Metals bioaccumulation, possible sources and consumption risk assessment in five Sillaginid species, a case study: Bandar Abbas (Persian Gulf) and Chabahar Bay (Oman Sea), Iran.

In this study, the concentrations of 10 metals (As, Al, Cd, Cr, Cu, Fe, Hg, Ni, Pb and Zn) in different tissues (gill, muscle and otolith) of five sillaginid species (Sillago arabica, S. attenuata and S. sihama from the Persian Gulf and S. indica, S. sihama and Sillaginopodys chondropus from the Oman Sea) were analyzed using ICP-MS, and the potential human health risk assessment for local consumers was also conducted using standard indices. The concentration of trace metals (µg g-1 dw) in fish ranged from 0.24 to 16.09 (As), 7.88 to 167.51 (Al), 0.005 > -0.866 (Cd), 0.006 > -7.95 (Cr), 1.02-5.58 (Cu), 24.86 to 390.85 (Fe), 0.005 > -1.93 (Hg), 0.021 > -7.80 (Ni), 0.33-4.41 (Pb) and 4.78-170.43 (Zn). The levels of trace metals varied significantly among sampling sites, fish species and their tissues. Gill tissues accumulate higher concentrations of the analyzed elements, except for As and Hg, whose higher concentrations were found in muscle tissues. Among the species, S. sihama in the Persian Gulf showed the highest levels of toxic metals compared to the other species. The dendrogram of metal association in fish muscle tissues revealed that Ni, Cr, Cd, Pb and Hg in muscles mainly originated from anthropogenic sources, especially petroleum activities. A second dendrogram based on the association of these five metals in the muscle tissue separated the sillaginid species of the Persian Gulf from the Oman Sea. The mean concentrations of the analyzed metals in the edible tissues were lower than international standards of maximum permissible limits (MPL), except for inorganic As (iAs) and Pb. The index of estimated daily intake (EDI) for Cr and Hg in all sillaginid species, and iAs, Pb and Ni only in the Persian Gulf's sillaginid species was higher than the recommended values. The value of the target hazard quotient (THQ) indicated that the intake of individual heavy metals due to the consumption of sillaginid species was safe for human health (except Hg in S. arabica) whereas combined heavy metals' intake revealed potential health problems in the case of increased consumption for all three sillaginids in the Persian Gulf. Target cancer risk (TR) for iAs in all species and Cd, Cr and Ni in Persian Gulf species was higher than the acceptable range. The results indicated the health issues associated with high consumption, especially for sillaginids in the Persian Gulf, which should be considered in food safety monitoring for local people in the area.

Seasonal occurrence, source apportionment, and cancer risk assessment of PAHs in the second largest international holy metropolitan: Mashhad, Iran.

Street dust resuspension is one of the main sources of particulate matter with impacts on air quality, health, and climate. This research was aimed to determine the concentration, source, and health risk of polycyclic aromatic hydrocarbons (PAHs) in street dust of Mashhad city. To this end, USEPA-regulated 16 PAHs were measured in 84 dust samples using gas chromatography coupled to mass spectrometry (GC-MS). The source of Σ16PAHs was identified using diagnostic ratios (DRs), positive matrix factorization (PMF), and principal component analysis (PCA). The measured Σ16PAHs demonstrated different spatial concentrations (from 1,005 to 9,138.96 µg kg-1) and showed higher levels in summer (1,206.21-9,138.96 µg kg-1), although 4-ring PAHs exhibited maximum levels in both summer and winter. The findings revealed that the dust-deposited PAHs are predominantly emitted through combustion of fossil fuels (such as diesel and gasoline) and natural gas. The total incremental lifetime cancer risk (ILCR) was assessed by considering three possible exposure routes separately for children and adults and calculated carcinogenic risk values of 2.24E-06 and 2.14E-06, respectively. ILCR is above the baseline value (1.0E-06) for children and adults in both seasons.

Invasive Weed Asystasia gangetica as a Potential Biomonitor and a Phytoremediator of Potentially Toxic Metals: A Case Study in Peninsular Malaysia.

The invasive weed Asystasia gangetica was investigated for its potential as a biomonitor and as a phytoremediator of potentially toxic metals (PTMs) (Cd, Cu, Ni, Pb, and Zn) in Peninsular Malaysia owing to its ecological resistance towards unfavourable environments. The biomonitoring potential of PTMs was determined based on the correlation analysis of the metals in the different parts of the plant (leaves, stems, and roots) and its habitat topsoils. In the roots, the concentrations (mg/kg dry weight) of Cd, Cu, Ni, Pb, and Zn ranged from 0.03 to 2.18, 9.22 to 139, 0.63 to 5.47, 2.43 to 10.5, and 50.7 to 300, respectively. In the leaves, the concentrations (mg/kg dry weight) of Cd, Cu, Ni, Pb, and Zn ranged from 0.03 to 1.16, 7.94 to 20.2, 0.03 to 6.13, 2.10 to 21.8, and 18.8 to 160, respectively. In the stems, the concentrations (mg/kg dry weight) of Cd, Cu, Ni, Pb, and Zn ranged from 0.03 to 1.25, 5.57 to 11.8, 0.23 to 3.69, 0.01 to 7.79, and 26.4 to 246, respectively. On the other hand, the phytoremediation potential of the five metals was estimated based on the bioconcentration factor (BCF) and the translocation factor (TF) values. Correlation analysis revealed that the roots and stems could be used as biomonitors of Cu, the stems as biomonitors of Ni, the roots and leaves as biomonitors of Pb, and all three parts of the plant as biomonitors of Zn. According to the BCF values, in the topsoil, the "easily, freely, leachable, or exchangeable" geochemical fractions of the five metals could be more easily transferred to the roots, leaves, and stems when compared with total concentrations. Based on the TF values of Cd, Ni, and Pb, the metal transfer to the stems (or leaves) from the roots was efficient (>1.0) at most sampling sites. The results of BCF and TF showed that A. gangetica was a good phytoextractor for Cd and Ni, and a good phytostabilizer for Cu, Pb, and Zn. Therefore, A. gangetica is a good candidate as a biomonitor and a phytoremediator of Ni, Pb, and Zn for sustainable contaminant remediation subject to suitable field management strategies.

Bioaccumulation of zinc in edible tropical vegetables in Peninsular Malaysia and its human health risk assessment based on various ethnicities in Malaysia.

Along with the growing utilization of zinc (Zn) and Zn-containing nanoparticles in various industries, Zn ecotoxicological evaluation on human food supply is necessary even though Zn is generally considered safe and rarely concentrated ecotoxicologically. This study aimed to investigate the bioaccumulation of Zn in 18 species of vegetables (seven leafy, nine fruity vegetables and one species each of tuber and legume) collected from two farming sites in the west coast of Peninsular Malaysia. A human health risk assessment (HHRA) was also conducted. In addition to HHRA based on the general population, HHRA based on each major ethnic group of the Malaysian society was also determined considering that the food consumption pattern would definitely be varied across ethnicities and age groups (children and adults). The study results showed that Zn concentrations were significantly higher (p < 0.05) in leafy vegetables than in other types of vegetables. However, the target hazard quotient (THQ) values were all found to be < 1.0. Therefore, based on the Malaysian ethnicities and age groups with their respective vegetable consumption patterns, the results indicated insignificant noncarcinogenic human health risk of Zn via oral consumption of vegetables by the Malaysian population. As a metric of measurement of HHRA, a comparison of THQ values could yield previously unreported insights into HHRA differences among the compared populations. A comparison of THQ values among the consumer groups indicated higher HHR for Chinese Malaysians and children due to their higher vegetable consumption and lower body weight, respectively. A comparison the Zn intakes of all the consumer groups with the recommended nutrient intakes indicated that the oral consumption of the vegetable species collected in this study would not result in Zn-related hazards and would not be able to fulfil the Zn dietary need of the individual consumer.

Modeling Sediment Ni and V Spatial Distribution to Identify Hotspots in the Shadegan Wildlife Refuge, at the Head of the Persian Gulf.

The distribution and origins of Ni and V were assigned in the surficial sediments from 160 stations in Shadegan international wetlands with 537,700 ha. The findings showed that the mean total content of Ni and V in the surface sediments were 45.08 ± 12.09 and 25.25 ± 20.8 µg g-1 dw, respectively. According to the analysis chemical speciation, the Ni and V residual fraction in the surface sediments were calculated for > 80% of the total level of metals, indicating that the metals may be an indicator for the input of natural resources. The analysis of the interpolation maps according to their chemical fractionation manifested that the Ni and V pollution hotspots have been happened in the northern, southern, and western points. Interpolation maps also highlighted that Ni and V are often controlled by natural factors like parent material; however, anthropogenic inputs have also caused the accumulation of these metals in the sediment.

Assessments of the Ecological and Health Risks of Potentially Toxic Metals in the Topsoils of Different Land Uses: A Case Study in Peninsular Malaysia.

Human activities due to different land uses are being studied widely in many countries. This study aimed to determine the ecological risks and human health risk assessments (HHRA) of Cd, Pb, Ni, Cu, and Zn in the topsoils of six land uses in Peninsular Malaysia. The ranges of the potentially toxic metals (PTMs) in the soils (mg/kg, dry weight) of this study were 0.24-12.43 for Cd (mean: 1.94), 4.66-2363 for Cu (mean: 228), 2576-116,344 for Fe (mean: 32,618), 2.38-75.67 for Ni (mean: 16.04), 7.22-969 for Pb (mean: 115) and 11.03-3820 for Zn (mean: 512). For the ecological risk assessments, the potential ecological risk index (PERI) for single metals indicated that the severity of pollution of the five metals decreased in the following sequence: Cd > Cu > Pb > Zn > Ni. It was found that industry, landfill, rubbish heap, and mining areas were categorized as "very high ecological risk". For HHRA, the land uses of industry, landfill and rubbish heap were found to have higher hazard quotient (HQ) values for the three pathways (with the order: ingestion > dermal contact > inhalation ingestion) of the five metals for children and adults, when compared to the mining, plantation, and residential areas. The values for both the non-carcinogenic (Cd, Cu, Ni, and Zn), and carcinogenic risks (CR) for inhalation (Cd and Ni) obtained for children and adults in this study showed no serious adverse health impacts on their health. However, of public concern, the hazard index (HI), for Pb of children at the landfill (L-3) and the rubbish heap (RH-3) sites exceeded 1.0, indicating non-carcinogenic risk (NCR) for children. Therefore, these PERI and HHRA results provided fundamental data for PTMs pollution mitigation and environmental management in areas of different land uses in Peninsular Malaysia.

Potential use of grapevine cv Askari for heavy metal phytoremediation purposes at greenhouse scale.

Grapevine varieties possess desirable characteristics for phytoremediation purposes. We investigated the potential of grapevine cv Askari in phytoremediation of heavy metal (HM) pollutions. In total 80 grapevine seedlings were exposed to four levels of HM stress (mild, low, moderate, and severe) in greenhouse condition during two growing years (2018 and 2019). The HM concentrations (Zn, Cu, Cd, Cr, and Pb) were subsequently determined in the soils, roots, and grapevine aboveground parts (AGPs), and then phytoextraction and phytostabilization potential assessment indices, i.e., biological absorption coefficient (BAC), bioconcentration factor (BCF), and translocation factor (TF), were calculated. Results led to ranking of the cumulative concentration order of the HMs, i.e.: soils (3476.6) > AGPs (1418.8) > roots (562.2) mg/kg-DW. The mean concentrations ranking order of studied HMs were in soil: Cu (1184.8) > Pb (865.5) > Cd (803.2) > Cr (623.0) > Zn (277.9) mg/kg-DW; roots, Cu (242.0) > Cd (239.5) > Zn (188.8) > Pb (63.5) > Cr (17.2) mg/kg-DW; and AGP environments, Cu (910.2) > Cd (322.9) > Zn (160.3) > Pb (152.9) > Cr (25.3) mg/kg-DW. Principal component analysis results demonstrated the same distribution pattern for the studied HMs between soil, root, and AGP environments, and the highest correlation coefficients were found for Cu, Zn, and Cd. Based on the obtained results (Cu-BAC (> 1), Zn-BCF (> 1), Zn-TF (< 1), Cu-AGP mean concentrations (> 1000 mg/kg-DW), and Cd-AGP mean concentrations (> 100 mg/kg-DW)), it can be concluded that grapevine cv Askari possesses potentials for phytoremediation purposes of Cu, Zn, and Cd. These results were acquired in a greenhouse environment and under controlled conditions; we suggest that the phytoremediation potential of this grapevine variety be assessed in a contaminated vineyard environment as well.

Human Health Risk Assessments of Trace Metals on the Clam Corbicula javanica in a Tropical River in Peninsular Malaysia.

This study aimed to analyse ten trace metal concentrations in the edible part of the freshwater clam Corbicula javanica and to provide a critical assessment of the potential risks to human health through consumption of this clam as food based on well-established indices and food safety guidelines. The clams were captured from a pristine original site and transplanted to other sites with different environmental qualities. The trace metal levels in the edible total soft tissue (TST) of the clam were below those of the food safety guidelines referred to except for Pb, which exceeded the permissible limit set by the European Commission (2006) and the US Food and Drug Administration/ Center for Food Safety and Applied Nutrition); Interstate Shellfish Sanitation Conference. (USFDA/CFSAN; ISSC) (2007). The estimated daily intake (EDI) values of the clam were found to be lower than the oral reference dose and the calculated target hazard quotient (THQ) and total THQ were found to be less than 1. Therefore, in conclusion, the human health risk for consumption of TST of C. javanica at both average and high-level were insignificant regardless of the environment it was exposed to.

The influence of human activity and morphological characteristics of beaches on plastic debris distribution along the Caspian Sea as a closed water body.

The Caspian Sea is the largest land-locked lake in the world that includes numerous endemic species. Because of its enclosed nature, the pollutants entering this water body become entrapped. The present paper examines the influence of human activity and beach morphology on the abundance and distribution of stranded plastic debris along the Caspian Sea coastlines. It would be possible by relating some characteristics of these beaches (population, urbanization, substrate type, and slope of beaches) with the abundance of plastic debris through a PCo analysis. The results showed that in our study area, the most effective factors on plastic debris distribution were urbanization and population followed by the slope and substrate of beaches. Three size classes of plastic debris were defined as "large microplastic" (1 to < 5 mm), "mesoplastic" (5 to < 25 mm), and "macroplastic" (> 25 mm). The density of the large microplastic, mesoplastic, and macroplastic materials on the Caspian Sea coastline was 8.43 ± 0.54, 8.74 ± 0.42, and 7.53 ± 0.30 particles/m2, respectively. Foam was the most abundant microplastic debris along the study area (47.58%), followed by resin pellets (33.93%) and fragments (16.30%), respectively. We also selected the Boujagh National Park with limited accessibility as an appropriate area for the study of marine debris as one sampling station. Cigarette butts and film pieces displayed a different distribution pattern compared to other debris types in the Boujagh National Park station likely due to their distinct buoyancy specification.

Geochemical imprints of occurrence, vertical distribution and sources of aliphatic hydrocarbons, aliphatic ketones, hopanes and steranes in sediment cores from ten Iranian Coral Islands, Persian Gulf.

The levels, vertical distribution and sources of hydrocarbons and petroleum biomarkers were estimated for the first time in sediment cores (0-40 cm) from ten coral Islands of the Persian Gulf, Iran. Discrepant hydrocarbons, including linear n-alkanes (n-C11 to n-C40) and isoprenoids (AHs), aliphatic ketones (AKs), hopanes and steranes were measured in all core samples, showing mean concentrations ranging from 209 to 5388 µg g-1dw (∑30AH), 2-244 µg g-1-dw (∑13AK), 189-3713 ng g-1dw (∑31hopane) and 42-3864 ng g-1dw (∑15sterane), respectively. All sediment cores were found to be petroleum polluted, with ∑30AH > ∑31hopane > ∑15sterane > ∑13AK, with higher levels recorded at 10-20 cm, mainly at industrial sites. Various diagnostic indices revealed that hydrocarbons derived mainly from anthropogenic inputs, with significant contribution of biogenic origin at sites less polluted. Moreover, total organic carbon (0.24-23.45 mg g-1-dw), terrestrial and marine organic matter had an overwhelming effect on hydrocarbons deposition in sediment cores. Overall, findings provide relevant information for monitoring and preventing petroleum pollution in the sensitive ecosystems of the Persian Gulf.

Distribution of linear alkylbenzenes as a domestic sewage molecular marker in surface sediments of International Anzali Wetland in the southwest of the Caspian Sea, Iran.

Due to directly receiving high volume of untreated urban and industrial sewage and in turn transferring the pollutants to fish and back to humans, the International Anzali Wetland has been considered to be urgently registered in the Montreux Record. Hence, the present study was aimed to determine the spatial distribution of the linear alkylbenzenes (LABs) in surface sediments of the wetland and its sewage contamination situation. The surface sediments (sampling stations = 167) were collected from the western, eastern, southwest, and central regions of the wetland. The samples were extracted, fractioned, and then analyzed using gas chromatography-mass spectrometry (GC-MS). The concentration of LABs in the sediment samples revealed a range from 394.12 to 109,305.26 ng g-1 dw. The concentrations of ΣLABs in the eastern region were significantly higher than that in the other regions. The occurrence of low ratio of internal to external isomers (I/E ratio) of LABs (from 0.65 to 1.30) and D% (from - 0.07 to 24.13) implied effluent row or poorly untreated sewage into the wetland. No correlation was observed between the detected LAB concentrations with total organic carbon (TOC) and grain size. Taken together, regional anthropogenic inputs are the controlling factors for the observed spatial distributions of ∑LABs in the International Anzali Wetland. The findings suggested that LABs are powerful indicators to trace anthropogenic sewage contamination and also highlighted the necessity of sewage treatment plants to be founded around the International Anzali Wetland, especially in the vicinity of the eastern and central regions.

Multivariate curve resolution of organic pollution patterns in mangrove forest sediment from Qeshm Island and Khamir Port-Persian Gulf, Iran.

Straight-chain alkanes (n-alkanes) have been proposed as biomarkers to assess petroleum pollution sources in marine environments. In this work, three sampling sites were selected along Iranian-protected mangrove forests in the Persian Gulf. Sample sites were chosen to represent different compositions and sources of n-alkanes in surface sediments (0-5 cm) from different locations in the Khamir Port, in the middle part of the Gulf, and in the Qeshm Island. Samples were analyzed by gas chromatography-mass spectrometry (GC-MS), and the obtained n-alkanes concentrations were analyzed by principal component analysis (PCA) and multivariate curve resolution alternating least squares (MCR-ALS) to deduce their possible sources and distribution patterns. Results revealed that n-alkanes have a dominant biogenic source in marginal Qeshm Island stations, which changed from biogenic to petrogenic sources in the Khamir Port areas. Sediment samples from the Khamir Port showed the significant presence of oil pollution due to transportation. These samples are being exposed to basic Persian Gulf currents entering from the Hormuz Strait causing oil pollution spread over the entire Gulf area. Sediment samples of the Middle Part stations located between two other sites show a combined condition of the two previous sections, with petrogenic and biogenic contributions. The present study demonstrates that the Hara Protected Area was already contaminated by background oil pollution as a result of continuous oil spills and war conflicts in the Persian Gulf.Additionally, the MCR-ALS method is shown to be a powerful chemometric tool for the investigation, resolution, identification, and description of pollution patterns distributed over a particular geographical area and environmental compartment. They can be used as well as parameters like unresolved to resolved ratio (U/R), pristane to phytane (Pr/Ph), n-C17/Pr, n-C18/Ph, and unresolved complex mixture (UCM) to assess petroleum pollution sources in the sediments.

Characterization and ecological risk of polycyclic aromatic hydrocarbons (PAHs) and n-alkanes in sediments of Shadegan international wetland, the Persian Gulf.

The distribution and sources of PAHs and n-alkanes were determined in the surface sediments from 202 locations in Shadegan international wetland with 537,700ha. The concentrations of total n-alkanes and PAHs ranged from 395.3 to 14933.46µgg-1dw and 593.74 to 53393.86ngg-1dw, respectively. Compared with other worldwide surveys, the concentration and contamination of sedimentary hydrocarbons were classified very high. A common petrogenic hydrocarbon source was strongly suggested in all sites by n-alkanes' profile with a Cmax at n-C20, Pr/Ph and CPI ratios<1 in all sites, and high percentage of UCM. Typical profile of petrogenic PAHs with alkyl-substituted naphthalenes and phenanthrenes predominance, various PAH ratios and multivariate analysis indicated that PAHs were mainly derived from petrogenic source. Naphthalene-derived compounds in all sites were significantly above their ERL, and adversely affected benthic biota. 92% of the sites had mean ERM values<0.1, indicating high ecological risk on the wildlife of the wetland.

Geochemical fractionation and pollution assessment of Zn, Cu, and Fe in surface sediments from Shadegan Wildlife Refuge, southwest of Iran.

This research focuses on the fractionation and distribution patterns of heavy metals (Zn, Cu, and Fe) in surficial sediments collected from Shadegan Wildlife Refuge, the biggest wetland in southern part of Iran, to provide an overall classification for the sources of metals in the study area using a sequential extraction method. For this purpose, a four-step sequential extraction technique was applied to define the partitioning of the metals into different geochemical phases of the sediment. The results illustrated that the average total level of Zn, Cu, and Fe in surface sediments were 55.20 ± 16.04, 22.86 ± 5.68, and 25,979.01 ± 6917.91 µg/g dw, respectively. On the average, the chemical partitioning of all metals in most stations was in the order of residual >oxidizable-organic > acid-reducible > exchangeable. In the same way, the results of calculated geochemical indices revealed that Cu, Zn, and Fe concentrations are mainly influenced by lithogenic origins. Compared with consensus-based SQGs, Cu was likely to result in occasionally harmful biological effects on the biota.

Seasonal variation of polycyclic aromatic hydrocarbons in the surface sediments of the southern Caspian Sea.

The concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) were determined in sediments from the southern Caspian Sea in fall 2015 and winter 2016. The sum of 16 PAH (ΣPAH) concentrations varied from 17.3±3.05 to 926.7±157.37ngg-1 dry weight and 14.3±0.58 to 85.8±4.41ngg-1 dry weight in fall and winter, respectively. There was no significant correlation between PAH and total organic carbon contents (p>0.05). PAH source identification showed that the PAHs in the sediments originated from petroleum and petroleum combustion. When classified according to the pollution levels, sediments from the southern Caspian Sea could be considered to be low to moderately polluted with PAHs.

Identifying the source of petroleum pollution in sediment cores of southwest of the Caspian Sea using chemical fingerprinting of aliphatic and alicyclic hydrocarbons.

In this study, the concentration and sources of aliphatic and petroleum markers were investigated in 105 samples of Anzali, Rezvanshahr and Astara cores from the southwest of Caspian Sea. Petroleum importation was diagnosed as a main source in most depths of cores by the results of unresolved complex mixture, carbon preference index and hopanes and steranes. From the chemical diagnostic parameters, petroleum inputs in sediment of cores were determined to be different during years and the sources of hydrocarbons in some sections differed than Anzali and Turkmenistan and Azerbaijan oils. Diagenic ratios in most sediments of upper and middle sections in Astara core were determined to be highly similar to those of Azerbaijan oil, while the presence of Turkmenistan and Anzali oils were detected in a few sections of Anzali and Rezvanshahr cores and only five layers of downer section in Anzali core, respectively.

Geochemical partitioning and pollution assessment of Ni and V as indicator of oil pollution in surface sediments from Shadegan wildlife refuge, Iran.

The total concentrations and chemical partitioning of Ni, V and Fe have been assessed in surface sediments from 160 sites along the Shadegan wildlife refuge. The results showed that the average total level of Ni, V and Fe in surface sediments were 45.08±12.09, 25.25±20.8 and 25,979.01±6917.91µg/g dw, respectively. On the average, the chemical speciation of Ni, V and Fe in most stations were in the order of residual>oxidisable-organic>acid-reducible>exchangeable. In all fractions, the residual was accounted the highest proportion for the metals analyzed. Among the non-residual phases, the proportion of heavy metals in organic matter fraction was higher than other phases collected from all locations. The comparison between measured values in this study and some fresh water sediment quality guidelines indicated that the levels of nickel would be expected to sporadically cause harmful biological impacts on biota in the Shadegan wildlife refuge.

Identification of sources of tar balls deposited along the Southwest Caspian Coast, Iran using fingerprinting techniques.

In 2012, a significant number of tar balls occurred along the Southwest coasts of the Caspian Sea (Iran). Several oil fields of Turkmenistan, Azerbaijan and Iran might be sources of oil spills and lead to the formation of these tar balls. For source identification, 6 tar ball samples were collected from the Southwest beaches of the Caspian Sea and subjected to fingerprint analysis based on the distribution of the source-specific biomarkers of pentacyclic tri-terpanes and steranes. Comparing the diagenic ratios revealed that the tar balls were chemically similar and originated from the same source. Results of double ratio plots (e.g., C29/C30 versus ∑C31-C35/C30 and C28 αßß/(C27 αßß+C29 αßß) versus C29 αßß/(C27 αßß+C28 αßß)) in the tar balls and oils from Iran, Turkmenistan and Azerbaijan indicated that the tar balls might be the result of spills from Turkmenistan oil. Moreover, principle component analysis (PCA) using biomarker ratios on the tar balls and 20 crude oil samples from different wells of Azerbaijan, Iran and Turkmenistan oils showed that the tar balls collected at the Southwest beaches are highly similar to the Turkmenistan oil but one of the Azerbaijan oils (from Bahar field oils) was found to be also slightly close to the tar balls. The weathering characterizations based on the presence of UCM (unresolved complex mixture) and low/high molecular weight ratios (L/H) of alkanes and PAHs indicated the tar ball samples have been significantly influenced by natural weathering processes such as evaporation, photo-degradation and biodegradation. This is the first study of its kind in Iran to use fingerprinting for source identification of tar balls.

Distribution and origins of n-alkanes, hopanes, and steranes in rivers and marine sediments from Southwest Caspian coast, Iran: implications for identifying petroleum hydrocarbon inputs.

The occurrence of n-alkanes and biomarkers (hopane and sterane) in surface sediments from Southwestern coasts of Caspian Sea and 28 rivers arriving to this lake, determined with a gas chromatography-mass spectrometry method, was used to assess the impacts of anthropogenic activities in the studied area. The concentrations of total n-alkanes (Σ21 n-alkane) in costal and riverine sediments varied from 249.2 to 3899.5 and 56 to 1622.4 µg g(-1), respectively. An evaluation of the source diagnostic indices indicated that petroleum related sources (petrogenic) were mainly contributed to n-alkanes in costal and most riverine sediments. Only the hydrocarbons in sediment of 3 rivers were found to be mainly of biogenic origin. Principal component analysis using hopane diagnostic ratios in costal and riverine sediments, and Anzali, Turkmenistan, and Azerbaijan oils were used to identify the sources of hydrocarbons in sediments. It was indicated that the anthropogenic contributions in most of the costal sediment samples are dominated with inputs of oil spills from Turkmenistan and Azerbaijan countries.