Hydrocarbons in coastal sediments from the Mediterranean sea (Gulf of Fos area, France)

Sedimentary hydrocarbons have been studied quantitatively and qualitatively in 11 coastal stations located in the Gulf of Fos (French Mediterranean coast). Hydrocarbon levels ranged from 10 to 260 mg kg(-1) sed. dry weight. A new parameter "NAR" (Natural n-alkane ratio) is proposed to evaluate the contribution of terrestrial inputs of hydrocarbons in the sediments. The origins of hydrocarbons are multiple: terrestrial inputs, biogenic, pyrolytic (industry emissions mainly steel and iron industries, ship and road traffic). Generally, the main source of contamination is not petroleum. Several ratios between parent polycyclic aromatic hydrocarbons show that the sources of hydrocarbons in the sediments are generally much more pyrolytic than petrogenic.     

PAH transport by sinking particles in the open Mediterranean Sea: a 1 year sediment trap study

One year time series of sinking particles were collected at two depths in the open Mediterranean Sea and analysed for polycyclic aromatic hydrocarbons (PAH). Average total PAH concentrations were 593+/-284 ng g(-1) at 250 m and 551 +/- 198 ng g(-1) at 2850 m. Total PAH fluxes averaged 73 +/- 58 ng m(-2) d(-1) at 250 m and 53 +/- 39 ng m(-2) d(-1) at 2850 m. Contamination levels and, thus, exposure of marine organisms to PAH are comparable in surface and deep waters. Deep waters appear as a significant, yet overlooked, PAH sink. PAH temporal patterns show noticeable seasonality. This is partly due to varying levels of specific components such as the winter increase of pyrolytic PAH. Downward transport processes and the nature of sinking particles also impact on PAH fluxes, as inferred during periods of increasing productivity. Different phase-associations and interactions with particulate organic carbon for low-MW fossil PAH and high-MW pyrolytic PAH influence their downward transport efficiency.     

The use of steroid markers to assess sewage contamination of the Black Sea

Analyses of faecal steroids in coastal sediments taken from throughout the Black Sea indicate chronic sewage contamination at some locations. These include Sochi, where concentrations of coprostanol up to 5400 ng g(-1) (dry wt) were recorded, and in the coastal areas adjacent to the Danube delta (2600 ng g(-1) dry wt). Comparatively high values of 5beta/(5beta+5alpha) isomeric ratios of cholestan-3-ol and cholestan-3-one are reported at these locations and are characteristic of sediments contaminated with sewage. Lower concentrations of coprostanol are reported for Bosphorus sediments (12-440 ng g(-1) dry wt) and in the region of Odessa (130-290 ng g(-1) dry wt). Isomeric ratios at these locations also confirm sewage as a significant contributor to steroids in the Bosphorus, but lower values of the ratios indicate only minor sewage inputs in Odessa. In contrast, steroid concentrations and compositions from most Ukrainian sites are characteristic of uncontaminated environments. To place these results into perspective, the range in levels of coprostanol in the Black Sea sediments compares to the lower to mid-range of concentrations reported for coastal sediments on a world-wide basis, with Black Sea sedimentary levels substantially below those previously reported for heavily impacted sites.     

Polycyclic aromatic hydrocarbons and changes in the trophic structure of polychaete assemblages in sediments of Todos os Santos Bay, Northeastern, Brazil

Polycyclic aromatic hydrocarbons (PAHs) and the trophic structure of polychaete assemblages were studied in sediments at 28 stations in Todos os Santos Bay. Total PAH concentrations varied from 8 to 4163 ng g(-1) dry weight. The indexes used for the determination of PAH origin suggested both pyrolytic and petrogenic sources. A total of 397 individuals of polychaetes was recorded which were classified in three trophic groups. The PCA ordination resulted in the formation of three groups of stations, Group I characterised by sandy sediments, low organic content, low total PAH concentration and percentage of potentially harmful PAH was dominated by subsurface deposit-feeders. The other two groups (IIa and IIb), showed similar percentages of silt and clay, however, Group IIb formed by those stations with high total organic carbon, total nitrogen, sulphur contents, high total PAH concentration and percentage of potentially harmful PAH was dominated by carnivores. Trophic changes could be explained by the level of exposure to PAH effects relative to differences in the life style and feeding strategies between deposit-feeders and carnivores.     

Spatio-temporal distribution and characteristics of PAHs in sediments from Masan Bay, Korea

The distribution of polycyclic aromatic hydrocarbons (PAHs) has been investigated in the surface and core sediments from Masan Bay, Korea. Total PAHs in the surface sediments ranged from 207 to 2670 ng/g dry weight with a mean value of 680 ng/g. Qualitative similarity and quantitative difference between inner and outer bay indicate that the main sources of PAHs are located in the inner bay and outer bay is also affected by the same sources. Vertical distribution of PAHs revealed that three distinctive stages could be differentiated with the help of PCA analysis. The highest concentration (industrialization stage) appeared between late 1950s and 1980, which was 10 years later than other developed countries. A strong pyrolytic source fingerprint has been detected with slight influence of petrogenic sources, and diagenetic PAH, perylene also contributed. Total organic carbon normalized PAHs (sum of 13 PAHs, 8.85-88.0 microg/g OC) were under the threshold effects concentration (TEC, 290 microg/g OC).     

The 1974 spill of the Bouchard 65 oil barge: petroleum hydrocarbons persist in Winsor Cove salt marsh sediments

Petroleum hydrocarbons persist in salt marsh sediments in Winsor Cove (Buzzards Bay, Massachusetts) impacted from the 1974 spill of No. 2 fuel oil by the barge Bouchard 65. Intertidal sediment cores were collected from 2001 to 2005 and analyzed for total petroleum hydrocarbons (TPHs). TPHs content was greatest (as high as 8.7 mg g(-1) dry weight) in the surface sediments and decreased with distance landward. Select samples were analyzed for polycyclic aromatic hydrocarbons (PAHs) with values as high as 16.7 microg g(-1) for total naphthalenes and phenanthrenes/anthracenes. These remaining PAHs are mainly C(4)-naphthalenes and C(1)-, C(2)-, and C(3)-phenanthrenes/anthracenes revealing preferential loss of almost all of the naphthalenes and the parent compound phenanthrene. Inspection of the data indicates that biodegradation, water-washing and evaporation were major removal processes for many of the petroleum hydrocarbons in the marsh sediments. In addition, historical data and photographs combined with their recent counterparts indicate that erosion has physically removed these contaminants from this site.     

A hierarchical approach measures the aerial extent and concentration levels of PAH-contaminated shoreline sediments at historic industrial sites in Prince William Sound, Alaska

A field study was conducted in 2003 to estimate the areal distribution and concentrations of polycyclic aromatic hydrocarbons (PAH) in intertidal sediments at sites of past human and industrial activity (HA sites) in Prince William Sound (PWS), Alaska, the site of the 1989 Exxon Valdez oil spill. More than 50 HA sites, primarily in western PWS, were identified through analysis of historic records and prior field studies, and nine sites were selected for detailed surveys. The areal assessment process consisted of seven steps: (1) identify site from historic records and field surveys; (2) locate visual evidence of surface oil/tar at a site; (3) prepare a site map and lay out a sampling grid over the entire site with 10-m grid spacing; (4) excavate pits to 50 cm depth on the grid; (5) perform a field colorimetric test to estimate total PAH (TPAH) in sediments from the wall of each pit and record the results in the ranges <1 ppm; 1-10 ppm; >10 ppm TPAH; (6) expand grid size if necessary if elevated PAH levels are detected colorimetrically; (7) select 20 samples from each site for same-day shipboard PAH analysis by immunoassay (SDI RaPID PAH) and, based on these results, select sediment samples from each site for full PAH analysis in the laboratory to identify PAH sources. A total of 416 pits were dug at the nine sites. Nine acres of sediments with TPAH >2500 ppb dry wt. were mapped at the nine sites. TPAH concentrations obtained by immunochemical analysis of 181 samples from the nine sites ranged from 20 to 1,320,000 ppb (wet wt.). The contaminants are mixtures of petroleum products (2-3 ring PAH) and combustion products (4-6 ring PAH) unrelated to the 1989 Exxon Valdez oil spill. Mussels and clams collected at these sites have elevated levels of PAH that are compositionally similar to the PAH in the sediments. These findings indicate that at least a portion of the sediment PAH is bioavailable. The PAH sources at these historic industrial sites are chronic. They include relict fuel oil tanks and works located above and within the intertidal zone, with contamination at some locations extending into nearshore sub-tidal sediments. This study shows how a hierarchical approach can be used to quickly and successfully map, quantify, and subsequently, identify sources of PAH in shoreline sediments.     

Sources and distribution of aliphatic and polyaromatic hydrocarbons in sediments of Jiaozhou Bay, Qingdao, China

The composition and distribution of aliphatic (n-alkanes) and polyaromatic hydrocarbons (PAHs) were measured for the surface sediments collected at 25 sites from Jiaozhou Bay, Qingdao, China. Total n-alkanes and PAH concentrations ranged from 0.5 to 8.2 microg/gdw and 0.02 to 2.2 microg/gdw, respectively, and the distribution of both n-alkanes and PAHs showed large spatial variations in the bay. The distribution of PAHs in the sediments was predominated by the three or more ring compounds. High hydrocarbon levels were generally found in the areas associated with high anthropogenic impact and port activities in the bay. The calculated hydrocarbon indexes suggest that petroleum contamination was the main source of n-alkanes, while both pyrolytic and petrogenic sources contributed PAHs to the surface sediments of Jiaozhou Bay. In comparison to other polluted coastal sediments, the level of contamination from both aliphatic hydrocarbons and PAHs in Jiaozhou Bay sediments is relatively low at the present time.     

Distribution, origin, and potential toxicological significance of polycyclic aromatic hydrocarbons (PAHs) in sediments of Kaohsiung Harbor, Taiwan

Sediment samples were collected from 12 locations of Kaohsiung Harbor, Taiwan and analyzed for polycyclic aromatic hydrocarbons (PAHs). Total PAH concentrations varied from 472 to 16,201 ng g(-1) dry weight. The highest PAH concentrations were from the industrial zone docks situated in south Kaohsiung Harbor. Diagnostic ratios showed that the possible source of PAHs in the industrial zone dock could be coal combustion while in the other zones it could be petroleum combustion. The toxic equivalent concentrations (TEQcarc) of PAHs varied from 55 to 1964 ng TEQ g(-1) dry weight. Higher total TEQcarc values were found at industrial zone docks (from 1404 to 1964 ng TEQ g(-1) dry weight). As compared with the US Sediment Quality Guidelines (SQGs), the observed levels of PAHs at industrial zone docks exceeded the effects range low (ERL), and could thus cause acute biological damage. However, the lower levels of PAHs at the other zones would probably not exert adverse biological effects.     

Distribution and origins of polycyclic aromatic hydrocarbons (PAHs) in riverine, estuarine, and marine sediments in Thailand

To assess the status of polycyclic aromatic hydrocarbon (PAH) contamination in coastal and riverine environments in Thailand, we collected 42 surface sediment samples from canals, a river, an estuary, and coastal areas in Thailand in 2003 and analyzed them for PAHs with 3-7 benzene rings by gas chromatography-mass spectrometry (GC-MS). The total concentration of PAHs ranged from 6 to 8399 ng/g dry weight. The average total PAH concentrations were 2290+/-2556 ng/g dry weight (n=8) in canals, 263+/-174 (n=11) in the river, 179+/-222 (n=9) in the estuary, and 50+/-56 (n=14) in coastal areas. Comparison of the concentration range with a worldwide survey of sedimentary PAH concentrations ranked PAH contamination in Thai sediments as low to moderate. The ratio of the sum of methylphenanthrenes to phenanthrene (MP/P ratio) allows discrimination of PAH sources between petrogenic (>2) and pyrogenic (<0.5) origins. Sediments from urban canals in Bangkok showed the highest PAH concentrations and petrogenic signatures (MP/P=1.84+/-0.98 [n=6] in canal sediments) with abundant alkylated PAHs, indicating major sources of petrogenic PAHs in the city. To identify the sources of the petrogenic inputs in Thailand, we analyzed triterpanes, biomarkers of petroleum pollution, in the sediment samples and in potential source materials. Hopane profiles were remarkably uniform throughout the nation, suggesting a diffuse single source (e.g. automobiles). Molecular profiles of hopanes and PAHs in sediments from the urban canals were similar to those in street dust, indicating that street dust is one of the major sources of petrogenic PAHs in the urban area. On the other hand, low levels of PAHs (approximately 50 ng/g) with a pyrogenic signature (MP/P ratio approximately 0.5) were widely recorded in remote areas of the coast and the Chao Phraya River. These pyrogenic PAHs may be atmospherically transported throughout the nation. Middle and lower reaches of the Chao Phraya River, the river mouth, and the upper Gulf of Thailand showed intermediate concentrations and profiles of PAHs, indicating mixtures of petrogenic and pyrogenic origins. Perylene was abundant in sediments, representing up to approximately 60% of total identified PAHs. High inputs of soil due to frequent heavy rains could contribute to the high perylene abundance in the sediments. Sedimentary PAH concentrations decreased offshore with a half distance of approximately 10 km in the upper Gulf off the mouth of the Chao Phraya River. This is probably due to active deposition of laterally transported riverborne particles.     

Assessment of polycyclic aromatic hydrocarbon input to urban wetlands in relation to adjacent land use

The relationship between polycyclic aromatic hydrocarbons (PAHs) in wetland surface sediments and adjacent land use was assessed in the Elizabeth River, VA, an urbanized sub-estuary of the Chesapeake Bay. Significant differences (p<0.05) in surface sediment PAH concentration between sites indicated adjacent land use had a substantial influence on PAH concentration in wetland sediments. Wetlands adjacent to parking lots and petroleum industrial sites exhibited the highest PAH concentrations of all wetlands examined. Overall, commercial land uses had the highest PAH concentrations and automotive sources dominated (52-69%) PAH input to wetland surface sediments irrespective of adjacent land use.     

Evaluation of surface sediment contamination by polycyclic aromatic hydrocarbons in the "Saco do Laranjal" - (Patos Lagoon, Brazil)

This paper evaluates the concentration of Polyaromatic hydrocarbons - PAHs in the Estuarine area of the Patos Lagoon, more precisely in a local named "Saco do Laranjal" in Pelotas City (southern Brazil). The samples were collected in May 2008. The concentrations of 16 US-EPA priority polycyclic aromatic hydrocarbons (PAHs) were determined by gas chromatography with a mass spectrometry detector (GC/MS). The sum of PAHs concentration ranged from 7.3 to 92.8μgkg(-1) in dry weight. The positive correlation (Pearson test) between the total organic material (TOM) and the total PAH concentration (0.98) suggests that TOM plays an important role in controlling the PAHs levels in the sediments. According to the observed ratios of individual PAHs, the contamination in the studied area is originated, predominantly pyrolytic sources. The values found are considered under normal levels and indicates a not impacted area.     

Accumulation of polycyclic aromatic hydrocarbons by Neocalanus copepods in Port Valdez, Alaska

Sampling zooplankton is a useful strategy for observing trace hydrocarbon concentrations in water because samples represent an integrated average over a considerable effective sampling volume and are more representative of the sampled environment than discretely collected water samples. We demonstrate this method in Port Valdez, Alaska, an approximately 100 km(2) basin that receives about 0.5-2.4 kg of polynuclear aromatic hydrocarbons (PAH) per day. Total PAH (TPAH) concentrations (0.61-1.31 microg/g dry weight), composition, and spatial distributions in a lipid-rich copepod, Neocalanus were consistent with the discharge as the source of contamination. Although Neocalanus acquire PAH from water or suspended particulate matter, total PAH concentrations in these compartments were at or below method detection limits, demonstrating plankton can amplify trace concentrations to detectable levels useful for study.     

Hydrocarbons in surface sediments from the Sfax coastal zone, (Tunisia) Mediterranean Sea

The Semi-enclosed Mediterranean Sea records various signals of high anthropic pressures from surrounding countries and the industrialized European countries. This is particularly true for oil pollution. Although accounting for 1% of the world's ocean surface, it receives about 25% of the petroleum inputs to the ocean. To achieve a global budget we need to collect information from different parts of the Mediterranean. Particularly, we focus in this paper on the Southern Mediterranean, where data are presently very scarce. In this context, the University of Sfax has undertaken an estimation of hydrocarbon pollution along the coasts of Sfax and Gabès Gulf. Non-aromatic hydrocarbons were analysed in 8 surface sediments by FT/IR and GC/MS. Non-aromatic hydrocarbon concentrations vary in the range 310-1406 microg g(-1) sediments dry weight, which is high, compared to other Mediterranean sites. GC/MS data indicate a large group of unresolved compounds suggesting a petroleum contamination, confirmed by the identification of hopanes with predominant C29 and C30alpha,beta compounds and steranes with predominance of C27 over C28) and C29 compounds.     

Historical polycyclic aromatic and petrogenic hydrocarbon loading in Northern Central Gulf of Mexico shelf sediments

The distribution of selected hydrocarbons within ten dated sediment cores taken from the Mississippi River Bight off coastal Louisiana suggests a chronic contaminant loading from several sources including the river itself, oil and gas exploration in the central Gulf of Mexico (GOM) shelf area, and natural geologic hydrocarbon seeps. Data were grouped as either total polycyclic aromatic hydrocarbons (PAH's), which were indicative of pyrogenic PAH's; or estimated total hopanes (indicative of petrogenic hydrocarbons). The total PAH concentrations and estimated total hopanes begin increasing above background levels (approximately 200 ng g(-1)) after the 1950s. The distribution of these hydrocarbons and hopanes within the dated sediment cores suggests that the Mississippi River is a regional source of pyrogenic PAH's, and that the hopanes are from natural geologic hydrocarbon seeps, oil and gas exploration in the GOM, or both.     

Inhomogeneous distribution of polycyclic aromatic hydrocarbons in different size and density fractions of contaminated sediment from Auckland Harbour, New Zealand: an opportunity for mitigation

Polycyclic aromatic hydrocarbons (PAHs) in sediment from Auckland Harbour (New Zealand) are not distributed evenly throughout bulk sediment, but highly concentrated in coarser, low-density fractions. Concentrations of 24 PAHs, measured in sediment that was separated into six size fractions that were furthermore separated into two density sub-fractions by flotation in sodium-polytungstate solution (rho = 2.15 g cm(-3)), varied between 4-103 microg g(-1)dw among grain size fractions and 2-998 microg g(-1)dw for density sub-fractions. Highest PAH concentrations were measured in the low density, 125-250 microm fraction. All sediment fractions had a similar relative PAH composition, dominated by >3-ring PAHs, suggesting a common pyrogenic origin. Low density material had 10-200 times higher PAH concentrations and 10-100 times higher organic carbon (OC) content, yet differences in OC content only partially accounted for variations in PAH concentration. Low density particles contributed more than 75% of the Sigma PAH, while comprising only 3% of bulk sediment dry weight. This may have significant utility for contaminant mitigation efforts in Auckland Harbour.     

Levels and spatial distribution of polycyclic aromatic hydrocarbons (PAHs) in superficial sediment from 15 Italian marine protected areas (MPA)

Surface sediment from 15 Italian marine protected areas (MPA) were analysed for polycyclic aromatic hydrocarbons (PAHs). The organic carbon percentage was also determined. Total PAH concentrations (ng g⁻¹ d.w.) ranged from 0.71 (Penisola del Sinis) to 1550 (Miramare). Individual PAH analysis showed that three and four rings PAHs were the most frequently detected isomers and accounted for 60-70% of the PAH total concentrations. PAH ratio analysis showed a prevalence of pyrolytic PAH origin at most of the MPAs with exception of Porto Cesareo and Ustica where a petrogenic origin was detected. Results for organic carbon percentages ranged from 0.3% (Capo Rizzuto) to 2% (Punta Campanella). These results are comparable to other Mediterranean marine environments. However, our results shows that some MPAs, such as Miramare, Porto Cesareo, Isola Capo Rizzuto and Punta Campanella, are subject to strong pressure from urban and industrial activities where high PAH levels were detected.     

Dynamic behaviour of polycyclic aromatic hydrocarbons in Brighton marina, UK

The distribution of polycyclic aromatic hydrocarbons (PAHs) between various phases is fundamental in the control of their movement and impact in the marine environment. In this study samples of water and sediments were regularly collected from Brighton marina, UK, to quantify the intensity, spatial and temporal variations of PAH contamination. The results show clearly that PAH behaviour in marine systems is highly complex, and controlled by the interplay of PAH sources, compound physicochemical properties, water and sediment movement, and field conditions. Levels of total PAHs (16 compounds) in the dissolved phase were found to vary between <2 and 11,400 ng/l, with higher values observed in the winter months. Total PAH concentration in sediment samples varied between 24 and 4710 ng/g dry weight. PAHs in water were dominated by low molecular mass compounds (2-ring), while PAHs in sediments were mainly derived from 2-4 ring compounds. In addition, dissolved concentrations were increased during sediment dredging and after a period of severe rainfall. PAHs in Brighton marina are likely to be from both pyrolytic and petrogenic sources; as a result, field-derived distribution coefficients for individual PAHs between sediment and water tend to follow the equilibrium partition models, although slight exceedance is apparent. The extended partition model incorporating soot carbon has achieved limited success in better predicting PAH behaviour.     

Organic pollutants (PAHs, PCBs) in sediments from the Mar Piccolo in Taranto (Ionian Sea, Southern Italy)

Polychlorinated biphenyls (PCBs) and 17 parent polycyclic aromatic hydrocarbons (PAHs) were determined in surface sediments from nine stations in the Mar Piccolo of Taranto (Ionian Sea, Southern Italy). Total PAH concentrations ranged from 380 to 12,750 microg/kg d.w., while total PCB levels ranged from 2 to 1684 microg/kg d.w.; this values were higher than those found in others marine coastal areas of the Mediterranean Sea. For PAHs, low molecular weight/high molecular weight, phenanthrene/anthracene and fluoranthene/pyrene ratio were used for discriminating between pyrolitic and petroleum origin. Results showed that PAHs were mainly of pyrolitic origin. PCB and PAH levels in sediments were compared with Sediments Quality Guidelines (ERM-ERL, TEL-PEL indexes) for evaluation probable toxic effects on marine organism. Finally, ERM and PEL quotients were used to evaluate the degree to which chemicals exceed guidelines. Results suggest an ecotoxicological risk for benthic organisms mainly in the first inlet, where high concentrations of PCBs were found in sediments influenced by harbour activities.     

Distribution and sources of aliphatic and polycyclic aromatic hydrocarbons in suspended particulate matter in water from two Brazilian estuarine systems

The levels of selected organic markers, including 17 polycyclic aromatic hydrocarbons (PAHs), 16 of which are classified as priority pollutants by the US-EPA and perylene, aliphatic hydrocarbons (total and linear alkanes) and petroleum biomarkers (hopanes and steranes), were measured in suspended particulate matter (SPM) of the Mundaú-Manguaba estuarine-lagoon system (MMELS) in northeastern Brazil and the Paraíba do Sul River (PSR) estuary in southeastern Brazil, both of which are affected by sugarcane agriculture and urbanization. A total of 33 surface water samples of SPM were collected (22 from the MMELS and 11 from the PSR). The ∑16PAH ranged from 221 to 1243 ng g⁻¹ in the MMELS and from 228 to 1814 ng g⁻¹ in the PSR. Hopane and sterane concentrations in the PSR were higher than in the MMELS due to the input from petrogenic sources in PSR. The contributions of higher plants were also observed by n-alkane analyses. The PAH isomeric ratios indicated that the SPM from MMELS showed characteristics of combustion from biomass or petroleum and PSR was associated to petrogenic input, either from combustion or from unburned petroleum. Three sampling sites located near to the sugarcane plant and mouth of the rivers showed higher PAH concentrations and may largely be considered as highly contaminated. However, levels of n-alkanes and petroleum biomarkers in both study areas were relatively low.