Distribution and Sources of Petroleum Hydrocarbons in Recent Sediments of the Imo River, SE Nigeria.

The distribution of aliphatic and aromatic hydrocarbons in surface sediments of the lower course of the Imo River (Nigeria) was investigated to determine the sources and fate of these compounds. The aliphatic fraction is characterized by a widespread contribution of highly weathered/biodegraded hydrocarbon residues (reflected in the absence of prominent n-alkane peaks coupled with the presence of 17α(H),21ß(H)-25-norhopane, an indicator of heavy hydrocarbon biodegradation) of Nigerian crude oils (confirmed by the occurrence of 18α(H)-oleanane, a compound characteristic of oils of deltaic origin). The concentrations of polycyclic aromatic hydrocarbons (PAHs) ranging from 48 to 117 ng/g dry weight (dw; ∑13PAHs) indicate a moderate pollution, possibly lowered by the sandy lithology and low organic carbon (OC) content of the sediments. Concentrations slightly decrease towards the estuary of the river, probably due to the fact that these stations are affected by tidal flushing of pollutants adsorbed on sediment particles and carried away by occasional storm to the Atlantic Ocean. A number of PAH ratios, including parent/alkylated and isomeric compounds, indicates a predominance of petrogenic sources, with a low contribution of pyrolytic inputs, particularly of fossil fuel combustion. On the basis of OC/ON (>10) and Per/ΣPAHpenta- (>10) values, a diagenetic terrigenous OC was proposed as a source of perylene to the river.

A comparative assessment of intensive and extensive wastewater treatment technologies for removing emerging contaminants in small communities.

Ecosystem pollution due to the lack of or inefficient wastewater treatment coverage in small communities is still a matter of great concern, even in developed countries. This study assesses the seasonal performance of 4 different full-scale wastewater technologies that have been used in small communities (<2000 population equivalent) for more than 10 years in terms of emerging contaminant (EC), chemical oxygen demand (COD), total suspended solids (TSS) and NH4-N removal efficiency. The studied technologies, which were selected due to their widespread use, included two intensive treatment systems (an extended aeration system (AS) and a rotating biological contactor (RBC)) and two extensive treatment systems (a constructed wetland (CW) and a waste stabilization pond (WSP)), all located in north-eastern Spain. The studied compounds belonged to the groups of pharmaceuticals, sunscreen compounds, fragrances, antiseptics, flame retardants, surfactants, pesticides and plasticizers. The 25 ECs occurred in wastewater at concentrations ranging from undetectable to 80 µg L(-1). The average removal efficiency was 42% for the CW, 62% for the AS, 63% for the RBC and 82% for the WSP. All the technologies except the WSP system showed seasonal variability in the removal of ECs. The ecotoxicological assessment study revealed that, whilst all the technologies were capable of decreasing the aquatic risk, only the WSP yielded no risk in both seasons.

Assessment of photochemical processes in marine oil spill fingerprinting.

Understanding weathering processes plays a critical role in oil spill forensics, which is based on the comparison of the distributions of selected compounds assumed to be recalcitrant and/or have consistent weathering transformations. Yet, these assumptions are based on limited laboratory and oil-spill studies. With access to additional sites that have been oiled by different types of oils and exposures, there is a great opportunity to expand on our knowledge about these transformations. Here, we demonstrate the effects of photooxidation on the overall composition of spilled oils caused by natural and simulated sunlight, and particularly on the often used polycyclic aromatic hydrocarbons (PAHs) and the biomarker triaromatic steranes (TAS). Both laboratory and field data from oil released from the Macondo well oil following the Deepwater Horizon disaster (2010), and heavy fuel-oil from the Prestige tanker spill (2002) have been obtained to improve the data interpretation of the typical fingerprinting methodology.

Evaluation of artificially-weathered standard fuel oil toxicity by marine invertebrate embryogenesis bioassays.

wWeathering of petroleum spilled in the marine environment may not only change its physical and chemical properties but also its effects on the marine ecosystem. The objective of this study was to evaluate the toxicity of the water-accommodated fraction (WAF) obtained from a standard fuel oil following an environmentally realistic simulated weathering process for a period of 80 d. Experimental flasks with 40 g L(-1) of fuel oil were incubated at 18°C with a 14 h light:10 h dark photoperiod and a photosynthetically active radiation (PAR) intensity of 70 µE m(-2) s(-1). Samples were taken at four weathering periods: 24 h, 7, 21 and 80 d. WAF toxicity was tested using the sea urchin (Paracentrotus lividus) and mussel (Mytilus galloprovincialis) embryo-larval bioassays and the aromatic hydrocarbons levels (AH) in the WAF were measured by gas chromatography/mass spectrometry. In contrast with the classic assumption of toxicity decrease with oil weathering, the present study shows a progressive increase in WAF toxicity with weathering, being the EC(50) after 80d eightfold lower than the EC(50) at day 1, whereas AH concentration slightly decreased. In the long term, inoculation of WAF with bacteria from a hydrocarbon chronically-polluted harbor slightly reduced toxicity. The differences in toxicity between fresh and weathered fuels could not be explained on the basis of the total AH content and the formation of oxidized derivatives is suggested to explain this toxicity increase.

The use of long-chain alkylbenzenes and alkyltoluenes for fingerprinting marine oil wastes.

Petroleum long-chain alkylbenzenes and alkyltoluenes are characterized and used for chemical fingerprinting of marine oil spills. Their distributions, extending from C10 to C35 can be used for a general oil type classification. Moreover, the relative distributions of specific components, namely the 3-methyl and 2-methyl-1-alkylbenzenes (m- and o-isomers), and the aryl isoprenoid 1-methyl-3-phytanylbenzene, are proposed as diagnostic markers for source identification. This approach has been exemplified in two case studies involving the spill of bilge oils, where a preliminary screening of the potential source was obtained.

Compositional properties characterizing commonly transported oils and controlling their fate in the marine environment.

Oil spills relating to shipping incidents remain of substantial concern with respect to marine pollution. Whilst most frequently a reactive approach is adopted in post-incident monitoring (for the specific product involved), this paper reports important physical and compositional characteristics of commonly transported oils and oil products to afford pro-active assessments. These properties include specific gravity, viscosity, elemental composition and, of particular relevance, the relative class compositions between aliphatics, aromatics, resins and asphaltenes. The latter were determined experimentally using thin layer chromatography with flame ionization detection. Diagnostic ratios of specific compounds are reported, statistically analysed, and their significance in identification of different oil types and the weathering processes is discussed. The influence of the properties on fates under different environmental conditions (selected to represent contrasting European regional seas) are examined using the NOAA Automated Data Inquiry for Oil Spills (ADIOS2) model. Relative contributions of the different environmental conditions and properties to the fate of the oil at sea are discussed.

Polyphasic approach for assessing changes in an autochthonous marine bacterial community in the presence of Prestige fuel oil and its biodegradation potential.

A laboratory experiment was conducted to identify key hydrocarbon degraders from a marine oil spill sample (Prestige fuel oil), to ascertain their role in the degradation of different hydrocarbons, and to assess their biodegradation potential for this complex heavy oil. After a 17-month enrichment in weathered fuel, the bacterial community, initially consisting mainly of Methylophaga species, underwent a major selective pressure in favor of obligate hydrocarbonoclastic microorganisms, such as Alcanivorax and Marinobacter spp. and other hydrocarbon-degrading taxa (Thalassospira and Alcaligenes), and showed strong biodegradation potential. This ranged from >99% for all low- and medium-molecular-weight alkanes (C(15)-C(27)) and polycyclic aromatic hydrocarbons (C(0)- to C(2)- naphthalene, anthracene, phenanthrene, dibenzothiophene, and carbazole), to 75-98% for higher molecular-weight alkanes (C(28)-C(40)) and to 55-80% for the C(3) derivatives of tricyclic and tetracyclic polycyclic aromatic hydrocarbons (PAHs) (e.g., C(3)-chrysenes), in 60 days. The numbers of total heterotrophs and of n-alkane-, aliphatic-, and PAH degraders, as well as the structures of these populations, were monitored throughout the biodegradation process. The salinity of the counting medium affects the counts of PAH degraders, while the carbon source (n-hexadecane vs. a mixture of aliphatic hydrocarbons) is a key factor when counting aliphatic degraders. These limitations notwithstanding, some bacterial genera associated with hydrocarbon degradation (mainly belonging to α- and γ-Proteobacteria, including the hydrocarbonoclastic Alcanivorax and Marinobacter) were identified. We conclude that Thalassospira and Roseobacter contribute to the degradation of aliphatic hydrocarbons, whereas Mesorhizobium and Muricauda participate in the degradation of PAHs.

Phase distribution of hydrocarbons in the water column after a pelagic deep ocean oil spill.

Spills from wrecks are a potential major source of pollution in the deep ocean. However, not much is known about the fate of a spill at several kilometers depth, beyond the oceans continental shelves. Here, we report the phase distribution of hydrocarbons released from the wrecks of the Prestige tanker, several years after it sank in November 2002 to depths between 3500 and 3800 m. The released oil reached the surface waters above the wrecks without any signs of weathering and leaving an homogenous signature throughout the water column. At depths of several kilometers below the sea surface, the occurrence and spread of the deep sea oil spill could be evaluated better by quantifying and characterizing the dissolved hydrocarbon signature, rather than just the investigation of hydrocarbons in the suspended particulate matter.

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 (Sigma13 parent components) were in the range of 22-47528 mug/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.

Assessment of cleanup needs of oiled sandy beaches: lessons from the Prestige oil spill.

Surveys of the oiled sandy beaches along the northern Atlantic coast of Spain, 2-5 years after the Prestige oil spill of November 2002, have provided new evidence regarding buried fuel and its behavior. The persistence and depth of burial of oil, and the capacity of the beach for natural regeneration, depend on beach morphodynamics, which drive a sequence of physicochemical processes that reduce subsurface tar balls to highly divided oil forms while also allowing appreciable weathering despite burial. These findings prompted reassessment of current spill evaluation strategies. A protocol is proposed that combines the modeling of beach morphodynamics, an environmentally friendly coring survey, and well-calibrated hydrocarbon analysis.

Bacterial communities from shoreline environments (costa da morte, northwestern Spain) affected by the prestige oil spill.

The bacterial communities in two different shoreline matrices, rocks and sand, from the Costa da Morte, northwestern Spain, were investigated 12 months after being affected by the Prestige oil spill. Culture-based and culture-independent approaches were used to compare the bacterial diversity present in these environments with that at a nonoiled site. A long-term effect of fuel on the microbial communities in the oiled sand and rock was suggested by the higher proportion of alkane and polyaromatic hydrocarbon (PAH) degraders and the differences in denaturing gradient gel electrophoresis patterns compared with those of the reference site. Members of the classes Alphaproteobacteria and Actinobacteria were the prevailing groups of bacteria detected in both matrices, although the sand bacterial community exhibited higher species richness than the rock bacterial community did. Culture-dependent and -independent approaches suggested that the genus Rhodococcus could play a key role in the in situ degradation of the alkane fraction of the Prestige fuel together with other members of the suborder Corynebacterineae. Moreover, other members of this suborder, such as Mycobacterium spp., together with Sphingomonadaceae bacteria (mainly Lutibacterium anuloederans), were related as well to the degradation of the aromatic fraction of the Prestige fuel. The multiapproach methodology applied in the present study allowed us to assess the complexity of autochthonous microbial communities related to the degradation of heavy fuel from the Prestige and to isolate some of their components for a further physiological study. Since several Corynebacterineae members related to the degradation of alkanes and PAHs were frequently detected in this and other supralittoral environments affected by the Prestige oil spill along the northwestern Spanish coast, the addition of mycolic acids to bioremediation amendments is proposed to favor the presence of these degraders in long-term fuel pollution-affected areas with similar characteristics.

Surface waters are a source of polychlorinated biphenyls to the coastal atmosphere of the North-Western Mediterranean Sea.

Atmospheric (gaseous and particulate) and seawater (dissolved and particulate in the surface microlayer and underlying waters) samples were collected in 2001 and 2002 in two North-Western Mediterranean contrasting coastal environments, Banyuls-sur-Mer (France) and Barcelona (Spain). The total aerosol suspended particle concentrations (microg m(-3)) were higher in Barcelona (266+/-132) than in Banyuls-sur-Mer (149+/-43), even under near-gale conditions. The influence of the marine aerosol in the total suspended particles (TSP) concentration was backed by both organic carbon (OC) and elemental carbon (EC) concentrations, as they exhibited lower levels in Banyuls (3+/-2 microg OC m(-3) and 0.4+/-0.3 microg EC m(-3)) than in Barcelona (31+/-26 microg OC m(-3) and 6+/-8 microg EC m(-3)). Moreover, samples from Barcelona, both atmospheric and seawater, showed greater variability than in Banyuls (Snedecor's test (p<0.001)) possibly reflecting the influence of urban sources of pollutants. Concentrations of atmospheric PCBs (Sigma41 congeners) off-shore Barcelona ranged from 389 to 1410 pg m(-3) in the gas phase and from 71 to 78 pg m(-3) in the aerosol phase. In Banyuls, concentrations were 30.7-858 pg m(-3) in the gas phase and 12.8-41.2 pg m(-3) in the aerosol phase. Their gas-particle partitioning suggested that PCBs in the samples were close to equilibrium (deduced from the regression of the experimental logK(p) and logP(l)(0)). Moreover, a positive correlation was found between wind direction, wind speed and atmospheric PCB concentrations, which is consistent with the fact the PCB concentration of the marine waters, influenced by coastal run-off, become a secondary source for these semi-volatile compounds after volatilization to the coastal atmosphere. This is supported by the high dissolved concentrations in the coastal surface waters, and specially by the enrichment found in the surface microlayer.

Fast preparation of the seawater accommodated fraction of heavy fuel oil by sonication.

The seawater accommodated fraction (SWAF) of oil is widely used for the assessment of its toxicity. However, its preparation in the laboratory is time consuming, and results from different authors are difficult to compare as preparation methods vary. Here we describe a simple and fast set up, using sonication, to produce reproducible SWAF in the laboratory. The system was tested on heavy fuel oil placed on seawater at different salinity and temperature conditions. Maximum dissolution of the oil was achieved after 24h, independently of both seawater salinity and temperature. Our findings are discussed in relation to the fate of the oil from the deep spill of the Prestige tanker. Changes in temperature in the open ocean are bound to have larger impact in the concentration of the SWAF than the corresponding values of sea water salinity. We anticipate that in this type of incident the highest SWAF, as the oil reaches the sea surface, should be expected in the warmest and less saline waters of the water column.

Toxicity and phototoxicity of water-accommodated fraction obtained from Prestige fuel oil and Marine fuel oil evaluated by marine bioassays.

Acute toxicity and phototoxicity of heavy fuel oil extracted directly from the sunken tanker Prestige in comparison to a standard Marine fuel oil were evaluated by obtaining the water-accommodated fraction (WAF) and using mussel Mytilus galloprovincialis and sea urchin Paracentrotus lividus embryogenesis bioassays, and copepod Acartia tonsa and fish Cyprinodon variegatus survival bioassays. Aromatic hydrocarbon (AH) levels in WAF were measured by gas chromatography. Prestige WAF was not phototoxic, its median effective concentrations (EC50) were 13% and 10% WAF for mussel and sea urchin respectively, and maximum lethal threshold concentrations (MLTC) were 12% and 50% for copepod and fish respectively. Marine WAF resulted phototoxic for mussel bioassay. EC50s of Marine WAF were 50% for sea urchin in both treatments and 20% for mussel under illumination. Undiluted Marine WAF only caused a 20% decrease in mussel normal larvae. Similar sensitivities were found among sea urchins, mussels and copepods, whilst fish were less sensitive. Unlike Marine WAF, Prestige WAF showed EC50 values at dilutions below 20%, and its toxicity was independent of lighting conditions. The differences in toxicity between both kinds of fuel could not be explained on the basis of total AH content.

The Prestige oil spill: bacterial community dynamics during a field biostimulation assay.

A field bioremediation assay using the oleophilic fertilizer S200 was carried out 12 months after the Prestige heavy fuel-oil spill on a beach on the Cantabrian coast (north Spain). This assay showed that S200-enhanced oil degradation, particularly of high-molecular-weight n-alkanes and alkylated PAHs, suggesting an increase in the microbial bioavailability of these compounds. The bacterial community structure was determined by cultivation-independent analysis of polymerase chain reaction-amplified 16S rDNA by denaturing gradient gel electrophoresis. Bacterial community was mainly composed of alpha-Proteobacteria (Rhodobacteriaceae and Sphingomonadaceae). Representatives of gamma-Proteobacteria (Chromatiales, Moraxellaceae, and Halomonadaceae), Bacteroidetes (Flavobacteriaceae), and Actinobacteria group (Nocardiaceae and Corynebacteriaceae) were also found. The addition of the fertilizer led to the appearance of the bacterium Mesonia algae in the early stages, with a narrow range of growth substrates, which has been associated with the common alga Achrosiphonia sonderi. The presence of Mesonia algae may be attributable to the response of the microbial community to the addition of N and P rather than indicating a role in the biodegradation process. The Rhodococcus group appeared in both assay plots, especially at the end of the experiment. It was also found at another site on the Galician coast that had been affected by the same spill. This genus has been associated with the degradation of n-alkanes up to C(36). Taking into account the high content of heavy alkanes in the Prestige fuel, these microorganisms could play a significant role in the degradation of such fuel. A similar bacterial community structure was observed at another site that showed a similar degree of fuel weathering.

Spatial and temporal trends of polycyclic aromatic hydrocarbons in wild mussels from the Cantabrian coast (N Spain) after the Prestige oil spill.

Polycyclic aromatic hydrocarbon (PAH) levels were determined in tissues of wild mussels (Mytilus galloprovincialis) collected at 17 stations along the Cantabrian coast (N Spain), from Navia (Asturias) to Fuenterrabía (Basque Country), in order to assess the extent of the environmental impact caused by the Prestige oil spill (November 13, 2002). Six sampling campaigns were carried out in April, June and November in 2003 and 2004. The comparison of PAH data with those obtained earlier in 2000 showed a widespread pyrolytic and petrogenic contamination and allowed an estimation, for the first time, of the background pollution in the region and identification of the chronic hotspots. The spatial distribution found in the first samples after the oil spill revealed the eastern area as the most affected due to the continuous arrival of fuel slicks since early summer 2003. Several stations in this area showed increased total PAH concentrations of up to 15 times the pre-spill levels, which did not recover until April 2004, more than one year after the accident. Molecular parameters within the aliphatic and aromatic fractions were determined to assess the presence of Prestige oil in these samples.

Prestige oil spill. III. Fate of a heavy oil in the marine environment.

More than 200 oil samples were collected along the Northern Spanish coast, from December 2002 to December 2003, as part of the extensive monitoring program carried out by the Spanish Marine Safety Agency after the Prestige heavy oil spill (November 13, 2002). The GC FPD/ FID and comprehensive GC x GC/TOFMS sample profiles revealed the main characteristics of the oil residues. Chemical fingerprinting of the aliphatic and aromatic fractions by GC/ MS was performed to determine the source of the oil as well as to follow its weathering at sea. The (n-C13 + n-C14)/(n-C25 + n-C26), n-C18/phytane, and methylnaphthalene [(N + N1)/N2] ratios were found to be useful for assessing the evaporation, biodegradation, and dissolution processes, respectively. Other indicators of more advanced degradation processes, including photo-oxidation, were unaltered, showing the low incidence of natural weathering processes on the spilled heavy oil 1 year after the accident. The survey also demonstrated the occurrence of continued discharges of ballast waters at sea and the need for a more stringent surveillance of the area, beyond accidental oil spills.

Screening ecological risk assessment of persistent organic pollutants in Mediterranean sea sediments.

A screening ecological risk assessment (ERA) was conducted for the first time in the Mediterranean basin in order to assess the toxicity posed to the benthic community by PCBs, DDTs and HCB in marine sediments. The characterization of the exposure was conducted by means of an extensive literature survey, generating a database with more than 2000 samples. The effects were assessed by the adoption of guidelines previously developed in the literature, because ecotoxicological information about persistent organic pollutants (POPs) in the Mediterranean sediments was lacking. Existing sediment quality guidelines (SQGs) for the target pollutants were compiled and consensus values were calculated for three different categories of toxicity, namely threshold effect concentration (TEC), probable effect concentration (PEC) and extreme effect concentration (EEC). The combination of exposure and effects characterization enabled the identification of some areas of concern in the vicinity of industrial and urban locations and in the mouths of the main Mediterranean rivers. Beyond the Mediterranean continental shelf, the level of toxicity for the benthic community was generally low. The evaluation of the toxicity induced by the mixture of the target pollutants spotted the importance of DDT contamination in the Mediterranean sediments, despite the fact that main inputs to the sea have been significantly reduced during the last decades.

Influence of water filtration on the determination of a wide range of dissolved contaminants at parts-per-trillion levels.

The adsorption of dissolved organic contaminants on glass fibre filters throughout water dissolved/particulate phase decoupling studies was examined. A total of 49 different compounds were considered at low concentration levels (ng L(-1)), including PAHs, PCBs, organochlorine and organophosphorus pesticides, triazines, thiocarbamates, pyrethroids, phosphate esters and caffeine. Their adsorption on the filters was positively correlated with their log Kow and solubilities, indicating that filter adsorption increased with hydrophobicity. The influence of water properties (i.e. salinity and dissolved organic carbon (DOC) content) was also studied by means of a star experimental design (n=11). Salinity was the main factor in increasing the adsorption, due to the salting out effect. The influence of DOC suggested that part of the contaminant losses during water filtration may have been caused by the retention on the organic matter adsorbed on the filter surface. Nevertheless, a decrease in filter retention was observed for water with the highest DOC contents, which was probably due to an enhancement of the contaminant solubility in these conditions. Although several factors may control the adsorption process in naturally occurring waters, the extent of the retention of dissolved target analytes on the glass fibre filters should not be underestimated in the analysis of hydrophobic contaminants in marine and estuarine waters at very low concentrations (ppt level).

Assessment of the Mediterranean sediments contamination by persistent organic pollutants.

A compilation of information about levels of selected persistent organic pollutants, namely polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroetane and its degradation products (DDTs) and hexachlorobenzene (HCB), in Mediterranean sediments, including data published from 1971 to 2005, has been conducted in order to assess their main drivers and pressures in the environment. The application of mapping tools (GIS) and statistical instruments enabled the assessment of geographical and temporal trends. Chemical contamination mainly originates from land-based sources, and decreases significantly when moving off-shore. Contamination hot spots are generally located along the Northern coastline. The data for open sea sediments enabled the establishment of background levels of contamination for the region. A decreasing temporal trend in concentrations was found, more evident in the case of DDTs probably due to a more efficient regulation of this chemical. Finally, some gaps in reliable data were also identified which were related to the lack of information in the southern and eastern parts of the Mediterranean as well as the variety of analytical methodologies used.