Contamination of Polycyclic Aromatic Hydrocarbons in Seawater and Sediments of West-Northern Coasts of the Persian Gulf
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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 coasts 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 oil spill. 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 human 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 fish 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). ecosystems. 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 1690 AAGH et al.: CONTAMINATION OF POLYCYCLIC AROMATIC HYDROCARBONS 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.