Petroleum hydrocarbon analyses conducted following the wreck of the supertanker Anoco Cadiz

Following the wreck of the AMOCO CADIZ on 16 March 1978, samples of water, sediment and oil were collected between April and June from the Brittany coast and western English Channel and were analysed for petroleum hydrocarbons by means of fluorescence spectroscopy, gas-liquid chromatography and gas chromatography-mass spectrometry.     

Hydrocarbons in the intertidal environment of Kachemak Bay,Alaska

Intertidal animals and sediment from Kachemak Bay, Alaska were analysed to determine the concentrations of hydrocarbons. At Coal Point the herbivorous limpet Collisella pelta contained petroleum within its tissues while intertidal algae of the area have previously been shown to accumulate petroleum as a surface coating. At Coal Bay, a locality where both petroleum and coal are present, the filter feeding mussel Mytilus edulis contained petroleum hydrocarbons whereas the deposit feeding clam Macoma balthica contained an array of hydrocarbons suggesting detrital coal as the source. Animals higher in the food web including the gastropod Nucella lima and the urchin Strongylocentrotus droebachiensis showed no evidence of petroleum. All samples contained biogenic hydrocarbons of algal and planktonic origin.     

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.     

The identification of some lipophilic contaminants in the gill neutral lipids of Gammarus duebeni

Two experimental populations of Gammarus duebeni have been found to contain high levels of what appeared to be pollutants in their gill neutral lipids. Detailed analysis, involving capillary gas chromatography-mass spectrometry, confirmed the presence of hydrocarbons, a plasticizer and silicone compounds. Such a localized concentration of lipophilic pollutants in a tissue such as the gills might be sufficient to influence the metabolism of the whole organism even though the total body burden is low.     

Determination of petroleum hydrocarbons in water, fish and sediments following the Ekofisk blow-out

Samples of fish, water and sediment were collected during the Ekofisk ‘Bravo’ blow-out and analysed for specific aliphatic and aromatic hydrocarbons. Analyses showed the presence of petroleum hydrocarbons from the blow-out in some of the water samples, but fish and sediments, collected up to a week after it began, showed no evidence of a contribution from the blow-out.     

Bioremediation perspective of historically contaminated sediment with polycyclic aromatic hydrocarbons

The purpose of the current study is to compare the influence of different aerobic conditions(biostimulation(BS),bioaugmentation(BA),and a combination of biostimulation and bioaugmentation(BB))on polycyclic aromatic hydrocarbons(PAH)degradation and compare the degraded amount with single step XAD-4 extraction as a new tool for bioavailability assessment for chronically contaminated sediment samples obtained from territory of Autonomous Province Vojvodina of Serbia(S1,S2,and S3).A great number of papers dealing with biodegradation of PAHs in spiked sediment or soil have been published,but to the authors’knowledge,a limited number of papers studied aged,historically polluted sediment and a sum of chosen U.S.Environmental Protection Agency(USEPA)PAHs.A significant reduction(up to67%)in PAH concentration was observed,while the percentage of reduction varied depending on the sediment sample and treatment used.BS treatment successfully stimulated growth of indigenous bacteria.Further,PAH-degrading strain Sphingomonas paucimobilis F8 inoculated in BA and BB treatment survived for up to 7 weeks after it was suppressed by unfavorable conditions or native microbes.Degraded amounts generally showed good correlation with results obtained from XAD-4 extraction.Results obtained in the current study represent a good start for standardizing a XAD-4 extraction technique as a simplified,easier,and lower cost method for bioavailability assessment.     

Toxicity studies of elemental sulfur in marine sediments

Elemental sulfur(ES) is a component essential for proper development of animals, but it can be toxic for aquatic organisms. The objectives of the study reported here included determination of ES concentrations in sediment collected in the area of the Gulf of Gdansk(Baltic Sea) and search for the possible correlations with the ecotoxicity results. Sediment samples were collected from four locations: the Vistula River mouth, in the Port Basin, in the area of discharge of the treated wastewater from the Wastewater Treatment Plant(WWTP) and in the area of the sunken World War Ⅱ s/s 'Stuttgart' shipwreck. The levels of elemental sulfur were determined using a gas chromatograph coupled with a mass spectrometer(GC-MS). Toxicity of marine sediment samples was estimated for three biotest organisms-bioluminescent bacteria Vibrio fischeri, crustacean Heterocypris incongruens, and Synapis alba plant. The highest toxicity of sediments for all indicator organisms was observed in samples taken at the place of the shipwreck(2-100%). The same samples had a high sulfur content(16.7-143.2 μg/g dry weight(d.w.))therefore, it was decided to investigate whether the presence of ES in the sediment in the studied area can have an impact on the results of the ecotoxicity determination in real samples. However, the removal of sulfur from the samples resulted in no significant changes in the level of toxicity of the samples. In this research it could not be confirmed that the presence of elemental sulfur is the only factor responsible for the observed sediment toxicity. It seems that other compounds or their mixtures present in the sediment may have a significant influence on the results obtained.     

Aliphatic and aromatic hydrocarbons in sediments of Santos and Cananéia, SP, Brazil.

Sediment samples from Santos and Cananéia, S?o Paulo Brazil were analysed by GC-FID and GC-MS for aliphatic and aromatic hydrocarbons in order to gather information on the degree of contamination by oil and other biogenic contributions. Concentrations of total n-alkanes in Santos varied from 1.05 to 4.29 microg g(-1) and aromatic hydrocarbons from 0.08 to 42.39 microg g(-1). In Cananéia total n-alkanes varied from 4.37 to 157.90 microg g(-1). However, aromatic hydrocarbons were not detected. In Cananéia n-alkanes of terrestrial plants with high molecular weight predominate (n-C25, n-C27, n-C29, n-C31 and n-C33). In Santos, a more uniform distribution of the n-alkanes and aromatic hydrocarbons was found at all the sediment stations. The hydrocarbon data from stations close to the Saboó Wharf, at Alemoa and in the COSIPA Channel revealed alarming levels of acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene and chrysene.     

Hydrocarbon concentrations in water and sediments from UK marine waters,determined by fluorescence spectroscopy

Between January 1978 and September 1979 samples of subsurface (1 m) water and surface sediment were collected from sites in the North Sea, English Channel, Irish Sea and a number of estuarine areas. These have been analysed by fluorescence spectroscopy (UVF) in order to provide information on the levels of hydrocarbons generally present in UK marine waters.Total hydrocarbon concentrations (THCs) of water samples ranged from 1.1–74 μg l.^?1 Ekofisk crude oil equivalents, all values greater than 3.5 μg l.^?1 occurring inshore. In offshore areas the mean THCs were: 1.3 μg l.^?1 in the northern North Sea, 1.5 μg l.^?1 in the western Channel, 2.5 μg l.^?1 in the eastern Channel and southern North Sea, and 2.6 μg l.^?1 in the Irish Sea.THCs of sediment samples ranged from 0.27–340 μ g^?1 dry weight Ekofisk crude oil equivalents, the highest concentration being in the Queen's Channel, the main entrance to the River Mersey.     

Aliphatic hydrocarbon concentrations in short sediment cores from the southern Okinawa Trough: Implications for lipid deposition in a complex environment

Seven short sediment cores from the southern Okinawa Trough were collected and analyzed for the aliphatic hydrocarbon concentrations by capillary gas chromatography to explore the deposition of hydrocarbons to this area. For all cores studied, ratios of Σhydrocarbons/TOC, (nC₂₇+nC₂₉+nC₃₁)/TOC, terrigenous/aquatic, and diploptene/ΣC_25–33n-alkanes fluctuated around a mean value with coefficients of variation ranging from 9.0% to 19.7%, 4.9% to 20.0%, 27.3% to 129%, and 3.8% to 163%, respectively. For the nC₃₁/(nC₂₇+nC₂₉+nC₃₁) ratio, only station 21 showed fluctuation. Moreover, the carbon preference indexes in the C₂₅–C₃₃n-alkane range also exhibited fluctuating values with coefficients of variation of 1.9–14.4%. These results indicate that concentrations of hydrocarbon inputs to the sampling sites vary with time; this may result from complex current flow and sediment transport, leading to variable lipid deposition. In addition, significant correlation between diploptene (hop-22(29)-ene) and higher plant n-alkanes was found for cores 21, 42 and 46, indicating that diploptene was predominantly from higher plant sources. However, no correlation between diploptene and higher plant n-alkanes was found for cores 20, 36, 43 and 44; autochthonous sources of diploptene in these cores were quite probable.     

Simulation experiments on gas production from hydrate-bearing sediments

Experiments were made on 58 sediment samples from four sites(1244,1245,1250 and 1251) of ODP204 at five temperature points(25,35,45,55 and 65℃) to simulate methane production from hydrate-bearing sediments.Simulation results from site 1244 show that the gas components consist mainly of methane and carbon dioxide,and heavy hydrocarbons more than C2+ cannot be detected.This site also gives results,similar to those from the other three,that the methane production is controlled by experimental temperatures,gene...     

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.     

Detection of aliphatic hydrocarbons derived by recent “bio-conversion” from fossil fuel oil in North Sea waters

The higher boiling point range of saturated aliphatic hydrocarbon fractions extracted from North Sea water have been re-investigated in detail with improved high resolution glass capillary columns suitable for high temperature gas-chromatography. The resulting chromatograms reveal hydrocarbon patterns, most of which have the same common feature: a smooth distribution of the long-chain n-alkanes combined with a lack of the branched alkanes normally expected for fossil fuel oil. Instead, two homologous series of iso- and anteiso-alkanes could be detected. Since this finding is always associated with traces of present or past fossil fuel oil contamination of the upper water column, these environmental n-, iso and anteisoalkanes are considered to be recently ‘bio-converted’ from fossil fuel oil hydrocarbons. They form a third group beside recent biogenic and fossil petrogenic hydrocarbons in the marine environment. Oil pollution records of the marine environment will have to take into account this group of microbial hydrocarbons.     

Increased levels of petroleum hydrocarbons in the surface sediments of Swedish coastal waters

Petroleum hydrocarbons in the sediments of the Bothnian Bay, Baltic proper, Öresund, Kattegatt and Skagerrak were analysed in a survey of oil pollution along the Swedish coast in 1974 and 1975. Sixty-one of these sediment stations were revisited in 1982 and analysed with the methods used in the first survey. The mean content of petroleum hydrocarbons (paraffin-naphthene fraction) in the sediment surface showed a statistically significant increase from 199 to 252 μg g^?1 dry wt. The main increase had taken place in the coastal areas. Within 0–20 km distance of urbanized areas (>20 000 inhabitants) petroleum hydrocarbons had increased from 371 to 447 μg g^?1. Sediment levels increased from 76 to 117 μg g^?1, 20–50 km from urbanized areas. The increase in these areas was equivalent to 0.119 g m^?2 yr^?1.     

Composition, distribution and sources of polycyclic aromatic hydrocarbons in sediments of the Gulf of Trieste, Northern Adriatic Sea

The composition, distribution and the sources of polycyclic aromatic hydrocarbons (PAHs) in the surficial sediments of the Gulf of Trieste were investigated. To document the spatial PAH input, surficial sediment samples from 17 locations throughout the Gulf were analysed. The total PAH load determined in the surficial sediment samples are between 30 and 600 ng g-1, and were the highest in the immediate vicinity of the Port of Trieste. The PAH contents decline rapidly with increasing distance from the shore. The ratios of methylphenanthrenes/phenanthrene and methylpyrene/pyrene are sensitive indicators of the origin of PAH pollution in the Gulf which is mostly pyrolitic. The phenanthrene/anthracene ratio was used to determine the approximate location and distance from the source of PAH pollution, while 1-methy 1-7-isopropylphenanthrene (retene) was used as indicator for forest fires. A sediment depth profile indicates a major increase in the PAH concentrations after the First World War.     

PCB and HCB in the sediments and waters of the Tiber estuary

The contamination by polychlorinated biphenyls (PCB) and hexachlorobenzene (HCB) in sea waters and sediments of Tiber River estuary has been studied in 1976 and 1977.PCBs have been detected in all the samples analysed at mean levels of 0.297 ppb (1976) and 0.135 ppb (1977); these levels are much higher than those proposed as acceptable for surface waters. Contamination increases with increasing distance from the shore.HCB has been identified in only 16% of the water samples analysed and it was found absent in sediment samples.The results are discussed relative to both the levels of PCB in other sea waters and the toxicity of these products to the aquatic animals.     

Origin and analysis of aliphatic and cyclic hydrocarbons in northeast United Kingdom coastal marine sediments

Sediment samples from multiple sites in the North Sea Coast of England were solvent extracted and analysed by a quadruple gas chromatograph equipped with a mass spectrometer detector in order to determine the concentration and distribution of aliphatic and alicyclic n-alkanes. Results indicate that most of the organic species present in the sediment samples consisted of anthropogenically derived long chain aliphatic and alicyclic n-alkanes (_nC_{10-15, 17, 19-21, 24, 26, 27, 29, 30, 33, 35, 36, 43}), n-alkanols, n-alkanals, n-alkanones, esters as well as many volatile organic compounds (VOCs). Chemical composition of samples and relative concentration were found to vary both spatially and temporally on all scales. These variations are mainly attributable to spatial and temporal variations in source but also parameters such as rainfall, turbulence and micro-organism activity also account for the observed trends.     

An experimental investigation of nitrogen gas produced during denitrification

In situ denitrification relies on indigenous microorganisms to reduce nitrate to N(2) gas. However, when initial nitrate concentrations are large, produced gas volumes also can be very large, potentially resulting in reduced water saturation and hydraulic conductivity in the treatment zone. In this study, we investigated the fate of N(2) and other gases produced during denitrification in a laboratory flow cell containing packed sediment. Denitrifying activity was stimulated by additions of nitrate and ethanol. Microbial activity was monitored by measuring nitrate, nitrite, and ethanol concentrations; gas saturations were measured during the experiment using a gamma imaging system. Biomass was measured using phospholipid fatty acid analysis of sediment samples. Bioenergetic calculations calibrated to measured nitrate consumed and biomass produced predicted that 1.2 L N(2) gas/L water should have been produced following the addition of 100 mM nitrate. However, the maximum measured gas saturation was only 23%, indicating substantial gas loss from the sediment pack. Temporal gamma images and visual observations confirm that small gas bubbles formed in the sediment pack coalesced into larger bubbles and migrated upward through gas-filled channels to the sediment pack surface. Although gas saturations increased, there was no significant change in sediment pack hydraulic conductivity. These results suggest that in permeable reactive barriers used for in situ denitrification, gas production will not necessarily lead to unlimited gas accumulation in the pore space and that the effects of gas production on water saturation and hydraulic conductivity may be relatively minor.     

Bubble populations and acoustic interaction with the gassy floor of Eckernförde Bay

Anomalies in data taken with acoustic profiling systems often have been interpreted as indications of the widespread occurrence of free gas (gaseous state compounds) in the continental margins of the world’s oceans. Direct demonstration of the correlation between seafloor free gas and such acoustic anomalies has been rare. Interpretations have relied on occasional measurements of gas concentration in recovered seafloor samples, indirect indicators of in situ seafloor free gas and presumed analogous dynamic response of bubbles in sediments to the response of gas bubbles in water. Here, examples are provided of the measurement of free gas bubbles under in situ conditions for samples from the floor of Eckernförde Bay on the Baltic coast of Germany. The occurrence of this population of sediment gas bubbles has been related to the measured acoustic response of the region’s seafloor via model calculations. Indications of volume scattering of the acoustic energy by bubbles in a buried gassy layer are contrasted with evidence of possible gas bubble returns from a thin surficial gassy zone.     

Dioxin-like compounds in HPLC-fractionated extracts of marine samples from the east and west coast of Sweden: Bioassay- and instrumentally-derived TCDD equivalents

Lipophilic extracts of sediment, settling particulate matter (SPM) and blue mussel (Mytilus edulis) samples, collected at coastal locations on the east and west coast of Sweden, were HPLC-separated into three fractions containing 1. monoaromatic/aliphatic, 2. diaromatic (e.g. polychlorinated biphenyls (PCBs), polychlorinated dibenzodioxins and polychlorinated dibenzofurans (PCDDs/Fs)), and 3. polyaromatic compounds (e.g. polycyclic aromatic hydrocarbons (PAHs)). The fractions were tested for dioxin-like effects using a sensitive bioassay, based on EROD-induction in cultured chicken embryo livers. The concentrations of PCDDs/Fs, PCBs and 15 PAHs in the samples were also determined. The polyaromatic fractions of the sediment samples were more potent as EROD-inducers than the diaromatic fractions. Only a small part of the EROD-induction caused by the polyaromatic fractions could be explained by the analysed PAHs in the samples, indicating presence of non-quantified polyaromatic EROD-inducing compounds in the samples. A greater pollution by EROD-inducing diaromatic and polyaromatic compounds on the east coast site than on the west coast site was seen. The filtration activities and faeces production of the mussels on the east coast experimental site increased the sedimentation of PCDDs/Fs, PCBs and PAHs. The described bioassay proved very useful in the assessment of dioxin-like compounds in both abiotic and biotic samples from the marine environment.