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Contamination of Polycyclic Aromatic Hydrocarbons in Seawater and Sediments of West-Northern Coasts of the Persian Gulf

Contamination of Polycyclic Aromatic Hydrocarbons in Seawater and Sediments of West-Northern Coasts of the Persian Gulf

Indian Journal of Geo Marine Sciences Vol. 45 (12), December 2016, pp. 1688-1695

Contamination of polycyclic aromatic hydrocarbons in seawater and sediments of West-Northern of the Persian Gulf

Homira Aagh1*, Shirin Rahmanpour1, Ehsane Abedi2, Imane Arebi2 & Ali Mahdinia1

1 Iranian National Institute for Oceanography Marine bio-living department 2 Iranian National center for Oceanography, Bushehr, Iran

*[E-mail: [email protected]]

Received 07 October 2013; revised 25 February 2014

In order to investigate the pollution levels of Polycyclic Aromatic Hydrocarbons (PAHs) in Deylam at Bushehr province of the Persian Gulf, samples of water and sediments were collected from 12 sampling sites and analyzed for PAHs by High- Performance Liquid Chromatography (HPLC). Results indicated low to high pollution levels in sediment samples and moderate to high contamination levels in seawater samples. To determine the source of pollution, the ratios of Low Molecular Weight/High Molecular Weight, Phenanthrene/Anthracene and, Fluoranthene/pyrene were calculated. According to the results, the main sources of PAHs in sediment and water samples in the studied area turned out to be from both pyrroletic and pertogenic inputs, with the predominance of petrogenic sources due to recent . Concentrations of tPAH in this study were about 42 to 180 times higher those in previous studies for water samples, which is a threat to the lives of aquatic biota, and hence beings.

[Key words: Polycyclic aromatic hydrocarbons, Persian Gulf, Water, Sediment, Pertogenic, Pyroletic, Gas Chromatography].

Introduction PAHs may contain four-, five-, six- or seven-member rings, but those with five or six Polycyclic aromatic hydrocarbons (PAHs) are most common. PAHs containing up to six are one of the most concerned organic pollutants fused aromatic rings are often known as "small" since some compounds have been categorized as PAHs, and those containing more than six carcinogenic, mutagenic, and teratogenicity1, 2, 3, 4. aromatic rings are called "large" PAHs. Detection A number of 16 PAH compounds are introduced of PAHs in materials is often done using gas as primary pollutants by US EPA5. PAH chromatography-mass spectrometry, liquid compounds are lipophilic so that they are found chromatography coupled with ultraviolet-visible primarily in soil, sediment and oily materials6. detector, or fluorescence spectroscopic Through accumulating in different tissues of the methods 13, 14. various specious, PAH compounds enter Persian Gulf is located between Arabian food chain and menace people's lives7. The larger Peninsula and Iran. Due to its natural compounds possess less water-solubility and less geographical location, spilled oil tends to volatility. Natural crude oil and coal deposits assemble in its environment rather than being strikingly encompass PAH compounds dispersed or degraded 15. According to various originating from chemical conversion of natural reports, Persian Gulf is one the most oil-polluted product molecules (petrogenic sources). water around the world 16, 17, 18, 19. Furthermore, incomplete combustion of carbon- In 2012 an oil spill occurred in Deylam, containing fuels can also cause the production of West Northern of the Persian Gulf, which may these compounds (pyroletic sources) 8, 9. The type cause serious threat to the lives of resident coastal and the relative amounts of individual produced and benthic organisms. Although the oil leakage PAHs differ from one type of combustion to covered an areas as 20*8 km2 of the water another, making the prosecution of the burning surface, but using skimmers could control the origin possible 4, 9, 8, 10, 11, 12. extent of it. After beach cleaning operation it was assumed that adverse effect of oil pollution was INDIAN J. MAR. SCI., VOL. 45, NO. 12, DECEMBER 2016 1689 dissolved. This led us to determine PAH levels in Province, Northern of the Persian Gulf, the seawater and sediments in Deylam. In this study geographic coordinates are 30°06'18N to the results were compared with sediment and 30°09'21N (Latitudes) and 50°06'37E to water guidelines and those of other marine 50°08'50E (Longitudes) (Figure. 1). . Extraction the sediment samples were Materials and Methods performed using dichloromethane in ultrasonic water bath at 30 ºC for one hour (standard Triplicate surface coastal waters and method, EPA methods3540C, 3550B, 1996; EPA sediment samples from top 5 cm were collected method 3630 C, 1996). Subsequently flask from 3 transects (9 sediments and 3 water containing the sample was place in bath at 30 ºC samples) 8 days after the accident, using Niskin for 24 hours; again, extraction was repeated by bottle and Van Veen grab, respectively. Sediment replacing the sample in ultrasonic bath for one samples were collected from sub tidal, intertidal hour and at the end the solution passed through and supra littoral as illustrated in figure 1. glass wool filter. Sixteen Aromatic Hydrocarbons Samples were placed into pre-labeled dark jars were determined using High Performance Liquid and aluminum vessels, respectively, shipped to Chromatography (HP LC, Agillent, 1100) (EPA the laboratory on ice and kept in -20°C prior to methods3540C, 3550B, 1996). the analysis. The study was carried out during February 2012. Deylam is located at Boshehr

Figure 1: The location of the sampling site in the Bushehr province

Quality control included the use of procedural was reported for each element. The limits of blanks and standard addition in each digestion detection (ng. g-1) were set as three times the batch. Recoveries foe 16 elements were 85-110% standard deviation of the procedural blanks and 80-97% for sediment and water samples, (Table 1). respectively. The average of triplicates analysis

Table 1: Detection limits (DL) of elements (ng g-1). Elements DL DL Elements DL DL sediment water sediment water Naphthalene 0.03 0.01 Benzo (A) Anthracen 0.06 0.03 Acenaphtylen 0.38 0.19 Chrysene 0.01 0.008 Acenaphthene 0.06 0.04 Benzo(B) Flouranthen 0.09 0.07 Fluorene 0.41 0.28 Benzo(K) Flouranthen 0.06 0.03 Phenanthrene 0.02 0.01 Benzo(A) Pyren 0.04 0.02 Anthracene 0.12 0.06 Dibenzo(A,H) Anthracen 0.04 0.028 Fluoranthene 0.73 0.30 Benzo(G,H,I) Perylen 0.04 0.01 Pyrene 0.07 0.05 Indeno(1,2,3-CD)Pyren 0.50 0.37

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Results and Discussion

Results of the 16 PAH compounds in CD)pyren, and benzo(G,H,I) perylen in transect 1 seawater of Deylam are shown in table 2. In our were not observed. From 9 stations, study, the detected concentrations of the elements Benzo(G,H,I) perylen as a five-membered ring (triplicate measurements) were higher than the PAH compound did not occur in transects 1 and corresponding detection limit. 3, while in transects 2 it demonstrated the figure of 4.2 ng L-1. Due to hydrophobic properties, Levels of the total PAHs in studied stations PAHs possess low solubility in water which range from 65 to 1059 ngL-1. Among 16 decreases with an increase in molecular weight, measured PAHs, compounds encompassing in a way that concentrations of the five- or six- indeno(1,2,3-CD)pyren, benzo(G,H,I) perylen, membered ring compounds is too low in seawater dibenzo(A,H) anthracen, benzo(A) pyren, and this compounds are more likely to precipitate benzo(K) flouranthen, benzo(B) flouranthen, and in sediments 20. Maximum and minimum benzo (A) anthracen in transect 3, compounds concentrations of the PAHs were related to the including dibenzo(A,H) anthracen, chrysene, indeno(1,2,3-CD) pyren in station 2 (875.4 ngL- benzo (A) anthracen, flouranthen and 1), and dibenzo(A,H) anthracen in station 1 (0.23 acenaphtylen in transect 2, and compounds ngL-1), respectively (Figure 2). including flouren, chrysene, indeno(1,2,3-

Table 2: Concentrations of the PAH compounds (ng L-1) in the seawater samples of Deylam. 1 Compounds Station 1 Station 2 Station 3 Average Guidelines Naphthalene 6.9±0.08 7.2±0.1 4.3±0.05 6.1 1 Acenaphtylen 5.3±0.5 - 4.2±0.18 4.7 Acenaphthene 3.0±0.01 3.0±0.01 2.9±0.004 3.0 6 Fluorene - 3.8±0.06 3.7±0.11 3.7 12 Phenanthrene 17.5±0.05 2.9±0.02 3.7±0.02 8.0 Anthracene 14.0±0.2 13.3±0.3 11.1±0.2 12.8 NR Fluoranthene 16.5±1.04 23.9±0.8 20.2 NR Pyrene 18.1±0.8 35.3±1.8 7.7±0.4 20.4 NR Benzo (A) Anthracen 22.6±1.4 - - 22.6 Chrysene - - 3.8±0.01 3.8 0.1 Benzo(B) Flouranthen 4.1±0.1 7.0±0.3 - 5.6 Benzo(K) Flouranthen 23.8±2.7 107.0±3.3 - 65.4 Benzo(A) Pyren 2.8±0.01 2.6±0.01 - 2.7 Dibenzo(A,H) Anthracen 0.2±0.001 - 0.2 Benzo(G,H,I) Perylen - 4.2±0.02 - 4.2 0.01 Indeno(1,2,3-CD)Pyren - 875.4±67.8 - 875.4 Total 135 1062 65 1059

Regarding the mentioned results, three- and Also, the study conducted on northwestern waters four-membered ring PAHs were predominantly of the Persian Gulf reported much higher amount present in the seawater of Deylam, which was in of three-membered ring PAHs in seawater accordance with the data reported by Zhou et al., samples 22. Mirza and coworkers (2011)11 (2003) 21 demonstrating the presence of three- and reported similar results from the analysis of the four-membered ring PAHs in seawater samples of seawater in Bushehr coastal areas. They claimed the Daya Bay in China. that three- and four-membered ring PAHs were more abundant than other compounds of this ilk. 1 Ministry of Environment – Environmental protection Division http://www.env.gov.bc.ca/wat/wq/BCguidelines/pahs/ pahs_over.html

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The results of this study on seawater samples communities (LC50), have been determined as of Deylam were compared with those of other less than 10 ppm 24, 25. Results of this study parts around the world (table 3). As it is apparent demonstrated that ∑PAH concentrations were from table 3, levels of ∑PAHs in seawater less than 10 ppm, hence coastal waters of the samples of Deylam was much less than those in studied stations were below the reported value for Bohai in China, Daya Bay in China, waters LC50 of marine organism communities, but this around wells and England, and Xiamen sea in concentrations were at risky levels in terms of China. However, measured concentrations of toxicity for marine organisms, because ∑PAH ∑PAHs in present study was higher than those concentrations were about 42 to 180 times higher reported in Jaspic outfall in America, Seine than those reported by Mirza and coworkers outfall and in France, Yeong Bay in Korea, (1390) in 2011 for the same stations. This striking Rijeka Bay Aderyatic sea, and obviously much rise in the levels of PAHs in this area was a higher than those reported in eastern consequence of the occurrence of the recent oil Mediterranean Ejeh sea and Baltic sea. spill. Regarding these findings accompanied by the fact that PAH compounds possess In comparison with reported levels in 2011 carcinogenic and mutagenic properties, it would for the same stations, tPAH concentrations were be essential for the region to be investigated about 42 to 180 times higher for water samples, promptly and especial considerations for the due to the recent oil spill 11. remediation of the place should be employed as soon as possible. Generally, low molecular weight PAH compounds are considered more toxic for marine Table 3: Comparison of the ∑PAH concentrations (ng L-1) in biota in comparison with heavier ones 23. Total water samples of the studied area with those of other PAH concentrations which cause the of 50 parts around the world. percent of the various marine organism Studied area PAH levels Reference Bohai sea in China 139-1718 36 Daya Bay in China 4228-29325 21 Ejeh sea (eastern Mediterranean) 0.1-0.5 37 Baltic sea 0.5-14 38 waters around wells and England <1-24821 23 Xiamensea in China 69600-26920 25 Jaspic outfall in America 20-66 39 Seine outfall and river in France 4-36 47 Yeong Bay in Korea 3-33 40 Rijeca Bay Aderyatic sea ND*-305 41 Persian Gulf, coastal waters of 1.6-6 11 Bushehr Deylam , Persian Gulf 0.2-1062 Present study

Figure 2: Comparing the average of PAHs values in different *ND: Non- Detectable stations (Station 2 with auxiliary axis).Table Determination of pollution source according stations 1 and 2 which mean that PAH to molecular ratios in seawater compounds are coming from petrogenic sources In many studies, in order to determine the 10, 28. Indeed, abundance of Pyrene in comparison sources of PAH compounds, molecular ratios are to Fluoranthene is a verification of the presence often calculated 26. In this favor, ratios of Phe/Ant of PAHs derived from petroleum10, 28. On the and Flu/Pyr were utilized here to find the source other hand, this ratio in station 3 is higher than 1 of pollution 8, 26, 27. The ratio of PHE/ANT<10 and which means PAH compounds were originating FLU/PYR>1 is a representation of the pyroletic from pyroletic sources10, 28. Regarding the source, whereas the ratio of PHE/ANT>10 and mentioned results, it can be concluded that FLU/PYR<1 indicates the PAHs from the stations 1 and 2 were more exposed to petrogenic petrogenic source 8, 10, 12, 28. Results obtained from pollution caused by oil spill, in comparison with the ratio of phenanthere to anteracene in seawater station 3. According to the measured molecular of the studied stations were less than 10 which is ratios, source of pollution in the studied areas an indication of pyroletic sources 10, 28. were both pyroletic and petrogenic sources with Results of the molecular ratios related to the predominance of petrogenic ones. In fact, Fluoranthene to Pyrene were less than 1 in entrance of PAHs to the seawater from cited oil

1692 AAGH et al.: CONTAMINATION OF POLYCYCLIC AROMATIC HYDROCARBONS spill is the main source of oil pollution in the area Mediterranean Sea, Tabasco state, and coastal investigated in the present study. area of Bahrian. Nevertheless, they were higher Concentrations of PAHs in sediments than costal area of Qatar, Coastal area of Results of the 16 PAH compounds in Bushehr; and much higher than those measured sediments of 9 stations in Deylam are shown in for coastal area of Oman, coastal area of UAE. table 4. Levels of the total PAHs in studied Similar values were reported for the Kyeonggi stations ranged between 15.3 and 759 ng.g-1. Bay, and Todos Santos Bay. In 1996, the Among 16 measured PAHs, stations including concentration limits of ΣPAHs for marine high tidal zone of station 2, sub tidal zone of sediments was considered as 4022 ng.g-1 and station 1 and intertidal zone of station 3 Canadian Environmental Quality Guidelines manifested only 6 compounds, and intertidal zone presents this value as 7071 ng.g-1, in 2002 30. of station 2 lacked 12 PAHs, showing just four According to NOAA sediment quality guideline, compounds. The least ∑PAH concentrations were concentration levels of ∑PAHs more than 4000 observed in intertidal zone of station 2 (15.3 ngg- ng g-1 dry weight is an indication of the very high 1), whereas ∑PAH levels was detected at high pollution and toxic state of the sediment tidal zone of station 3 (759 ngg-1). Highest levels environment, and the levels below 100 ng.g-1 dry of ∑PAHs were observed in high tidal and sub weight shows the areas with no pollution to PAH tidal zones of station 3 and next in intertidal zone compounds 31. According to the guideline of station 1. PAH compounds are most likely to suggested by Baumared and coworkers 10, PAH accumulate in sediments and floating particles in levels can be assigned as low, moderate, high and seawater, due to low solubility and hydrophobic very high when tPAH concentrations are 0- properties 23, 29. 100,100-1000,1000-5000, and >5000 ng.g1, The results of this study on sediment respectively. samples of Deylam were compared with those of other parts around the world (table 5). Pollution levels measured in the present study were lower than those reported for Northwest Mediterranean Sea, Caspian sea, West

Table 4: Concentrations of the PAH compounds in sediment samples of Deylam. Zones High tidal intertidal sub tidal Mean Station 1 2 3 1 2 3 1 2 3 Naph 8.4 nd nd 4.5 4.5 5.2 nd nd nd 2.5 Acenaphthylene 10.4 Nd 17.7 6.1 Nd 6.6 6.1 5.6 6.7 6.6 Acenaphten 3.2 nd nd nd nd nd nd nd nd 0.4 Flouren 39.6 nd 12.3 10.6 nd 16.1 3.7 4.6 4.5 10.2 Phenantheren 3.4 3.7 9.7 3.8 Nd 11 4.1 4.1 5.8 5.1 Anthracen nd nd 233.6 62.8 nd 136.5 18.6 nd nd 50.2 Flouranthen nd 23.6 46.3 30.7 5.8 nd 10.8 23.1 131 30.2 Pyren 3 2.1 4.1 1.9 1.8 2.2 2.0 1.8 10.0 3.2 Benzo (A) anthracen 0.05 nd 2.2 0.2 nd nd nd nd 0.5 0.3 Crysen 4.3 3.2 6.8 4.2 3.2 nd nd 3.6 4.5 3.3 Benzo(B) flouranthen 4.5 4.6 48.2 18.7 nd nd nd 9.3 21.6 11.9 Benzo(K) flouranthen nd nd 234.5 48.4 nd nd nd 39.4 26.2 38.7 benzo(A) pyren nd 2.6 6.9 2.7 nd nd nd 3.3 4.7 2.3 Dibenzo(A,H) anthracen nd nd 0.9 0.6 nd nd nd 04 0.6 0.3 Benzo(G,H,I) perylen nd nd 6.7 4.8 nd nd nd nd 5.4 1.9 Indeno(1,2,3-CD)pyren nd nd 129.1 nd nd nd nd nd 43.9 19.2 Total 76.8 40 758.9 200 15.3 177.5 45.4 95.3 265.8 186.1 St: Station H: High tidal L: sub tidal M: intertidal

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Owing to the concentration of PAHs in the study area, its concentration level was not still Table 5: Comparison of the ∑PAH concentrations (ng/L) in sediment samples of the studied area with those of other meet the NOAA sediment quality guideline value -1 parts around the world. (ERL= 4022 ng.g dry weight). Studied area PAH levels Reference 32 Notar and coworkers assigned Northwest Coast Mediterranean Sea 86.5-48090 42 concentration levels of PAH in range between 50 Caspian sea, Azerbaijan 338-2988 43 and 250 ng.g-1 as low to moderate polluted Kyeonggi Bay, Korea 10-1400 44 West Mediterranean Sea 1.5-20440 10, 28 sediments and samples with PAH concentrations -1 Todos Santos Bay, Mexico 7.6-813 45 more than 500 ng.g , as polluted sediments. On Tabasco state, Mexico 454-3120 46 the basis of the comparison results and regarding Gulf and the Gulf of Oman, Oman 1.6-30 14 these classifications and guidelines, pollution Gulf and the Gulf of Oman, Bahrian 13-6600 14 Gulf and the Gulf of Oman, Qatar 0.55-92 14 levels of the investigated area in this study were Gulf and the Gulf of Oman, UAE 0.6-9.4 14 assigned as low to moderate and in some cases Coastal area of Bushehr, Persian Gulf 41.7-227.5 11 high, for sediment samples. The results of this Coastal area of Bushehr, Persian Gulf 15.28-759 Present study were almost 1000 times higher than those study in Nayband areas. Mean concentrations of the detected PAH of Pyrene in comparison to Fluoranthene is a compounds in this survey and Interim Marine verification of the presence of PAHs derived Sediment Quality Guidelines (ISQG) or threshold from petroleum 10, 28. On the other hand, this ratio effect level (TEL), Probable Effect Levels (PEL), is higher than 1 for other stations which means effect range low (ERL), and effect range median PAH compounds are originating from pyroletic (ERM) are indicated in table 6 33, 34, 35. As it is sources10, 28. Regarding the mentioned results, it apparent from this table, in some cases, mean can be concluded that high tidal zone of station 1 concentrations of the detected PAHs in this study and intertidal zone of station 3 were more exceed some of the standards, especially ISQC; exposed to petrogenic pollution caused by oil which means that the area is at the risky levels of spill, in comparison with other stations. pollution. According to measured molecular ratios, source of pollution in studied areas are both pyroletic Determination of pollution source according to and petrogenic sources. In fact, entrance of PAHs molecular ratios in sediment samples to the seawater from cited oil spill is the main petrogenic source. However, most of the PAH Results of the molecular ratios related to compounds have not had enough time to Fluoranthene to Pyrene were less than 1 in high precipitate into the sediments. Anthracen was not tidal zone of station 1 and intertidal zone station detected in stations including high tidal zone of 3, which means that PAH compounds are coming stations 1, 2, sub tidal zone of stations 2, 3 and from petrogenic sources 10, 28. Indeed, aboundance intertidal zone of station 2.

Table 6: Concentrations of PAHs (ng.g-1 d.w) in contrast with standards and guidelines. PAH Type PEL ERL ERM TEL or ISQC Water, Present Sediments, USA study Present study Acenaphthylene 128 44 640 5.87 3.1 6.6 Acenaphthene 88.9 16 500 6.71 2.9 0.4 Fluorene 144 19 540 21.2 2.5 10.2 Phenanthene 544 240 1500 86.7 8.03 5.1 Anthracene 245 85.3 1100 46.9 12.8 50.2 Fluoranthene 1494 600 5100 113 13.5 30.2 Pyrene 1398 665 2600 153 20.4 3.2 Chrysene 846 384 2800 108 1.3 3.3 Benz[a] anthracene 693 261 1600 74.8 7.5 0.3 Benzo (a)pyrene 763 430 1600 88.8 1.8 2.3 napthalene 391 160 2100 34.6 6.1 2.5 benzo[b]fluoranthene Na Na Na Na 3.7 12 benzo[k]fluoranthene Na Na Na Na 43.6 39 indeno(1,2,3-CD)pyren Na Na Na Na 292 19 Benzo[ghi]perylene Na Na Na Na 1.4 1.9 dibenz[a,h]anthracene 135 63.4 260 6.22 0.1 0.3 ERL: effect range low ERM: effect range median TEL: threshold effect level PEL: probable effect level

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