,000 1.5–20,440 10–530 5020–981,000 118,280–1,099,410
6.01 × 105 – –
Telli-Karakoc et al., 2002 Fang et al., 2003 Viguri et al., 2002 Martínez-Lladó et al., 2007 Liu et al., 2001 Men et al., 2009 Tronczynsky et al., 2004 De Luca et al., 2004 Lin et al., 2003 Yuan et al., 2001 Mai et al., 2001 Benlahcen et al., 1997 Huang et al., 2012 Huang et al., 2012 Wang et al., 2001 Hartmann et al., 2004 Baumard et al., 1998 Readman et al., 2002 Dudhagara et al., 2016a, 2016b Present study
1152.08 743.03 – – 256.1 437.21 1587 – 103.91 315.98 – 21,100 – – 345,000 321,635
Fig. 2. Abundance of PAHs in the surface sediments of the Gulf of Kutch.
The majority of the PAHs in marine sediments originate from pyrogenic and petrogenic sources. Pyrolytic PAHs are produced from incomplete combustion of carbon and wood fossil fuels, and they are characterized by compounds with 4–6 aromatic rings, while petrogenic PAHs are generally of LMW. The ratio LMW/HMW PAHs differentiates petrogenic (> 1) and pyrogenic (< 1) sources. LMW/HMW PAH ratio of the 12 sediment samples (S1–S12) in this study ranged from 1.29 to 14.45, which suggests that the contamination was due to petrogenic sources [Fig. 3(A)] (Liu et al., 2008; Soclo et al., 2000). Phe has two thermodynamically stable structural isomers. Therefore, a higher Phe/ Ant ratio (> 10) was observed in petrogenic sources and a lower ratio (< 10) in pyrolytic sources (De Luca et al., 2004; Soclo et al., 1986). Fig. 3(B) shows that Phe/Ant ratio ranged from 0.151 to 13.37, suggesting that the PAHs in surface sediments could have originated from mixed sources. Fig. 3(B) also shows that the ratios of Ant/Ant + Phe in S1 and S7 were 0.09 and 0.06 (< 0.1), respectively, whereas the rest of the samples had a value > 0.1, suggesting the dominance of pyrogenic over petrogenic contamination (Rahmanpoor et al., 2014; Yunker et al., 2002). The ratio Flt/Pyr in most sediment samples was < 1, indicative of contamination by petrogenic sources (Magi et al., 2002). When Flt/(Flt
Fig. 2 shows the group profile of the 16 PAHs. The PAHs detected were categorized into four groups depending on the number of aromatic rings (Essien et al., 2012): group i: 2–3-ring PAHs accounting for 79.09% of the total PAHs, group ii: 4-ring PAHs accounting for 17.20% of the total PAHs, group iii: 5-ring PAHs contributing the least, only 1.61%, to the total PAHs, and group iv: 6-ring PAHs representing 2.09% of the total PAHs. This profile suggested that petrogenic PAHs such as 2–3-ring PAHs have contributed the most to the total PAHs. A remarkable observation was that the presence and concentration of 6ring PAHs (group iv) were slightly higher than those of 5-ring PAHs (group iii). The findings suggest that the persistence of 6-ring PAHs in sediments may be because they are resistant to microbial attack or cannot be used as carbon and energy sources. The characteristics of PAH pattern in marine sediments are subjected to different emission sources. It is necessary to determine the PAH sources for controlling their input and allocating responsibility for bioremediation activity (Zhang et al., 2016). To recognize the sources of PAHs, we compared the characteristic isomeric PAH ratios of LMW/ HMW, Ant/Ant + Phe, Phe/Ant, Flt/Pyr, and Flt/(Flt + Pyr) found in the present study with those reported in previous studies (Eguvbe et al., 2015; He et al., 2014; Yunker et al., 2002). 4
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Fig. 3. Cross-plots for the isomeric ratios (A) Flu/Flu + pyr vs. LMW/HMW, (B) Ant/Ant + Phe vs. Phe/Ant, and (C) Flu/Flu + pyr vs. Flu + Pyr.
These ratios revealed that surface sediments were contaminated because of petroleum-based inputs and combustion of fossil fuels, while the contribution of pyrogenic sources was less significant (Oros and Ross, 2004). SQG is an imperative tool for the assessment of contamination in sediment core and freshwater, marine, and estuarine sediments (MacDonald et al., 2000; Long et al., 2006). PAH concentrations less than the ERL indicate little or no harmful effects on organisms, with 15% incidence value. PAH concentrations between the ERL and ERM,
+ Pyr) ratios were < 0.4, 0.4–0.5, and > 0.5, the contamination was due to petrogenic sources, petroleum combustion, and wood or coal combustion, respectively. Flt/(Flt + Pyr) ratios in samples S1, S2, S9, and S11 were < 0.4, which indicates that the contamination was due to petroleum-based inputs, whereas that in S3 and S7 was between 0.4 and 0.5, which indicates that the contamination was due to combustion of fossil fuels, crude oil, and gasoline. Flt/(Flt + Pyr) ratio in samples S4 and S12 was > 0.5, suggesting that the contamination was possibly due to coal and wood combustion [Fig. 3(C)] (Rahmanpoor et al., 2014). 5
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Table 3 Sediment quality analysis of the present study site based on SQGs (Long et al., 1995; MacDonald et al., 1996). SQG (ng g− 1)
PAHs
Concentration range (ng g− 1)
< ERL
ERL-ERM
> ERM
ERL
ERM
LMW Ace Acel Ant Flu Phe ΣLMW PAHs
16 44 85.5 19 160 240
500 640 1100 540 2100 1500
5330–430,000 7040–56,240 5060–103,050 2040–5570 8050–260,330 83,790–876,400
– – – – – –
– – – – – –
S1–S12 S1–S12 S1–S12 S1–S12 S1–S12 S1–S12
HMW BaA BaP Chr DahA Flt Pyr ΣHMW ΣLMW + ΣHMW PAHs
552 261 340 384 63.4 600 1700 4022
3100 1600 1600 2800 260 5100 9600 44,792
545–116,730 2150–12,510 1250–57,550 1140–2590 3060–45,600 870–48,720 25,030–233,010 118,280–1,099,410
– – – – – – – –
S9 – S9, S11 S1–S12 – S11, S12 – –
S1–S8, 10–12 S1–S12 S1–S8, S10,12 – S1–S12 S1–S10 S1–S12 S1–S12
concentration of seven potential carcinogenic PAHs listed by the International Agency for Research on Cancer (IARC, 1987): BaA, Chr, BbF, BkF, BaP, DahA, and IP (Li et al., 2015; Orecchio et al., 2010). The potential toxicity based on the total concentration of the six detected carcinogenic PAHs (ΣCPAH6) in the study area ranged from 8120 to 160,000 ng g− 1 dw, with a mean concentration of 63,810 ng g− 1 dw. The values are much higher than those specified in the SQGs of CPAHs, in which the ERL is set as 1373 and the ERM is set as 8410 ng g− 1 (Long et al., 1995). The results of this study indicate that the site is contaminated with an alarmingly high amount of CPAH6, thus posing threat to the entire marine ecosystem in the Gulf of Kutch. The potential toxicity of the contaminated marine sediment samples was assessed using the total BaP equivalent quotient (TEQ) for seven carcinogenic PAH components (Pérez-Fernández et al., 2015; BorteySam et al., 2014; Nasher et al., 2013; Chen and Chen, 2011), which was calculated using the following equation:
with 30% to 50% incidence, indicate occasional harmful effects. When the concentration exceeds the ERM, the incidence ranges from 75% to 100%, indicating acute, adverse biological effects (Burton, 2002; Long et al., 1998, 1995; MacDonald et al., 1996). SQGs for PAHs in the marine sediments of the Gulf of Kutch are presented in Table 3. The data obtained from the present study indicate that the concentrations of most of the individual PAHs in the 12 sediment samples exceeded the ERM. The concentrations of LMW, HMW, and total PAHs were 83,790–876,000, 25,030–233,010, and 118,280–1,099,410 ng g− 1, respectively, which were also significantly higher than the ERM, suggesting adverse ecological risk on marine and coastal human life. However, concentrations of BaA in sample S9 (545 ng g− 1), Chr in samples S9 (1560 ng g− 1) and S11 (1250 ng g− 1), Pyr in samples S11 (5070 ng g− 1) and S12 (870 ng g− 1), and DahA in all sediment samples were between the ERL and ERM (Table 3). This is suggestive of occasional adverse effects, with an incidence value of 30–50%. In the present study, the biological effects of these PAHs in 12 sediment samples were also evaluated according to SQCs applied in Canada (ECM, 2007). The concentrations of 12 PAHs were higher than the FEL, indicative of more frequent adverse biological effects to the ecosystem (Table S2) (He et al., 2014). M-ERM-Q analysis is also a useful method to evaluate the ecological risk caused by multiple toxic compounds in sediments whose concentrations exceed the ERM values (Long and MacDonald, 1998). M-ERMQ can be calculated using the following equation:
MERMQ =
Total TEQcarc =
∑ Ci × TEF carc i
where Ci is the concentration of an individual CPAH (ng g− 1) and TEFicarc (toxic equivalence factor) is the toxic factor of this CPAH relative to BaP. TEFs for BaP, BaA, Chr, BbF, BkF, IP, and DahA were 1, 0.1, 0.001, 0.1, 0.01, 0.1, and 1, respectively. The total TEQ6carc relative to BaP in sediment samples ranged from 150.47 to 26,330 ng g− 1 BaPeq, with a mean concentration of 8633 ng g− 1 BaPeq. TEQ6carc in the present investigation was found to be higher than the cited data (Table 4). The contribution of carcinogenic PAHs to the total TEQ6carc is in the following order: BaP (50.63%) > DahA (31.07%) > BaA (15.27%) > IP (1.77%) > BkF (0.53%) > Chr
∑ C i ERM i n
where Ci is the concentration of compound i in a sediment sample, ERMi is the ERM for compound i, and n is the number of compounds. M-ERM-Q values were classified into four classes, < 0.1, 0.11–0.5, 0.51–1.5, and > 1.5, indicating low, medium-low, medium-high, and high priority sites, with equivalence to ≤ 11%, 25–30%, 46–53%, and ≥ 75% incidence of acute toxicity, respectively (Li et al., 2015). M-ERM-Q values for samples S1, S2, and S3 were 2.45, 2.2, and 1.14, respectively, indicating a high incidence (> 75%) of acute toxicity, whereas those for samples S4–S12 were 0.41, 0.34, 0.5, 0.44, 0.47, 0.34, 0.51, 0.42, and 0.43, respectively, indicating the incidence of acute toxicity at a medium-high (25–30%) level. Variations in M-ERL-Q may be because of temporal shifts in horizontal PAH concentrations along the shoreline, probably attributed to the release of industrial effluents, petrochemical transport, and accidental spills (Olawoyin et al., 2012; Neff et al., 2005). The toxicity of sediment samples was assessed according to the total
Table 4 Toxicity of BaPeq at various coastal areas. Sr. no
Sites
TEQCarc
Range (ng g− 1 BaPeq)
Reference
1
Napals Harbor, Italy
TEQ5carc
2–4723
2
Barents Sea, Russia
TEQ7carc
18–300
carc
94–856
Sprovieri et al., 2007 Savinov et al., 2003 Qiao et al., 2006
carc
TEQ7
76.3–174.6
TEQ7carc
3.9–1970
TEQ6carc
150.47–26,330
3 4 5 6
6
Meilianag Bay, China Langkawi Island, Malaysia Kaohsiung Harbor, Tiawan Gulf of Kutch, Gujarat, India
TEQ7
Nasher et al., 2013 Chen et al., 2013 Present study
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Environment Canada and Ministère du développement durable, de I'Environment et des Parcs du Québec, 2007. Criteria for the Assessment of Sediment Quality in Quebec and Application Frameworks: Prevention, Dredging and Remediation. Library and Archives Canada Cataloguing in Publication, Québec, pp. 1–39. Essien, J.P., Ebong, G.A., Asuquo, J.E., Olajire, A.A., 2012. Hydrocarbons contamination and microbial degradation in mangrove sediments of the Niger Delta region (Nigeria). Chem. Ecol. 28 (5), 421–434. Fang, M.D., Lee, C.L., Yu, C.S., 2003. Distribution and source recognition of polycyclic aromatic hydrocarbons in the sediments of Hsin-ta Harbour and adjacent coastal areas, Taiwan. Mar. Pollut. Bull. 46, 941–953. Hartmann, P.C., Quinn, J.G., Cairns, R.W., King, J.W., 2004. The distribution and sources of polycyclic aromatic hydrocarbons in Narragansett Bay surface sediments. Mar. Pollut. Bull. 48 (3), 351–358. He, X., Pang, Y., Song, X., Chen, B., Feng, Z., Ma, Y., 2014. Distribution, sources and ecological risk assessment of PAHs in surface sediments from Guan River Estuary, China. Mar. Pollut. Bull. 80 (1), 52–58. Huang, W., Wang, Z., Yan, W., 2012. Distribution and sources of polycyclic aromatic hydrocarbons (PAHs) in sediments from Zhanjiang Bay and Leizhou Bay, South China. Mar. Pollut. Bull. 64 (9), 1962–1969. International Agency for Research on Cancer (IARC), 1987. Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to Humans, IARC, Lyons. (Suppl. 7). Jiang, Y.F., Wang, X.T., Wang, F., Jia, Y., Wu, M.H., Sheng, G.Y., Fu, J.M., 2009. Levels, composition profiles and sources of polycyclic aromatic hydrocarbons in urban soil of Shanghai, China. Chemosphere 75 (8), 1112–1118. Kim, K.H., Jahan, S.A., Kabir, E., Brown, R.J., 2013. A review of airborne polycyclic aromatic hydrocarbons (PAHs) and their human health effects. Environ. Int. 60, 71–80. Li, J., Dong, H., Zhang, D., Han, B., Zhu, C., Liu, S., Liu, X., Ma, Q., Li, X., 2015. Sources and ecological risk assessment of PAHs in surface sediments from Bohai Sea and northern part of the Yellow Sea, China. Mar. Pollut. Bull. 96 (1), 485–490. Lin, J.Q., Wang, X.H., Hong, H.S., Chen, W.Q., Liu, R.X., Huang, Z.Q., 2003. PAHs' distribution and source analysis in surface sediments of the Meizhou Bay. J. Xiamen Univ. (Nat. Sci.) 42, 633–638. Liu, X.M., Xu, X.R., Zhang, X.T., Zhou, C.G., Li, H., 2001. A preliminary study on PAHs in the surface sediment samples from Dalian Bay. Acta Sci. Circumst. 21, 507–509. Liu, Y., Chen, L., Jianfu, Z., Qinghui, H., Zhiliang, Z., Hongwen, G., 2008. Distribution and sources of polycyclic aromatic hydrocarbons in surface sediments of rivers and an estuary in Shanghai, China. Environ. Pollut. 154 (2), 298–305. Long, E.R., MacDonald, D.D., 1998. Recommended uses of empirically derived, sediment quality guidelines for marine and estuarine ecosystems. Hum. Ecol. Risk. Assess. 4 (5), 1019–1039. Long, E.R., MacDonald, D.D., Smith, S.L., Calder, F.D., 1995. Incidence of adverse biological effects within ranges of chemical concentrations in marine and estuarine sediments. Environ. Manag. 19 (1), 81–97. Long, E.R., Field, L.J., MacDonald, D.D., 1998. Predicting toxicity in marine sediments with numerical sediment quality guidelines. Environ. Toxicol. Chem. 17, 714–727. Long, E.R., Ingersoll, C.G., MacDonald, D.D., 2006. Calculation and uses of mean sediment quality guideline quotient: a critical review. Environ. Sci. Technol. 40, 1726–1736. MacDonald, D.D., Carr, R.S., Calder, F.D., Long, E.R., Ingersoll, C.G., 1996. Development and evaluation of sediment quality guidelines for Florida coastal waters. Ecotoxicology 5 (4), 253–278. MacDonald, D.D., Ingersoll, C.G., Berger, T.A., 2000. Development and evaluation of consensus-based sediment quality guidelines for freshwater ecosystems. Arch. Environ. Contam. Toxicol. 39, 20–31. Magi, E., Bianco, R., Ianni, C., Di Carro, M., 2002. Distribution of polycyclic aromatic hydrocarbons in the sediments of the Adriatic Sea. Environ. Pollut. 119 (1), 91–98. Mai, B.X., Fu, J.M., Zhang, G., Lin, Z., Min, Y.S., Sheng, G.Y., Wang, X.M., 2001. Polycyclic aromatic hydrocarbons in sediments from the Pearl river and estuary, China: spatial and temporal distribution and sources. Appl. Geochem. 16, 1429–1445. Martínez-Lladó, X., Gibert, O., Martí, V., Díez, S., Romo, J., Bayona, J.M., de Pablo, J., 2007. Distribution of polycyclic aromatic hydrocarbons (PAHs) and tributyltin (TBT) in Barcelona harbour sediments and their impact on benthic communities. Environ. Pollut. 149 (1), 104–113. Men, B., He, M.C., Tan, L., Lin, C.Y., Quan, X.C., 2009. Distribution of polycyclic aromatic hydrocarbons in the Daliao River Estuary of Liaodong Bay, Bohai Sea (China). Mar. Pollut. Bull. 58, 818–826. Nasher, E., Heng, L.Y., Zakaria, Z., Surif, S., 2013. Assessing the ecological risk of polycyclic aromatic hydrocarbons in sediments at Langkawi Island, Malaysia. Sci. World J. 2013. Neff, J.M., Stout, S.A., Gunster, D.G., 2005. Ecological risk assessment of polycyclic aromatic hydrocarbons in sediments: identifying sources and ecological hazard. Integr. Environ. Assess. Manag. 1 (1), 22–33. Olawoyin, R., Grayson, R.L., Okareh, O.T., 2012. Eco-toxicological and epidemiological assessment of human exposure to polycyclic aromatic hydrocarbons in the Niger Delta, Nigeria. Toxicol. Environ. Heal. Sci. 4 (3), 173–185. Orecchio, S., Cannata, S., Culotta, L., 2010. How building an underwater pipeline connecting Libya to Sicilian coast is affecting environment: polycyclic aromatic hydrocarbons (PAHs) in sediments; monitoring the evolution of the shore approach area of the Gulf of Gela (Italy). J. Hazard. Mater. 181 (1), 647–658. Oros, D.R., Ross, J.R., 2004. Polycyclic aromatic hydrocarbons in San Francisco Estuary sediments. Mar. Chem. 86 (3), 169–184. Pérez-Fernández, B., Viñas, L., Franco, M.Á., Bargiela, J., 2015. PAHs in the Ría de Arousa (NW Spain): a consideration of PAHs sources and abundance. Mar. Pollut. Bull. 95
(0.29%). Hence, BaP has been proved to be the most potential human carcinogen prevalent at the contaminated site contributing to maximum toxicity. In conclusion, the present study extensively portrays the lessexplored coastline of Gujarat in terms of thorough assessment, occurrence, and exposure to legacy pollutants, i.e., PAHs. The site has been meticulously studied and has been highlighted on a global scale as the site possesses elevated levels of LMW and HMW PAHs. The ecological risk and potential toxicity assessments of PAHs indicated high probability of adverse effects on marine sediments of the Gulf of Kutch. The study revealed that the Gulf of Kutch bears a great risk and can be considered a historically contaminated site when compared to the existing data at other sites globally. The present study would be incontestably valuable to the global database by providing fresh information for regulatory agencies to improve the environmental quality. Acknowledgment The authors are thankful to the Gujarat State Biotechnology Mission (GSBTM) (Grant no. GSBTM/MD/PROJECT/SSA/3392/2012-13) and the Earth System Sciences Organization (ESSO), Ministry of Earth Sciences, Government of India, New Delhi (Grant no. MoES/16/06/ 2013-RDEAS), for their financial assistance to conduct this research. Appendix A. Supplementary data Supplementary data to this article can be found online at http://dx. doi.org/10.1016/j.marpolbul.2017.04.039. References Barakat, A.O., Mostafa, A., Wade, T.L., Sweet, S.T., El Sayed, N.B., 2011. Distribution and characteristics of PAHs in sediments from the Mediterranean coastal environment of Egypt. Mar. Pollut. Bull. 62 (9), 1969–1978. Baumard, P., Budzinski, H., Garrigues, P., 1998. Polycyclic aromatic hydrocarbons in sediments and mussels of the Western Mediterranean Sea. Environ. Toxicol. Chem. 17, 765–776. Benlahcen, K., Chaoui, A., Budzinski, H., Bellocq, J., Garrigues, P., 1997. Distribution and sources of polycyclic aromatic hydrocarbons in some Mediterranean coastal sediments. Mar. Pollut. Bull. 34, 98–305. Bhatt, J.K., Ghevariya, C.M., Dudhagara, D.R., Rajpara, R.K., Dave, B.P., 2014. Application of response surface methodology for rapid chrysene biodegradation by newly isolated marine-derived fungus Cochliobolus lunatus strain CHR4D. J. Microbiol. 52, 908–917. Bortey-Sam, N., Ikenaka, Y., Nakayama, S.M., Akoto, O., Yohannes, Y.B., Baidoo, E., Mizukawa, H., Ishizuka, M., 2014. Occurrence, distribution, sources and toxic potential of polycyclic aromatic hydrocarbons (PAHs) in surface soils from the Kumasi Metropolis, Ghana. Sci. Total Environ. 496, 471–478. Burton Jr., G.A., 2002. Sediment quality criteria in use around the world. Limnology 3 (2), 65–76. Chen, C.W., Chen, C.F., 2011. Distribution, origin, and potential toxicological significance of polycyclic aromatic hydrocarbons (PAHs) in sediments of Kaohsiung Harbor, Taiwan. Mar. Pollut. Bull. 63, 417–423. Chen, C.F., Chen, C.W., Dong, C.D., Kao, C.M., 2013. Assessment of toxicity of polycyclic aromatic hydrocarbons in sediments of Kaohsiung Harbor, Taiwan. Sci. Total Environ. 463, 1174–1181. Dave, B.P., Ghevariya, C.G., Bhatt, J.K., Dudhagara, D.R., Rajpara, R.K., 2014. Enhanced biodegradation of total polycyclic aromatic hydrocarbons (TPAHs) by marine halotolerant Achromobacter xylosoxidans using Triton X-100 and b-cyclodextrine a microcosm approach. Mar. Pollut. Bull. 79, 123–129. De Luca, G., Furesi, A., Leardi, R., Micera, G., Panzanelli, A., Piu, P.C., Sanna, G., 2004. Polycyclic aromatic hydrocarbons assessment in the sediments of the Porto Torres Harbor (Northern Sardinia, Italy). Mar. Chem. 86 (1), 15–32. Dudhagara, D.R., Rajpara, R.K., Bhatt, J.K., Gosai, H.B., Sachaniya, B.K., Dave, B.P., 2016a. Distribution, sources and ecological risk assessment of PAHs in historically contaminated surface sediments at Bhavnagar coast, Gujarat, India. Environ. Pollut. 213, 338–346. Dudhagara, D.R., Rajpara, R.K., Bhatt, J.K., Gosai, H.B., Dave, B.P., 2016b. Bioengineering for polycyclic aromatic hydrocarbon degradation by Mycobacterium litorale: statistical and artificial neural network (ANN) approach. Chemometr. Intell. Lab. 159, 155–163. Eguvbe, P.M., Iwegbue, C.M., Egboh, S.H., Ogala, J.E., Nwajei, G.E., 2015. Source apportionment and identification of polycyclic aromatic hydrocarbons (PAHs) in sediment cores of selected Creeks in Delta State, Nigeria. Environ. Forensic 16 (1), 51–75.
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R.K. Rajpara et al.
Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) distributions in the Bay of Marmara sea: Izmit Bay. Environ. Pollut. 119, 383–397. Tronczynsky, J., Munschy, C., Héas-Moisan, K., Guiot, N., Truquet, I., Olivier, N., Men, S., Furaut, A., 2004. Contamination of the Bay of Biscay by polycyclic aromatic hydrocarbons (PAHs) following the T/V “Erika” oil spill. Aquat. Living Resour. 17, 243–259. USEPA, 1993. Provisional Guidance for Quantitative Risk Assessment of Polycyclic Aromatic Hydrocarbons. (Washington, DC). Viguri, J., Verde, J., Irabien, A., 2002. Environmental assessment of polycyclic aromatic hydrocarbons (PAHs) in surface sediments of the Santander Bay, Northern Spain. Chemosphere 48, 44–60. Wang, X.C., Zhang, Y.X., Chen, R.F., 2001. Distribution and partitioning of polycyclic aromatic hydrocarbons (PAHs) in different size fractions in sediments from Boston Harbor, United States. Mar. Pollut. Bull. 42 (11), 1139–1149. Wattiau, P., 2002. Microbial aspects in bioremediation of soils polluted by polyaromatic hydrocarbons. In: Biotechnology for the Environment: Strategy and Fundamentals. Springer, Netherlands, pp. 69–89. Yuan, D.X., Yang, D.N., Wade, T.L., Qian, Y.R., 2001. Status of persistent organic pollutants in the sediment from several estuaries in China. Environ. Pollut. 114, 101–111. Yunker, M.B., MacDonald, R.W., Vingarzan, R., Mitchell, R.H., Goyette, D., Sylvestre, S., 2002. PAHs in the Fraser River basin: a critical appraisal of PAH ratios as indicators of PAH source and composition. Org. Geochem. 33 (4), 489–515. Zhang, D., Liu, J., Jiang, X., Cao, K., Yin, P., Zhang, X., 2016. Distribution, sources and ecological risk assessment of PAHs in surface sediments from the Luan River Estuary, China. Mar. Pollut. Bull. 102, 223–229.
(1), 155–165. Pietzsch, R., Patchineelam, S.R., Torres, J.P., 2010. Polycyclic aromatic hydrocarbons in recent sediments from a subtropical estuary in Brazil. Mar. Chem. 118 (1), 56–66. Qiao, M., Wang, C., Huang, S., Wang, D., Wang, Z., 2006. Composition, sources, and potential toxicological significance of PAHs in the surface sediments of the Meiliang Bay, Taihu Lake, China. Environ. Int. 32, 28–33. Rahmanpoor, S., Ghafourian, H., Hashtroudi, S.M., Bastami, K.D., 2014. Distribution and sources of polycyclic aromatic hydrocarbons in surface sediments of the Hormuz strait, Persian Gulf. Mar. Pollut. Bull. 78 (1), 224–229. Readman, J.W., Fillmann, G., Tolosa, I., Bartocci, J., Villeneuve, J.P., Catinni, C., Mee, L.D., 2002. Petroleum and PAH contamination of the Black Sea. Mar. Pollut. Bull. 44, 48–62. Savinov, V.M., Savinova, T.N., Matishov, G.G., Dahle, S., Næs, K., 2003. Polycyclic aromatic hydrocarbons (PAHs) and organochlorines (OCs) in bottom sediments of the Guba Pechenga, Barents Sea, Russia. Sci. Total Environ. 306, 39–56. Soclo, H.H., Garrigues, P., Ewald, M., 1986. Analyse quantitative deshydrocarbures aromatiques polycycliques dans les se'diments re'centspar chromatographie en phase liquid et de'tection spectrofluorime'trique. Analusis 14 (7), 344–350. Soclo, H.H., Garrigues, P.H., Ewald, M., 2000. Origin of polycyclic aromatic hydrocarbons (PAHs) in coastal marine sediments: case studies in Cotonou (Benin) and Aquitaine (France) areas. Mar. Pollut. Bull. 40 (5), 387–396. Sprovieri, M., Feo, M.L., Prevedello, L., Manta, D.S., Sammartino, S., Tamburrino, S., Marsella, E., 2007. Heavy metals, polycyclic aromatic hydrocarbons and polychlorinated biphenyls in surface sediments of the Naples harbor (southern Italy). Chemosphere 67, 998–1009. Telli-Karakoc, F., Tolun, L., Henkelmann, B., Klimm, C., Okay, O., Schramm, K., 2002.
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