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.     

Hydrocarbons in surface sediments from the Changjiang (Yangtze River) Estuary, East China Sea

Sedimentary aliphatic (AH) and polycyclic aromatic hydrocarbons (PAHs) were studied in the Changjiang Estuary and the adjacent East China Sea. Total AH ranged from 2.20 to 11.82 μg g⁻¹ and consisted of n-alkanes and a dominant petroleum-related unresolved complex mixture (UCM). Within the n-alkanes, terrestrial plant wax compounds prevailed at nearly all stations. Of the PAHs, biogenic perylene dominated at stations receiving riverine inputs. Anthropogenic PAHs originating from combustion/pyrolysis processes varied from 17 to 157 ng g⁻¹, while fossil PAH concentrations ranged from 42 to 187 ng g⁻¹. Both biogenic and anthropogenic hydrocarbons are primarily derived from riverine discharges and accumulate at shallow-water stations. Distinct phase associations lead, nevertheless, to different sedimentation patterns. Fossil PAHs are enhanced at offshore stations where they are introduced directly by shipping activities. Biomarker fingerprints ascribe their source to Chinese crude oils. The overall levels of anthropogenic hydrocarbons are low compared to relevant areas worldwide and reveal a low/moderate level of hydrocarbon pollution.     

Revisiting hydrocarbons source appraisal in sediments exposed to multiple inputs

The aim of this work was to test the efficiency of statistical methods as compared to the traditional diagnostic ratios to improve hydrocarbon source identification in sediments subjected to multiple inputs. Hydrocarbon determination in Guanabara Bay sediments pointed out high degradation and ubiquitous petrogenic pollution through the presence of high unresolved complex mixture. Polycyclic aromatic hydrocarbon (PAHs) ratios suggested pervasive contamination derived from combustion in all sediments and failed discriminating samples despite the specificity of sources in different sampling sites. Principal component analysis (PCA) effectively distinguished the petrogenic imprint superimposed to the ubiquitous combustion contamination, since this technique reduces the influence of PAHs distribution which is common to all samples. PCA associated to multivariate linear regression (MLR) allowed a quantitative assessment of sources confirming predominance of the pervasive contaminant component superimposed to a generalized petrogenic imprint. The pervasive component derives from combustion contributions as well as from differential PAHs degradation.     

Source apportionment of polycyclic aromatic hydrocarbons in surface sediment of mud areas in the East China Sea using diagnostic ratios and factor analysis

Polycyclic aromatic hydrocarbons (PAHs) and aliphatic hydrocarbons (AHs) have been quantified for surface sediments collected from the East China Sea (ECS). Our results showed that relatively high levels of PAHs and AHs occurred in both the inner and outer mud areas, while their concentrations at the control site were much lower. AHs for all samples were dominated by the unresolved complex mixture (UCM). Results from diagnostic ratios revealed that sedimentary PAHs were mainly originated from mixed combustion residues of biomass, coal, and petroleum. Combustion residues of petroleum and oil were responsible for the presence of high AHs concentrations. We also conducted factor analysis (FA) to further characterize the PAH and AH sources. Four factors were identified based on the loading of components and attributed to coal and wood combustion (Factor 1), traffic-related sources (Factor 2), petrogenic source (Factor 3) and natural gas combustion (Factor 4).     

Distribution and sources of aliphatic hydrocarbons in surface sediments of Sergipe River estuarine system

The assessment of aliphatic hydrocarbons was performed in the Sergipe River estuarine system, northeastern Brazil. Aliphatic hydrocarbons concentration ranged from 9.9 ug g?1 up to 30.8 ug g?1 of dry sediment. The carbon preference index (CPI, based on nC?? to nC?? range), indicated predominance of petrogenic input in two of the sites analyzed (P4 and P5). The unresolved complex mixture (UCM) was found to be present in seven of the nine sites sampled (except for P4 and P5). Overall, the results of this work suggest that there is a mix of organic matter sources to the sediment. Although the coast of Sergipe has an intense off shore petroleum exploration and the Sergipe River crosses the entire city of Aracaju, the capital city of Sergipe, non-significant anthropogenic fingerprint was assessed.     

Steroid markers to assess sewage and other sources of organic contaminants in surface sediments of Cienfuegos Bay,Cuba

Analyses of faecal steroids in coastal sediments from Cienfuegos Bay Cuba indicate chronic sewage contamination at the main outfalls from the city, where concentrations of coprostanol up to 5400 ng g⁻¹ (dry wt) were measured. In contrast, steroid concentrations and compositions from sites from the south part of the Bay are characteristic of uncontaminated sewage environments. The levels of coprostanol in the Cienfuegos sediments compares to the lower to mid-range of concentrations reported for coastal sediments on a world-wide basis, with sedimentary levels markedly below those previously reported for heavily impacted sites. This study delivers baseline data for further investigation of the effectiveness of the proposed sewerage plan promoted by the GEF project in Cienfuegos. Investigations on the correlations between faecal steroids and other organic contaminants confirmed that the major source of petroleum hydrocarbons within the bay was associated with the sewage effluents from the Cienfuegos city.     

Natural and anthropogenic hydrocarbons in sediments from the Chubut River (Patagonia, Argentina)

In March of 2001 a study was carried out to evaluate hydrocarbon levels in the lower course of the Chubut River. The study included 12 sample stations along the river from San Cristóbal Bridge to the confluence with the sea, in a 25 km straight-line extension in a urbanized area. In the first 11 stations, resolved aliphatic (RAli) hydrocarbons presented low values, between 0.07 and 0.96 microg/g dry weight (dw); the unresolved complex mixture (UCM) between 0.42 and 2.72 microg/g dw, and the total aliphatic (TAli) hydrocarbons between 0.55 and 3.07 microg/g dw. In the last station, at the mouth of Chubut river, these values increased to 460, 284, and 741 microg/g dw for RAli, UCM and TAli, respectively. The n-alkanes distribution indices and the compositional parameters suggested a predominantly biogenic origin in eleven stations, and a predominantly anthropogenic origin in the last station, with the highest hydrocarbon values. It is possible to conclude that the stations with low hydrocarbon values and biogenic origin predominance would constitute the baseline of aliphatic hydrocarbons for river sediments at this zone. The station with the highest hydrocarbon concentration and predominantly anthropic origin was related to the presence of Rawson city's port, where its activities (harbor and fishing vessels) generate hydrocarbon wastes unrelated to the river base profile in the study zone. Offshore, but within the river influence, there is an important fishing area of Argentine Red and Patagonian shrimps (Pleoticus muelleri and Artemesia longinaris, respectively).     

Polycyclic aromatic hydrocarbons in the sediments of the Yalujiang Estuary,North China

Selected polycyclic aromatic hydrocarbons (PAHs) in surface sediments of the Yalujiang Estuary, North China, have been investigated by gas chromatography-mass spectrometry (GC-MS) for flood season (August, 1994) and dry season (May, 1996), respectively. PAHs concentrations from sediments range from 68 to 1500 ngg(-1) depending upon the sample locations. The most contaminated sediment samples are found in the turbidity maximum area for both dry and flood seasons. The source of PAHs is most likely pyrolytic, with minor contributions from petrogenic and diagenetic PAHs for some samples. Perylene is mainly derived from biogenic inputs, and occurs at almost stations. In the Yalujiang Estuary, both biogenic and anthropogenic hydrocarbons are primarily derived form riverine discharges and are accumulated in the mixing zone. The overall levels of PAHs in this study are low compared to other regions and reveal moderate PAHs pollution in the Yalujiang Estuary.     

‘Fingerprinting’ petroleum hydrocarbons in bottom sediment,plankton, and sediment trap collected seston

Water carried particulate matter (seston) collected in sediment traps has been used for fingerprinting petrogenic hydrocarbons (PHC) along an urban influenced transect in the Stockholm archipelago. Gas-chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) have been used for identification and quantification of n-alkanes, the isoprenoids pristane and phytane, pentacyclic triterpanes, the unresolved complex mixture (UCM) and total hydrocarbon content (THC). Preserved seston has been compared with anoxic seston and anoxic bottom surface sediments to establish the effects of degradation processes, and with spring bloom plankton as a reference of biological material. The results show that samples of seston, collected and preserved in sediment traps, are very suitable for carrying out fingerprint analyses of petrogenic hydrocarbons. A gradient of increasing PHC downflux towards the urban area was found and petrogenic contamination of the waters was detected along the whole transect.     

Aliphatic and aromatic hydrocarbons in coastal Caspian Sea sediments

This investigation represents the first extensive study of the spatial distribution and sources of aliphatic (n-alkanes and unresolved complex mixture of fossil hydrocarbons) and polycyclic aromatic hydrocarbons (PAHs) in coastal sediments from the Caspian Sea. PAH concentrations, n-alkanes and biomarker profiles all suggested that there was limited petrogenic contamination in the shallow North Caspian Sea sediments, which are coarse with a low total organic carbon content. In contrast, moderate to high petrogenic contamination was found in the South Caspian Sea, in particular in the offshore oil fields near Baku, Azerbaijan. Contaminant patterns indicated that the PAHs were mainly from fossil sources, with higher contributions of pyrolytic only near industrialized and urban areas. A high contribution of perylene, a geochemically derived PAH, to the total PAHs was found in the west and south at sites influenced by the Kura, Safid Rud, Terek, Sulak and Samur Rivers.     

Aliphatic and aromatic hydrocarbons in marine biota and coastal sediments from the Gulf and the Gulf of Oman

The composition and spatial distribution of aliphatic and polycyclic aromatic hydrocarbons (PAHs) were investigated in biota and coastal sediments from four countries surrounding the Gulf (Bahrain, Qatar, United Arab Emirates and Oman). The levels of total petroleum hydrocarbons (TPH), aliphatic unresolved mixture and PAHs in sediments and biota were relatively low compared to world-wide locations reported to be chronically contaminated by oil. Only in the case of the sediments collected near the BAPCO oil refinery in Bahrain, having concentrations of 779 μg g⁻¹ total petroleum hydrocarbon equivalents and 6.6 μg g⁻¹ ∑PAHs, can they be categorized as chronically contaminated. Some evidence of oil contamination was also apparent in sediments and bivalves around Akkah Head and Abu Dhabi in the UAE, and near Mirbat in Oman. Contaminant patterns in sediments and biota indicated that the PAHs were mainly from fossil sources, with the exception of the high PAH concentrations in sediments near the BAPCO refinery that contained substantial concentrations of carcinogenic PAH combustion products.     

Hydrocarbon contamination in sediments from urban stormwater runoff

This investigation showed that urban stormwater runoff provides a significant amount of petrogenic material to receiving waters and sediments. A characteristic hydrocarbon ‘fingerprint’ for sediments and particulate matter in the Hillsborough Reservoir, Hillsborough River and upper Hillsborough Bay was provided. Determination of source material for petroleum contamination in stormwater runoff and river sediment indicated that crankcase oil was a primary contributor to sediment hydrocarbon contamination. A comparison of sediment hydrocarbons with hydrocarbons from stormwater runoff showed that the most probable source of crankcase oil-like petrochemicals found in sediment was the stormwater runoff.A comparison of hydrocarbon composition in suspended particulate matter with that of accumulated bottom sediments in the reservoir, river and bay, during a non-storm period and rising tide showed no resuspension and upriver transport of petroleum contaminated bay sediment. No special influence of the bay upon the lower river was observed relative to hydrocarbon tracers, indicating that most contaminated sediment transport was downriver during storm events. Additional studies should be performed over various tidal cycles and storm events incorporating sediment cores, sediment grain size analysis and hydrocarbon characterization at more closely spaced stations near the river mouth to address adequately the question of specific hydrocarbon pollution sources, rate of petroleum influx and persistence of petrochemical contaminants in the sediment.     

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.     

Sources of sedimentary PAHs in tropical Asian waters: Differentiation between pyrogenic and petrogenic sources by alkyl homolog abundance

We collected surface sediment samples from 174 locations in India, Indonesia, Malaysia, Thailand, Vietnam, Cambodia, Laos, and the Philippines and analyzed them for polycyclic aromatic hydrocarbons (PAHs) and hopanes. PAHs were widely distributed in the sediments, with comparatively higher concentrations in urban areas (∑PAHs: ∼1000 to ∼100 000 ng/g-dry) than in rural areas (∼10 to ∼100 g-dry), indicating large sources of PAHs in urban areas. To distinguish petrogenic and pyrogenic sources of PAHs, we calculated the ratios of alkyl PAHs to parent PAHs: methylphenanthrenes to phenanthrene (MP/P), methylpyrenes + methylfluoranthenes to pyrene + fluoranthene (MPy/Py), and methylchrysenes + methylbenz[a]anthracenes to chrysene + benz[a]anthracene (MC/C). Analysis of source materials (crude oil, automobile exhaust, and coal and wood combustion products) gave thresholds of MP/P = 0.4, MPy/Py = 0.5, and MC/C = 1.0 for exclusive combustion origin. All the combustion product samples had the ratios of alkyl PAHs to parent PAHs below these threshold values. Contributions of petrogenic and pyrogenic sources to the sedimentary PAHs were uneven among the homologs: the phenanthrene series had a greater petrogenic contribution, whereas the chrysene series had a greater pyrogenic contribution. All the Indian sediments showed a strong pyrogenic signature with MP/P ≈ 0.5, MPy/Py ≈ 0.1, and MC/C ≈ 0.2, together with depletion of hopanes indicating intensive inputs of combustion products of coal and/or wood, probably due to the heavy dependence on these fuels as sources of energy. In contrast, sedimentary PAHs from all other tropical Asian cities were abundant in alkylated PAHs with MP/P ≈ 1-4, MPy/Py ≈ 0.3-1, and MC/C ≈ 0.2-1.0, suggesting a ubiquitous input of petrogenic PAHs. Petrogenic contributions to PAH homologs varied among the countries: largest in Malaysia whereas inferior in Laos. The higher abundance of alkylated PAHs together with constant hopane profiles suggests widespread inputs of automobile-derived petrogenic PAHs to Asian waters.     

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).     

Investigation of natural and anthropogenic hydrocarbon inputs in sediments using geochemical markers. I. Santos, SP--Brazil

A study on the inputs of organic matter to marine sediments of Santos Bay and Estuary, located in southeastern S?o Paulo State, Brazil, is presented here. The following geochemical markers were identified and quantified: aliphatic hydrocarbons (normal and isoprenoid alkanes), petroleum biomarkers, linear alkylbenzenes (LABs) and polycyclic aromatic hydrocarbons (PAHs). Sediment samples, collected at 15 sites in the bay and surrounding channels, were extracted and analyzed by gas chromatography with flame ionization and mass spectrometer detectors. Total concentrations varied from 0.17 to 107.80 microg g(-1) for aliphatics, from 47.2 to 2560.1 ng g(-1) for petroleum biomarkers, from 16.9 to 430.6 ng g(-1) for LABs and from 79.6 to 15389.1 ng g(-1) for PAHs. Anthropogenic contributions were apparent, indicating the influences of the Cubatao industrial complex, sewage outfalls along the area, the waste deposit of Santos city and storage facilities for petroleum and derivatives, based on the higher concentrations of geochemical markers detected.     

Hydrocarbon composition and distribution in a coastal region under influence of oil production in northeast Brazil

Waters and sediments from the Potiguar Basin (NE Brazilian coast) were investigated for the presence and nature of polycyclic aromatic hydrocarbons (PAH) and aliphatic hydrocarbons. The region receives treated produced waters through a submarine outfall system serving the industrial district. The total dispersed/dissolved concentrations in the water column ranged from 10-50 ng L⁻¹ for ∑16PAH and 5-10 μg L⁻¹ for total aliphatic hydrocarbons. In the sediments, hydrocarbon concentrations were low (0.5-10 ng g⁻¹for ∑16PAH and 0.01-5.0 μg g⁻¹ for total aliphatic hydrocarbons) and were consistent with the low organic carbon content of the local sandy sediments. These data indicate little and/or absence of anthropogenic influence on hydrocarbon distribution in water and sediment. Therefore, the measured values may be taken as background values for the region and can be used as future reference following new developments of the petroleum industry in the Potiguar Basin.     

Hydrocarbon contamination of coastal sediments from the Sfax area (Tunisia), Mediterranean Sea

The coastal area off the city of Sfax (730,000 inhabitants), well-known for fisheries and industrial activities, receives high inputs of organic matter mostly anthropogenic. Eighteen stations were selected in the vicinity of the direct discharge of industrial sewage effluents in the sea in order to study the spatial distribution of the organic contamination. Surface sediments sampled in the shallow shelf were analysed for hydrocarbons by Fourier transform infrared spectroscopy, gas chromatography and gas chromatography/mass spectrometry. Total hydrocarbon distributions revealed high contamination as compared to other coastal Mediterranean sites, with an average concentration of 1865 ppm/dry weight sediment. Gas chromatographic distribution patterns, values of unresolved mixture/n-alkane ratio and distributions of steranes and hopanes confirmed a petroleum contamination of the Arabian light crude oil type. Biogenic compounds were also identified with a series of short-chain carbon-numbered n-alkenes in the carbon range 16-24.     

Source apportionment of sedimentary hydrocarbons in the Segara Anakan Nature Reserve,Indonesia

The study aimed to determine the spatial distribution of n-alkanes and polycyclic aromatic hydrocarbons (PAHs) in surface sediments of the Segara Anakan nature reserve and their potential origins using gas chromatography–mass spectrometry. Total alkane concentrations ranged from 3755 to 129,027 μg kg⁻¹, and the concentrations of 16 PAHs ranged from 375 to 29,517 μg kg⁻¹. The ratios of specific n-alkanes (e.g., CPI_24–34, WaxC_n, and Paq), including a new proposed index, terrestrial–marine discriminant (TMD), as well as the ratios of selected PAHs (e.g., Ant/∑178, Fl/∑202, BaAnt/∑228, and IPyr/∑276), showed that the sources of hydrocarbons in the sediments were generally biogenic, including both terrigenous and marine, with an anthropogenic pyrolytic contribution (petrogenic and biogenic combustion). For the environmental risk assessment, a sediment quality guideline (SQGs) comparison indicated that the station risk levels ranged from low to medium-low, except for R6, which has a greater impact on the ecological risk for marine organisms.     

Distribution and source recognition of polycyclic aromatic hydrocarbons in the sediments of Hsin-ta Harbour and adjacent coastal areas,Taiwan

Thirty-three sediment samples from Hsin-ta Harbour and neighboring coastal areas were analyzed by GC-MS for polycyclic aromatic hydrocarbons (PAHs). Total concentrations of 30 analyzed parental and alkylated PAHs ( summation operator PAH) varied from 98.1 to 3382 ng/g dry weight. MP/P (methylphenanthrenes/phenanthrene) values larger than 2 coincided with very low P/A (phenanthrene/anthracene) values at inner harbour stations, revealing that a significant portion of low molecular weight PAHs are probably from petrogenic pollution sources, specifically, illegal disposal of used motor oil. The 4,6-dimethyldibenzothiophene/3,6-dimethylphenanthrene (4,6-C(2)D/3,6-C(2)P) ratio is found to be more useful than the MP/P ratio in tracing petrogenic PAHs from the inner harbour area to the adjacent coastal environment. In addition, according to hierarchical cluster analysis, collected sediments cluster in three major groups, Off-shore Group, Near-shore Group and Inner Harbour Group. Three diagnostic ratios, 4,6-C(2)D/3,6-C(2)P, PER/ summation operator PAH (perylene to summation operator PAH) and BaA/CHR (benzo(a)anthracene/chrysene), representing petrogenic, biogenic and pyrogenic origins, are found to be effective in differentiating and characterizing sediments among the groups in this study. Enrichment of pyrogenic and petrogenic PAHs in sediments collected exhibits mixing or dilution, spatially, by biogenic (or natural) PAHs.