Recurrent arrival of oil to Galician coast: the final step of the Prestige deep oil spill.

Yearly monitoring in one of the most affected coastal zones by the Prestige oil spill, namely Nemiña and O Rostro beaches (NW Spain), has been carried out since 2004. Topographic data of beaches revealed seasonal altimetric changes up to 4m that would prevent the on shore persistence of oil. However, surficial and subsurficial oil was detected in the intertidal area of both beaches in all campaigns. The hydrocarbon analysis confirmed that this oil corresponded to the Prestige oil, even nine years after the accident. Tar balls were highly biodegraded suggesting that the oil was accumulated on the subtidal sediments for a long time and transported to the coast by the action of waves. The present work provides new evidence of the long term persistence of deep oil spills from wrecks in marine areas where the hydrodynamic conditions play a twofold key role, in determining the exposed coastal area to recurrent contamination and in burying and resurfacing the oil in the intertidal zone.

Quantification and source identification of polycyclic aromatic hydrocarbons in core sediments from Sundarban mangrove wetland, India.

The distribution and potential sources of 16 polycyclic aromatic hydrocarbons (PAHs) in sediment cores (<63 microm particle size) of the Sundarban mangrove wetland, northeastern coast of Bay of Bengal (India), were investigated by gas chromatography coupled to mass spectrometry. The total concentrations of 16 PAHs ( summation operator(16)PAHs) ranged from 132 to 2938 ng/g, with a mean of 634 ng/g, and the sum of 10 out of 16 priority PAHs ( summation operator(10)PAH) varied from 123 to 2441 ng/g, with a mean of 555 ng/g, and the 5 carcinogenic PAHs (benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, and dibenz[a,h]anthracene) accounted for 68-73% of the priority PAHs. Maximum concentrations of the sediment core were obtained at subsoil depth of 12-16 cm. The prevalence of four to six aromatic ring PAHs and cross-plots of specific isomer ratios such as phenanthrene/anthracene, fluoranthene/pyrene, and methylphenanthrenes/phenanthrene suggested the predominance of wood and coal combustion sources, the atmospheric deposition, and surface runoff to be the major transport pathways. A good correlation existed between the benzo[a]pyrene level and the total PAH concentrations, making this compound a potential molecular marker for PAH pollution. Total TEQ (S) (carc) values calculated for samples varied from 6.95 ng/g TEQ (S) (carc) to 119 ng/g TEQ (S) (carc) , with an average of 59 ng/g dry weight TEQ (S) (carc) . The baseline data can be used for regular monitoring, considering the industrial and agricultural growth around this coastal environment.

Accumulation trends of petroleum hydrocarbons in commercial shellfish from the Galician coast (NW Spain) affected by the Prestige oil spill.

Aliphatic and aromatic hydrocarbons were determined in three species of commercial shellfish, namely razor shells (Ensis arcuatus and Ensis siliqua), goose barnacle (Pollicipes cornucopia) and sea urchin (Paracentrotus lividus), living in different habitats and exhibiting different feeding behaviors. The samples were collected monthly, from January 2003 to October 2004, in three stations of the Galicia coast (NW Spain), following the Prestige oil spill, with the aim of assessing their response to the spill and, therefore, their suitability for monitoring purposes. The aliphatic fractions were mostly dominated by biogenic hydrocarbons, reflecting the diet composition of the organisms and their low metabolic capacity. The presence of oil was assessed by the determination of chemical markers. The analysis of the aromatic fractions revealed the occurrence of 3-6 ring parent and alkylated PAHs, consistent with a mixed petrogenic-pyrolytic origin, with the common feature of the predominance of chrysene in all samples collected after the spill. However, the distributions exhibited both temporal and interspecies variations. The PAH concentrations (Sigma13) increased significantly after the spill and decreased 6-7 months later close to background levels for the region. One year after the accident, the median values were: 58 microg/kg for razor shells, 26 microg/kg for barnacles, and 25 microg/kg for sea urchins. The temporal evolution of the PAH concentrations along the survey period was used to estimate loss rates for bioavailable PAHs in barnacles and sea urchins after the spill. Half-life values were in the order of 30 and 60 d, respectively. The results of the study demonstrate that barnacles can be suitable species for oil spill monitoring.

Determination of organochlorine compounds in neuston from the Mediterranean.

A reliable analytical procedure was developed to determine trace levels of organochlorine compounds in neuston samples. Freeze-dried samples were extracted by sonication (3 x 15 ml cyclohexane, 15 min) followed by gel permeation chromatography (GPC) and gas chromatography electron capture detection (GC-ECD) determination. Neuston samples may present great differences in their lipid content, which may become a drawback for the analytical determination of hydrophobic pollutants. In this way, GPC fractionation combined with Florisil cleanup was successfully used to avoid potential lipidic interferences in the GC-ECD determination. Organochlorine compounds were determined by GC-ECD and a standard addition method was performed to evaluate the recoveries of 41 PCB individual congeners (80 +/- 20%). The congeners with lower K(ow) (octanal water partition coeeficient) values showed lower recoveries (54 +/- 7%) than the more lipophylic ones (80 +/- 7%). The limits of detection ranged from 0.001 to 0.211 ng g(-1) of wet samples. The reproducibility of the developed analytical methodology for independent replicates (n = 3) at low pg g(-1) levels was quite satisfactory (RSD 18 +/- 10%).

Assessment of in vivo effects of the prestige fuel oil spill on the mediterranean mussel immune system.

A laboratory experiment was carried out to study immune function alteration of the mussel Mytilus galloprovincialis when exposed to the Prestige oil spilled in November 2002 on the northwestern Spanish coast. Mussels were maintained for 4 months in tanks with flowing seawater and with 1, 2, and 0 kg (controls) Prestige fuel oil. Polycyclic aromatic hydrocarbon concentrations, which were determined in gills and digestive glands, were higher in digestive glands. The methylphenantrene and dibenzothiophene profiles confirmed the real exposure of mussels to the fuel oil. Immune data analysis revealed that no differences between fuel-treated and control animals were found in the cellular immune parameters measured (hemocyte viability, phagocytic activity, nitric oxide production, and chemiluminescence emission). In addition, histologic observations did not reveal tissue lesions in any of the samples, probably because of the short time of fuel-oil exposure. In contrast, significant differences were found in serum protein concentration and lysozyme activity between the fuel-treated mussels and controls. However, these humoral immune parameters were dependant on numerous environmental and physiologic factors, so it was difficult to ascertain the real effect of the fuel oil on their variability. Because hemocytes are the primary line of defense of bivalve mollusks, the results obtained in the present study suggest that the mussel immune system was not significantly affected by exposure to the Prestige fuel oil.

Fingerprinting petroleum hydrocarbons in plankton and surface sediments during the spring and early summer blooms in the Galician coast (NW Spain) after the Prestige oil spill.

Plankton samples (20-350 microm and >350 microm) collected at three transects along the Galician coast (NW Spain) were analysed for individual aliphatic and aromatic hydrocarbons by GC-MS. Sample collection was performed in April-July 2003, after the Prestige oil spill (November 2002), to determine whether the hydrocarbons released into the water column as a consequence of the spill were accumulated by the planktonic communities during the subsequent spring and early summer blooms. Surface sediments were also collected to assess the presence of the spilled oil, removed from the water column by downward particle transport. Plankton concentrations of PAHs (Sigma14 parent components) were in the range of 25-898 ng g(-1)dw, the highest values being close to coastal urban areas. However, the individual distributions were highly dominated by alkyl naphthalenes and phenanthrenes, paralleling those in the water dissolved fraction. The detailed study of petrogenic molecular markers (e.g. steranes and triterpanes, and methyl phenanthrenes and dibenzothiophenes) showed the occurrence of background petrogenic pollution but not related with the Prestige oil, with the possible exception of the station off Costa da Morte in May 2003, heavily oiled after the accident. The dominant northerly wind conditions during the spring and early summer 2003, which prevented the arrival of fresh oil spilled from the wreck, together with the heavy nature of the fuel oil, which was barely dispersed in seawater, and the large variability of planktonic cycles, could be the factors hiding the acute accumulation of the spilled hydrocarbons. Then, with the above exception, the concentrations of PAHs found in the collected samples, mostly deriving from chronic pollution, can be considered as the reference values for the region.

Spatial and temporal trends of petroleum hydrocarbons in wild mussels from the Galician coast (NW Spain) affected by the Prestige oil spill.

Polycyclic aromatic hydrocarbons (PAHs) were determined in tissues of wild mussels (Mytilus galloprovincialis) from the Galicia coast (NW Spain) in order to assess the extent of the environmental impact caused by the Prestige oil spill (November 13, 2002). Three sampling campaigns were carried out in February, June and November 2003 at 24 stations along the Galicia coast, from La Guardia (Pontevedra) to Ribadeo (Lugo). The spatial distribution of PAHs found in the first sampling period, clearly revealed the central area (Costa da Morte) as the most affected by the oil spill. In these stations, concentrations up to 7780 microg/kg dw of the sum of 13 parent PAHs were found 2-3 months after the spill. Molecular parameters within the aliphatic and aromatic fractions confirmed the presence of the Prestige oil in these samples. The levels markedly decreased at most of the stations in the second sampling and recovered to levels found before the spill in November 2003, 1 year after the accident (29-279 microg/kg dw, av. 133+/-83 microg/kg dw). However, a certain increase was observed in some sites which could be related to the remobilization of oil residues from still unclean intertidal spots or sediments due to the winter marine weather conditions.

Spatial and temporal distribution of dissolved/dispersed aromatic hydrocarbons in seawater in the area affected by the Prestige oil spill.

Seawater samples collected at three depths from 68 stations along the Northern Spanish coast were analysed for dissolved/dispersed petroleum aromatic hydrocarbons by UV-fluorescence and for 25 individual compounds by GC-MS. Sampling was performed in December 2002, just after the Prestige oil spill, and in February-March and September 2003. Higher concentrations of total aromatic hydrocarbons were found at all depths in the samples collected during December 2002 off the Galicia coast, with levels ranging between 0.19 and 28.8 microg/L eq. oil (0.1-4.8 microg/L chrysene eq.). These values decreased in the following cruises, till <0.05-2.86 microg/L oil eq. (av. 0.23 microg/L chrysene eq.) in September 2003, possibly representing the background levels for the region. However, in the Cantabrian coast they were still high at the surface in the March cruise, probably by the late arrival of the fuel-oil to this area. Some coastal hot spots were also identified, with values up to 29.2 microg/L fuel-oil eq., close to river mouths and urban areas. The individual PAH distributions in the December 2002 sampling off-Galicia were dominated by alkyl-naphthalene derivatives, consistently with the pattern distribution shown by the fuel-oil water accommodated fraction. The higher concentrations were found in the subsurface samples along the Costa da Morte, the area most heavily affected by the spill (av. 0.46 microg/L Sigma16 PAHs). The rest of the samples collected in other areas exhibited lower concentrations and a more even distribution of 2-4 ring PAHs, that ranged from 0.09 to 0.37 microg/L (av. 0.15 microg/L Sigma16 PAHs), with decreasing trends offshore and downward the water column. In September 2003, the values were rather uniform, averaging 0.09 microg/L (Sigma16 PAHs).

Spatial distribution and ecotoxicity of petroleum hydrocarbons in sediments from the Galicia continental shelf (NW Spain) after the Prestige oil spill.

The distribution of aliphatic and aromatic hydrocarbons was determined in surface sediments collected at 36 stations along the Galicia continental shelf (NW Spain), following the Prestige oil spill. Sampling was performed in December 2002, just after the accident, and in February and September 2003. Concentrations of PAHs (summation operator 13 parent components) were in the range of 0.9-422 microg/kgdw, the highest values being close to coastal urban areas (e.g. Pontevedra and A Coruña), whereas in the stations of the area most heavily impacted by the spill (off Costa da Morte) concentrations were in the range of 14.8-89.6 microg/kgdw, with a certain predominance of alkylated compounds, which may suggest a mixture of petrogenic and pyrolytic sources. The detailed study of petrogenic molecular markers (e.g. steranes and triterpanes) showed the occurrence of an old (weathered) petrogenic chronic pollution in the shelf sediments but not of the Prestige oil, with the possible exception of few stations in the area of Costa da Morte. This was attributed to the heavy nature of the spilled oil that was barely dispersed in the water column and mainly stranded on the coast or sedimented in the form of oil patches. The addition of increasing amounts of fuel oil to a representative sediment sample showed that the molecular indices were indicative of the presence of the Prestige oil when the amount was above 1g/kg of sediment. The toxicity of selected samples (showing the higher PAH concentrations) was tested using the bivalve embryogenesis bioassay. Embryogenesis success reached high values in all cases (80-88%, with 86% in the control), indicating a lack of toxicity in the sediments and supporting the conclusion that the patchiness of the fuel eventually reaching the seafloor reduced its impact on the benthic communities of the Galician shelf.

Comparison of sampling devices for the determination of polychlorinated biphenyls in the sea surface microlayer.

Over 30 sea surface microlayer (SML) samples from two contrasting sites in the North Western Mediterranean -- Barcelona (Spain) and Banyuls-sur-Mer (France) -- were collected using three different sampling devices, namely, glass plate, metal screen (MS) and a surface slick sampler (SS), and compared with the corresponding underlying water (16 samples). The distributions of 41 polychlorinated biphenyl congeners (PCBs) were determined in the different phases: particulate (1.17-10.8 SigmaPCB ng L(-1)), truly dissolved (0.080-16.7 SigmaPCB ng L(-1)) and colloidal matter (1.17-43.0 SigmaPCB ng L(-1)), being the last two estimated from the analysis of the apparently dissolved phase. Concentrations of PCBs in the SML were higher than those in the underlying water (ULW), giving rise to enrichment factors (EF=[C](SML)/[C](ULW)) up to first-order of magnitude. The ANOVA statistical approach was used to assess differences of bulk data (e.g. dissolved organic carbon, DOC; particulate organic carbon, POC; suspended particulate matter, SPM) among sampling devices, whilst p-tailed t paired tests were used in order to compare the enrichments obtained for each sampling date. In this respect, no significantly different enrichment factors were found among sampling devices (p < 0.05), although the surface SS showed lower enrichments, probably due to the dilution of the SML with the ULW during sampling. The MS seemed to be the most suitable device for the determination of PCBs in the SML in terms of sampling efficiency under a variety of meteorological conditions.

Evaluation of sampling devices for the determination of polycyclic aromatic hydrocarbons in surface microlayer coastal waters.

The sea surface microlayer (SML) may play an important role on the transport and fate of persistent organic pollutants in the marine environment. In order to evaluate the appropriateness of a number of sampling devices for the analysis of 14 parent polycyclic aromatic hydrocarbons (3-5 aromatic rings), marine SML waters were sampled using a glass plate, a rotating drum/roller, a metal screen and a surface slick sampler. The underlying waters were also sampled for the determination of the corresponding enrichment factors (EF = [C](microlayer)/[C](underlying water)). The EFs were phase dependent, ranging from 1 to 3 for the dissolved phase and between 4 and 7 for the particulate phase. In order to better assess the performance of the different sampling methods, in terms of phase partitioning, the truly dissolved and colloidal phases were also estimated. Generally, no significant differences were found for the enrichment factors provided by the different methods, due to the observed large variability in concentrations that can be attributed to small-scale coastal processes. However, the metal screen is recommended as the most efficient sampling method for the study of PAHs taking into account the amount of water collected versus time.

Factors affecting the organochlorine pollutant load in biota of a rice field ecosystem (Ebro Delta, NE Spain).

The concentrations of PCBs, DDTs, HCHs, HCB and OCS were determined in sediments and associated biota, both invertebrates (Physella acuta, Hirudo medicinalis, chironomid larvae, Hydrous pistaceus, Helochares lividus) and vertebrates (Rana perezi), in a temporary aquatic system, a rice field in the Ebro Delta (NE Spain). The qualitative and quantitative distribution of organochlorine compounds in sediments and aquatic biota has been explained by two mechanisms: equilibrium partitioning and/or biomagnification through the trophic web. Nevertheless, bioaccumulation processes are by far more complex, since several biotic and abiotic factors contribute to the observed pollutant loads in the organisms. In this respect, the biological characteristics of the organisms considered (e.g. species, age, lipid contents, feeding habits, etc.), as well as ecological factors (e.g. the habitat of the species and vertical distribution), have been shown to account for the organochlorine levels observed.

The aegean sea oil spill in the Galicia Coast (NW Spain). I. Distribution and fate of the crude oil and combustion products in subtidal sediments.

The spatial distribution and fate of petrogenic and pyrogenic hydrocarbons in coastal sediments following the Aegean Sea oil spill (Galicia, NW Spain) was investigated through a detailed study of chemical markers. Alkanes and acyclic isoprenoid hydrocarbons were degraded within six months of the accident, but triterpane and sterane distributions were still detectable and were useful in monitoring, respectively, the oil source and weathering. Aromatic steranes were also useful source indicators, and oil degradation was clear from the decrease of certain alkyl dibenzothiophene and phenanthrene isomers. The pyrogenic polycyclic aromatic hydrocarbons produced in the tanker wreck were found more persistent than the petrogenic ones. However, the presence of the oil in the sediments was recognized even one year after the accident and was found particularly preserved in the subsurface layers.

A potential source of organic pollutants into the northeastern Atlantic: the outflow of the Mediterranean deep-lying waters through the Gibraltar Strait.

Small and large-size particles were collected in the water column (50-3000 m) of a Northeastern Atlantic area where deep Mediterranean waters, outflowing through the Strait of Gibraltar, are incorporated at mid-depth. Particles collected by water filtration (0.7 micron pore size) and by vertical hauls of a neuston net (50 microns mesh size) were analyzed for organic pollutants, namely aliphatic and aromatic hydrocarbons, and organochlorine compounds. Small-size particles represented the largest bulk of particulate organic carbon as well as of hydrophobic organic pollutants. Surface concentrations of n-alkanes [C14-C35), aromatic hydrocarbons (12 parent compounds), PCBs (7 congeners), and DDTs (DDT + DDE) were, respectively, in the range of 50-63 ng/L, 23-68 pg/L, 8-13 pg/L, and 0.05-1.7 pg/L. These concentrations showed a general decrease with depth, particularly significant in the upper 200 m, consistently with the POC contents. Compositional changes with depth were also evident in small-size particles and included the depletion of low molecular weight n-alkanes and low chlorinated PCB congeners as well as a decrease of the fossil to pyrolytic PAHs ratio. Unusual increases of concentrations were observed at mid-depths (900-1100 m), indicating additional particle inputs, either by in-situ formation or by advective transport from the Mediterranean. The latter was recognized because small-size particles within these water veins exhibited distribution patterns out of the vertical sequence and similar to those of deep Mediterranean waters. An input of 8 and 0.5 tons per year of the above PAH and PCB compounds, respectively, has tentatively been calculated as the contribution of these Mediterranean waters to the Northeastern Atlantic.

The integrated use of chemical analysis, cytochrome P450 and stress proteins in mussels to assess pollution along the Galician coast (NW Spain).

Aliphatic and polycyclic aromatic hydrocarbons (PAHs) as well as biochemical markers, such as cytochrome P450, benzo(a)pyrene hydroxylase (BPH) and stress-70 proteins, were determined in mussels (Mytilus galloprovincialis) collected in October 1995 from several locations along the Galician coast (NW Spain). The survey proved the existence of a pollution gradient among sampling sites and a chronic exposure to petrogenic and pyrolitic hydrocarbons. This was reflected in mussel tissue levels of PAHs which ranged from 22 to 562 ng/g wet weight. High levels of total cytochrome P450 were detected in mussels from the most polluted sites, but differences were not statistically significant. BPH activity did not show either differences among sampling sites. Conversely, stress-70 proteins were significantly induced in the most polluted locations, and levels of the 72-kDa band correlated well (r2 = 0.854) with the sum of the PAHs from four to six rings accumulated by mussels.

Sequential method for the field determination of nanomolar concentrations of dimethyl sulfoxide in natural waters.

A procedure for the determination of dimethyl sulfoxide (DMSO), along with dimethyl sulfide (DMS) and dimethyl sulfoniopropionate (DMSP), at nanomolar levels in natural waters has been developed. After removal of DMS by purge and cryotrapping, DMSP is removed by the same method after alkaline hydrolysis, and DMSO is reduced to DMS using a combination of sodium borohydride and hydrochloric acid. The DMS produced is stripped, cryotrapped, and analyzed by gas chromatography. Detection of 3 pmol of DMSO was achieved, resulting in a detection limit of 0.05 nM for a 50 mL sample. Mean yield for standards in the range 0.7-130 nM (n = 31) was 95%, and mean precision (as coefficient of variation) was 14%. Precision for replicates of natural seawater samples was always ≤10%. Mean yields of the sequential analysis of DMS + DMSP + DMSO (1.5-25 nM) standard mixtures in seawater were >90% for the three species. Filtered seawater samples stored frozen (-20 °C) showed no significant changes in DMSO concentration. Since DMSP is the only compound, other than DMSO, that gives rise to DMS upon reduction with NaBH(4), tests were performed to ensure that DMSP is quantitatively removed before the DMSO analysis. Boranes were identified as the substances that produced two major peaks in the chromatogram of the reduction products. Adequate chromatographic conditions were established to avoid their coelution with DMS. This entire protocol allows the sequential determination of DMS, DMSP, and DMSO in natural waters and is suitable for field work, so it should be very useful in studies of dimethyl sulfur biogeochemistry. Some examples of DMSO (along with DMS and DMSP) measurements in the Mediterranean Sea are presented.

Dioxins, furans and AHH-active PCB congeners in eggs of two gull species from the western Mediterranean.

Polychlorinated biphenyls, dibenzodioxins and dibenzofurans were analysed in eggs of a protected gull species, the Audouin's Gull (Larus audouinii) and compared to those of the Yellow-legged Gull (Larus cachinnans), both breeding in the Western Mediterranean (Ebro Delta and Medes Islands, respectively). Differences in concentrations as well as in congener profiles reflected differences in both habitat and diet of the two species. Levels of AHH-active PCB congeners were lower in Yellow-legged Gull (0.4-1.6 micrograms/g d.w) than in Audouin's Gull eggs (1.2-33.9 micrograms/g d.w.). These concentrations, expressed in international toxic equivalence factors (i-TEQ/g d.w.), were on average 24 times higher in the Audouin's gull. I-TEQ levels due to dioxins were also higher in this species by a factor of ca. 7. I-TEQ levels related to PCBs resulted 90-230 times higher than those of dioxins and furans. Thus, AHH-inducing PCBs might represent even higher toxicological hazards than dioxins and furans to some populations of seabirds. The necessity of assessing the impact of these compounds in rare and protected species is pointed out.

The use of biomarkers for assessing the effects of organic pollution in mussels.

Wild mussels were collected from two stations with different pollution loads. Soft tissues were analyzed for their aromatic hydrocarbon and polychlorinated biphenyl content. Mixed function oxidase (MFO) system components and antioxidant defenses (catalase, superoxide dismutase and glutathione peroxidase) were determined in digestive gland microsomal and cytosolic fractions, respectively, and the magnitude of biochemical responses related with pollutant tissue levels. Results showed that significant differences existed in hydrocarbon content between mussels from the two stations, while a smaller difference in the biological response was detected.

Sources and seasonal variability of mutagenic agents in the Barcelona City aerosol.

Organic extracts (dichloromethane) isolated from airborne particulate matter, collected in two sampling sites located in the Barcelona City, were mutagenic in the Salmonella typhimurium (TA98 +/-S9) bioassay. The highest direct-acting mutagenicity (69-78 rev m-3) was detected during fall and spring, which corresponds to the highest levels of mutagenic nitroarenes (248 to 350 pg m-3). On the other hand, the highest level of indirect-acting mutagenicity was obtained in summer, paralleling with the highest concentrations of polycyclic aromatic ketones and polycyclic aromatic quinones. Furthermore, the sources of PAH in the urban particulate matter were estimated from the ratio of the less reactive components (i.e. benzofluranthenes/benzo[e]pyrene, indeno[1,2,3-cd]pyrene/benzo[ghi]perylene, methylphenantherenes/phenanthrene) and reflected a predominance of pyrolytic mobile sources (i.e. vehicular emissions). Nevertheless, a contribution of stationary sources in winter was also apparent. Finally, the seasonal variability of polycyclic aromatic ketones, quinones, aromatic lactones and aldehydes reflected a major contribution of the atmospheric transformation processes from related PAH rather than a direct emission from combustion sources.