Distribution and sources of hydrocarbons in surface sediments of Gemlik Bay (Marmara Sea, Turkey)

Seabottom sediments from Gemlik Bay, one of the most polluted spots in SW Marmara Sea, were analyzed for parent polycyclic aromatic hydrocarbons (PAHs) using gas chromatography-mass spectrometry. The concentration of 14 PAH compounds in sediment samples collected from 61 locations are distributed in a broad spectrum from low to very high concentration levels (50.8-13482 ng g-1). No significant correlation was found between summation operatorPAHs and organic carbon content while summation operatorPAHs increase slightly with silt/clay ratio. Therefore the distribution and concentrations of PAHs would be determined more by direct input, rather than by the type of sediment found locally. The most polluted areas are distributed nearshore eastern (Gemlik) and southern (Kursunlu, Mudanya and Trilye) coasts which are mainly influenced by rapid ecotourism development, direct discharges from rivers, surface run-off and drainage from port areas, domestic and industrial effluent discharges through outfalls and various contaminants from ships. Special PAH compound ratios, such as Phe/Anth, Flu/Py, B[a]A/Chry; LMWPAH/HMWPAH; Per/; Per/summation operatorPAH; Per/summation operator(penta-aromatics) and Flu/(Py+Flu), were calculated to evaluate different hydrocarbon origins and their relative importance. Pyrolytic activity is dominant along the highly-populated eastern and southern coasts. Meanwhile, petrogenic activity mixed with pyrolytic activity is a matter of fact in front of the main industrial-tourism ports and anchoring areas as well. Higher concentration of perylene are distributed along the mostly polluted eastern and southern coastal areas, however, the concentrations of perylene relative to the penta-aromatic isomers are dominant especially in the northern and deepest sectors of the bay, indicating diagenetic origin for the presence of perylene.     

Polycyclic aromatic hydrocarbons (PAHs) in surface sediments of Liaodong Bay,Bohai Sea,China

Materials and methods  

The levels and possible sources of 16 polycyclic aromatic hydrocarbons (PAHs) were investigated in the surface sediments of Liaodong Bay, Bohai Sea, China.     

Environmental assessment of polycyclic aromatic hydrocarbons (PAHs) in surface sediments of the Santander Bay,Northern Spain

Samples of intertidal surface sediments (0-2 cm) were collected in 17 stations of the Santander Bay, Cantabric Sea, Northern Spain. The concentrations of polycyclic aromatic hydrocarbons (PAHs), 16, were analysed by HPLC and MS detection. Surface sediments show a good linear correlation among the parameters of the experimental organic matter evaluation, where total carbon (TC) and loss on ignition (LOI) are approximately 2.5 and 5 times total organic carbon (TOC). A wide range of TOC from 0.08% to 4.1%, and a broad distribution of the sum of sigma16PAHs, from 0.02 to 344.6 microg/g d.w., which can be correlated by an exponential equation to the TOC, has been identified. A qualitative relationship may be established between the industrial input along the rivers and the concentration of sigma6PAHs in the sediments of the estuaries: Boo estuary (8404-4631 microg/g OC), Solia-San Salvador estuaries (305-113 microg/g OC) and Cubas estuary (31-32 microg/g OC). This work shows a dramatic change in the spatial distribution in the concentration of PAHs of intertidal surface sediments. The left edge of the Bay has the main traffic around the city and the major source of PAHs is from combustion processes and estuarine inputs, leading to medium values of PAHs in the sediments; the right edge of the Bay has much lesser anthropogenic activities leading to lower values of PAHs in sediments. The distribution of individual PAHs in sediments varies widely depending on their structure and molecular weight; the 4-6 ring aromatics predominate in polluted sediments due to their higher persistence. The isomer ratio does not allow any clear identification of the PAHs origin. Environmental evaluation according to Dutch guidelines and consensus sediment quality guidelines based on ecotoxicological data leads to the same conclusion, sediments in the Santander Bay show a very different environmental quality depending on the spatial position from heavily polluted/medium effects to non-polluted/below threshold effects. These results indicate that local sources of PAHs, especially estuary discharges, lead to very different qualities of sediments in coastal zones, where traffic and industrial activities take place.     

Mercury methylation by a microbial community from sediments of the Adour Estuary (Bay of Biscay, France)

In order to study the influence of microorganisms on the mercury biogeochemistry, the metal content and the structure of microbial communities were determined in sediments from stations along the Adour Estuary. The comparison of the bacterial communities and their distribution in function of the environmental parameters by Canonical Correspondence Analysis (CCA) revealed the influence of metals on the bacterial communities structure. Sediments where the bacterial communities are mostly influenced by methylmercury were incubated in slurries with or without mercury, under oxic and anoxic conditions. Methylmercury production was detected in the anoxic biotic slurries with a net methylation yield of 0.3% after 24 h. CCA based on T-RFLP profiles revealed the impact of mercury addition on the bacterial communities structure. In addition, 17 bacterial strains, mainly sulphate-reducing bacteria involved in mercury methylation, were isolated and identified.     

Spatial and temporal distribution of polycyclic aromatic hydrocarbons (PAHs) in sediments from Daya Bay, South China

The spatial and temporal distribution of polycyclic aromatic hydrocarbons (PAHs) has been investigated in Daya Bay, China. The total concentration of the 16 USEPA priority PAHs in surface sediments ranged from 42.5 to 158.2 ng/g dry weight with a mean concentration of 126.2 ng/g. The spatial distribution of PAHs was site-specific and combustion processes were the main source of PAHs in the surface sediments. Total 16 priority PAH concentration in the cores 8 and 10 ranged from 77.4 to 305.7 ng/g and from 118.1 to 319.9 ng/g respectively. The variation of the 16 PAH concentrations in both cores followed the economic development in China very well and was also influenced by input pathways. Some of the PAHs were petrogenic in core 8 while pyrolytic source was dominant in core 10. In addition, pyrolytic PAHs in both cores were mainly from the coal and/or grass and wood combustion.     

Sources and historical record of tin and butyl-tin species in a Mediterranean bay (Toulon Bay,France)

Concentrations of inorganic tin (Sn_inorg), tributyltin (TBT) and its degradation products dibutyltin (DBT) and monobutyltin (MBT) were measured in surface sediments and in two cores from the Toulon Bay, hosting the major French military harbour. Anticipating planned dredging, the aim of the present work is to map and evaluate for the first time the recent and historic contamination of these sediments by inorganic and organic Sn species derived from antifouling paints used for various naval domains including military, trade, tourism and leisure. Tin and butyl-Sn concentrations in the bay varied strongly (4 orders of magnitude), depending on the site, showing maximum values near the shipyards. The concentrations of total Sn (1.3–112 μg g^?1), TBT (<0.5–2,700 ng g^?1), DBT (<0.5–1,800 ng g^?1) and MBT (0.5–1,000 ng g^?1) generally decreased towards the open sea, i.e. as a function of both distance from the presumed main source and bottom currents. Progressive degradation state of the butyl-Sn species according to the same spatial scheme and the enrichment factors support the scenario of a strongly polluted bay with exportation of polluted sediment to the open Mediterranean. Low degradation and the historical records of butyl-Sn species in two ²¹⁰Pb-dated sediment cores, representative of the Northern Bay, are consistent with the relatively recent use of TBT by military shipyards and confirm maximum pollution during the 1970s, which will persist in the anoxic sediments for several centuries. The results show that (a) degradation kinetics of butyl-Sn species depend on environmental conditions, (b) the final degradation product Sn_inorgBT is by far the dominant species after 10–12 half-life periods and (c) using recent data to reliably assess former TBT contamination requires the use of a modified butyl-Sn degradation index BDI_mod. Resuspension of extremely contaminated subsurface sediments by the scheduled dredging will probably result in mobilization of important amounts of butyl-Sn species.     

Induction of the P450 reporter gene system bioassay by polycyclic aromatic hydrocarbons in Ulsan Bay (South Korea) sediments

Polycyclic aromatic hydrocarbons (PAHs) and induction of the P450 reporter gene system (RGS) for 6- and 16-h exposure periods were determined in organic extracts of Ulsan Bay (South Korea) sediments to assess the utility of this bioassay as a screening tool for PAH contamination. The sum of the concentrations of 23 individual PAHs in 30 sediment samples (sigma PAH) based on GC-MS analysis ranged from 0.05 to 6.1 micrograms/g dry wt. P450 RGS fold induction ranged from 4.0 to 320 micrograms/g based on benzo[a]pyrene toxic equivalents (BaPEq). P450 RGS BaPEq and the 'chemical BaPEq', defined as the sum of the products of individual PAH concentrations and pre-determined toxic equivalency factors, exhibited very strong positive correlations with sigma PAH (r2 > 0.90; P < 0.001). Fold induction did not increase (and in some cases decreased) after the optimal incubation period (6 h) for PAHs, indicating that other compounds known to induce the P450 RGS (e.g. chlorinated organics) were not present at levels effecting significant induction. This was supported by GC-ECD analysis where non-ortho and mono-ortho polychlorinated biphenyls (PCBs) known to be strong P450 RGS inducers were found to be at very low or non-detectable levels in samples with the highest P450 RGS responses. The profound difference in PAH profiles for the two most contaminated sites suggested that this assay is especially sensitive for selected PAHs with greater than four rings. Combined with previous results, the P450 RGS shows promise as a useful screening tool for predicting deleterious biological effects resulting from CYP1A1-inducing, sediment-associated chemicals, particularly high molecular weight PAHs.     

Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) distributions in the Bay of Marmara sea: Izmit Bay

In 1999, the concentrations of 16 polycyclic aromatic hydrocarbons (PAHs), the total PAH and polychlorinated biphenyls (PCBs) were measured in sea water, sediment and mussels collected along the coast of Izmit Bay, the most important bay of the Marmara Sea. The total-PAH concentrations, measured by Spectrofluorometry were in the range of 1.16-13.68 microg/l in sea water, in the range of 30.0 1670.0 microg/g dry weight in sediments and in the range from 5.67 to 14.81 microg/g wet weight in edible part of mussel. HPLC revealed Phenanthrene (three rings), chrysene (four rings) and benz[a]antracene (five rings) to be the dominant PAHs in sea water, while 16 different PAHs compounds were observed and measured in mussel samples. The most pollution occured at Dogu Kanali and Dil Deresi where were the main rivers containing wastes fall into the the Izmit Bay. Although the maximum mono-ortho PCB concentrations in sea water were measured in the Dil Deresi River (26.33 ng/l) and the Solventa? (22.19 ng/l) stations, maximum PCB concentrations in mussels were measured in the SEKA (28.11 microg/kg) and the Dil Deresi River (25.68 microg/kg). The dominant congeners of PCBs were from tetra to hexachlorobiphenyls. The toxicity equivalent values were very low in sea water and mussels.     

Distribution of polycyclic aromatic hydrocarbons in water and surface sediments from Daya Bay,China

Marine culture is thriving in China and represents a major component of the regional economy in coastal zones, yet the environmental quality of many of those areas has never been studied. This paper attempts to investigate the quality status of Daya Bay, a key aquaculture area in China. The levels of 16 polycyclic aromatic hydrocarbons (PAHs) were determined in water and sediment samples of the bay. The total concentrations of 16 PAHs varied from 4228 to 29325 ng l(-1) in water, and from 115 to 1134 ng g(-1) dry weight in sediments. In comparison to many other marine systems studied, the PAH levels in Daya Bay waters were relatively high, and at six sites they were sufficiently high (> 10 microg l (-1)) to cause acute toxicity. The PAH composition pattern in sediments suggest dominance by medium to high molecular weight compounds, and the ratio of certain related PAHs indicate important pyrolytic and petrogenic sources. Further analysis showed that the distribution coefficient (KD) increased with the particular organic carbon content of sediments, consistent with the PAH partition theory. The organic carbon normalised distribution coefficient (K(oc)) also increased with the compounds' octanol/water partition coefficient (K(ow)), confirming the potential applicability of the linear free energy relationships in the modelling and prediction of PAH behaviour in marine environments.     

Enrichment of polycyclic aromatic hydrocarbons (PAHs) in mariculture sediments of Hong Kong

Surface and core sediments collected from six fish farms in Hong Kong and from reference sites were investigated for the enrichment and sources of polycyclic aromatic hydrocarbons (PAHs). Moderately high ∑PAH₁₆ levels (123-947 ng g⁻¹, mean: 450 ng g⁻¹) were found in the surface aquaculture sediments. In comparison with the sediments from the reference sites, the average enrichment percentage of total organic carbon (TOC) and PAHs in surface sediments were 21.4 and 43.8%, respectively, and in the core sediments, 24.6 and 73.7%, respectively. Mathematical source apportionment analyses (i.e. isomer ratios, hierarchical cluster analysis, principal components analysis with multiple linear regression analysis) suggested a higher percentage of petrogenic sources in aquaculture sediments. The fish feeds might be the main source of the enriched PAHs in the aquaculture sediments. To our knowledge, this is the first study showing that PAHs in aquaculture sediments could be attributed to human aquaculture activities.     

Persistence of polycyclic aromatic hydrocarbons in sediments in the deeper area of the Northern Adriatic Sea (Mediterranean Sea)

The Po Valley is the most important agricultural and industrial area of Adriatic basin. In this area there are several rivers which transport polycyclic aromatic hydrocarbons (PAHs) into the sea via suspended particulate matter. This study describes the persistence of PAHs in the deep and coastal sediments of the Northern Adriatic. Different environmental conditions were studied: salinity, temperature, sunlight, sediment particle size and organic matter in sediment. The average conditions in the deep areas of the Northern Adriatic are: salinity higher than 37, temperature lower than 11 °C, darkness and clayey sediments with a high organic matter content. These conditions increase the persistence of the PAHs in the deep area of the Northern Adriatic.     

A novel approach for characterization of polycyclic aromatic hydrocarbon (PAH) pollution patterns in sediments from Guanabara Bay, Rio de Janeiro, Brazil

A novel multivariate method based on principal component analysis of pre-processed sections of chromatograms is used to characterize the complex PAH pollution patterns in sediments from Guanabara Bay, Brazil. Five distinct sources of 3- to 6-ring PAHs could be revealed. The harbour is the most contaminated site in the bay, its plume stretches in a South West to North East direction and the chemical profile indicates mainly pyrogenic sources mixed with a fraction of high-molecular-weight petrogenic PAHs. Rio São João de Meriti is the second largest source of PAHs, and introduces mainly a fraction of low-molecular-weight petrogenic PAHs from the western region of Rio de Janeiro. The sites close to the ruptured pipeline at the Duque de Caxias Refinery show a distinctive pollution pattern indicating a heavy petroleum fraction. The method also led to the identification of new potential indicator ratios also involving coeluting peaks (e.g., triphenylene and chrysene).     

Aliphatic hydrocarbons, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, organochlorine, and organophosphorous pesticides in surface sediments from the Arc river and the Berre lagoon, France

Introduction  

The Arc River and Berre lagoon are one of important river basin hydrosystem in the South of France that receives industrial and municipal wastewaters from the adjacent area.     

Sources of fluorescent dissolved organic matter in high salinity seawater (Bohai Bay, China)

Fluorescent dissolved organic matter (FDOM) identified in coastal waters within a large salinity range had been widely reported in previous studies, which stated that conservative mixing of terrestrially derived and river-transported FDOM by clear seawaters could account for the relatively low FDOM fluorescence signals in high salinity seawaters. This study aimed at testing the conservative mixing model in high salinity seawaters in a shallow bay (Bohai Bay, China) with low river flow in a dry season. The water showed high salinities varying in a narrow range (30.52???2.07), and salinity effects on fluorescence quantum yields therefore less likely introduced complications to fluorescence data analyses. By applying a parallel factor analysis to fluorescence excitation emission matrices of the water samples, we identified a tyrosine-like FDOM component, a tryptophan-like FDOM component, and two humic substances-like FDOM components. Based on a theoretical analysis, we found that dissolved organic carbon concentrations and suspended solid concentrations of the bulk-water samples as well as the maximum fluorescence signals of each identified FDOM component showed spatial distributions that could not be accounted for by the conservative mixing model. Marine autochthonous processes including microbial activities and FDOM releasing from resuspended sediment were likely to be invoked.     

Chlorinated hydrocarbons in coastal bottom sediments of the Japan Sea

Data on distribution of chlorinated hydrocarbons in coastal bottom sediments of different areas of the Japan Sea are presented. Results obtained during the autumn 1994 expedition in Peter-the-Great Bay were compared with the data of previous surveys in the D.P.R. Korea coastal zone and Tatarsky Strait (Sakhalin Island). Concentrations of DDT metabolites and HCH isomers appear to be related mainly to pesticide usage in agriculture. Mean concentrations of total DDTs decreased from 12.5 ng g(-1) in the D.P.R.K. coastal zone to 2.2 ng g(-1) at Sakhalin Island shelf, whereas total HCH concentrations decreased from 3.4 to 0.4 ng g(-1). Differences in chemical composition of pesticides used in the D.P.R.K. and Russia were evident. The importance of further monitoring of persistent organochlorines in bottom sediments and the need for regulation of wastewater discharges is stressed.     

Polychlorinated naphthalenes (PCNs) in riverine and marine sediments of the Laizhou Bay area, North China

PCN congeners were analyzed in marine and riverine sediments of the Laizhou Bay area, North China. Concentrations of PCNs ranged from 0.12 to 5.1 ng g⁻¹ dry weight (dw) with a mean value of 1.1 ng g⁻¹ dw. The levels of PCNs varied largely, with industrial group approximately ten folds higher than those of the rural in riverine sediment. A strong impact by direct discharge from local factories was suggested. Similar compositional profiles were found within groups. High resemblance of compositional profiles between industrial samples and Halowax 1014 was observed. It was indicated that PCNs in riverine sediments were mainly from release of industrial usage, with additional contributions from industrial thermal process at certain sites. In marine sediments, it was suggested that PCNs along the coast of Laizhou Bay were mainly controlled by riverine input. While in the central bay, PCN distributions were possibly impacted by combined multiple factors.     

Uptake of polycyclic aromatic hydrocarbons (PAHs) in salt marsh plants Spartina alterniflora grown in contaminated sediments

Polycyclic aromatic hydrocarbon (PAH) concentrations were measured in Spartina alterniflora plants grown in pots of contaminated sediment, plants grown in native sediment at a marsh contaminated with up to 900 microg/g total PAHs, and from plants grown in uncontaminated control sediment. The roots and leaves of the plants were separated, cleaned, and analyzed for PAHs. PAH compounds were detected at up to 43 microg/g dry weight in the root tissue of plants grown in pots of contaminated soil. PAH compounds were detected at up to 0.2 microg/g in the leaves of plants grown in pots of contaminated soil. Concentrations less than 0.004 microg/g were detected in the leaves of plants grown at a reference site. Root concentration factor (RCF) values ranged from 0.009 to 0.97 in the potted plants, and from 0.004 to 0.31 at the contaminated marsh site. Stem concentration factor (SCF) values ranged from 0.00004 to 0.03 in the potted plants and 0.0002 to 0.04 at the contaminated marsh. No correlation was found between the RCF value and PAH compound or chemical properties such as logKOW. SCF values were higher for the lighter PAHs in the potted plants, but not in the plants collected from the contaminated marsh. PAH concentrations in the roots of the potted plants are strongly correlated with soil concentrations, but there is less correlation for the roots grown in natural sediments. Additional plants were grown directly in PAH-contaminated water and analyzed for alkylated PAH homologs. No difference was found in leaf PAH concentrations between plants grown in contaminated water and control plants.     

Sources and distribution of polycyclic aromatic hydrocarbons in sediments from the Spanish northern continental shelf. Assessment of spatial and temporal trends

The distribution of polycyclic aromatic hydrocarbons was determined in surface sediments collected at 36 stations along the Spanish Northern continental shelf in March and September 2003, and February 2005. Concentrations of PAHs (Σ13 parent components) were in the range of 22-47528 μg/kg dw, the highest values corresponding to coastal urban-industrial hotspots and decreasing offshore. Sediment quality guidelines (SQGs) showed that concentrations of total PAHs were below the threshold effect level (TEC) in 27 stations (81%) and above in 7, two of which (Gijon and Bilbao) were above the probable effect concentration (PEC). The detailed study of diagnostic ratios suggested a rather uniform mixture of petrogenic and pyrolytic PAH sources along the continental shelf, with a slight decrease of the latter moving westwards and offshore. In order to assess the incidence of sediment sampling on the variability of the results, selected stations were also monitored in February and September 2004 and September 2005. The average field variance of the values obtained for each station was 31% that decreased to 23% when the values were normalized to TOC.     

Polycyclic aromatic hydrocarbons in the sediments of the South China Sea

Sixteen sediment samples, collected from the South China Sea, were analyzed for 11 parent polycyclic aromatic hydrocarbons (PAHs) using gas chromatography and gas chromatography-mass spectrometry. Total concentrations of the 11 PAHs studied in the sediments ranged from 24.7 to 275.4 ng/g with a mean of 145.9 ng/g dry sediment. PAH concentrations displayed a consistent distribution trend with the sediment organic carbon content. The linear regression analysis showed that the total concentration of PAHs in the sediment was significantly correlated to the sediment organic carbon content with a correlation coefficient of 0.735 (n=16). Special PAH compound ratios, such as phenanthrene/anthracene and fluoranthene/pyrene, were calculated to evaluate the relative importance of different origins. The collected data showed that pyrolytic input from anthropogenic combustion processes was predominant at almost all the stations investigated. Only one station, located in the proximity of oil wells, appeared to be contaminated predominantly by petrogenic input. Three anthropogenic PAHs, i.e. pyrene, benzo[a]pyrene and benzo[e]pyrene, exhibited similar distribution patterns in the studied area, implying that these compounds possess identical sources. However, perylene did not entirely follow the distribution trend of the three PAHs, suggesting that the sediment perylene probably derived from other sources such as in situ biogenic origins. Dibenzothiophene, a sulfur heterocyclic aromatic compound, was also measured in this study.     

Heavy metals, polycyclic aromatic hydrocarbons and polychlorinated biphenyls in surface sediments of the Naples harbour (southern Italy)

The Naples's harbour is one of the largest and most important commercial and tourist port of the Mediterranean basin. It is located on the southeast coast of Italy and receives industrial and municipal wastewaters from the city of Naples. Due to its social and economic impact, a comprehensive assessment of levels and sources of contamination of bottom sediments in this area of the Mediterranean basin is essential to identify potential danger due to mobilization of contaminants produced by managing of the same sediments. In this study, superficial sediments collected from 189 sampling sites were analyzed for grain size, heavy metals (Cr, Cu, Ni, Pb, V, Zn, Co, Sn, Cd, Hg, As, Al and Fe), 16 priority polycyclic aromatic hydrocarbons (PAHs) and perylene and 38 individual polychlorinated biphenyl (PCB) congeners. Compared to the estimated local background, Cu, Zn, Pb, Cd, Sn and Hg show enrichment factors >3 and only Hg evidences a median value higher than the NOAA (effects range - median) guidelines. Principal component analysis allowed us to clearly discriminate two areas mainly affected by heavy metals contamination and influenced by different sources related to industrial, commercial and/or urban activities. Priority PAHs are predominantly represented by three-five-ring compounds with concentrations ranging between 9 and 31774 ng g(-1) and frequently higher than the NOAA ER-M index. A prevalent pyrolitic origin of PAH was assessed on the basis of the relative abundance of the different congeners and selected isomer ratios. The concentrations of PCBs, as sum of the 38 congeners, ranged from 1 to 899 ng g(-1), with a predominance of highly chlorinated (tetra- and penta-chlorobiphenyls) congeners. WHO-TEQ values, calculated for the PCDD-like PCB congeners, suggest a relatively high level of toxicity. Generally, the concentration of PAHs and PCBs were higher near the sites of intense industrial, shipping and/or commercial activities suggesting a direct influence of these sources on the pollutant distribution patterns.