High-resolution multivariate analysis of the hydrochemical signature of water corridors in the upper Río de la Plata estuary, Argentina.

Major world river-estuaries integrate the hydrochemical characteristics of the basin with specific signatures which are maintained until complete mixing or discharge to the sea. The chemical signature of distinct water masses and the anthropogenic impact in the Upper Río de la Plata estuary (RLP) were evaluated by high-resolution continuous monitoring (i.e. every 200 m) of conductivity, turbidity, pH, temperature, chlorophyll a and coloured dissolved organic matter (CDOM), discrete analysis of suspended particulate matter (SPM) grain size composition combined with multivariate analysis (K-means clustering, Principal Component Analysis). The characteristic signatures of main RLP tributaries such as the Paraná River, yielding higher conductivity, CDOM, turbidity and coarser SPM, and the Uruguay River, with clearer, more eutrophic waters enriched in very fine SPM, were maintained 60 km seaward from the estuary head. Across the river, three water corridors with distinct signatures and variable widths (3-20 km) were identified reflecting the transition from Paraná to Uruguay River waters. Multivariate techniques also allowed the identification of a polluted coastal corridor (higher conductivity and CDOM and lower turbidity) impacted by wastewater discharges from the metropolitan Buenos Aires and La Plata cities extending 100 km seaward. The combined strategy of high-resolution monitoring, discrete sampling and multivariate techniques was a useful tool to identify water masses, corridors of flow and anthropogenic sources in a heavily urbanized estuary.

Fatty acid alterations in the detritivorous Prochilodus lineatus promoted by opportunistic feeding on sewage discharges in the Río de la Plata estuary.

Muscle fatty acid profiles and PCB contents of the detritivorous species Prochilodus lineatus and its diet (stomach contents, settling particles and sediments) were analysed from reference and polluted areas of the Paraná-Rio de la Plata basin, to evaluate the alterations produced by opportunistic feeding on sewage discharges. Overall muscle fatty acid composition was dominated by saturated and monounsaturated 16 and 18 carbon (18 C-FA) components with reduced long-chain polyunsaturated fatty acids (LC-PUFA). Compared to sediments, settling particles and stomach contents were enriched in lipids and had a similar fatty acid composition. Opportunistic feeding on sewage detritus at Buenos Aires resulted in enhanced PCB and triglyceride accumulation, with higher proportions of 18 C-FA and lower proportions of 16:1 and LC-PUFA compared to fish from northern pristine reaches of the basin. Mid-Paraná showed intermediate values reflecting mixing of the North stock with migrating Buenos Aires P. lineatus identified by their lipid and contaminant profile. According to multivariate analyses, this geographical variation of fatty acid composition was strongly influenced by PCB concentration. Prochilodus lineatus assimilates the energy subsidy of sewage inputs through enhanced lipogenesis with dominant 18 C-FA and significant amounts of valuable LC-PUFA. This lipid alteration facilitates the bioaccumulation of PCBs which in turn may reinforce the adipogenic effect of sewage feeding.

Airborne PCDD/F profiles in rural and urban areas of Buenos Aires Province, Argentina.

Passive air samplers were deployed in 18 rural and urban locations in the densely populated Buenos Aires district to investigate airborne polychlorinated dibenzo-p-dioxin and polychlorinated-dibenzofuran (PCDD/Fs) profiles, sources and spatial patterns. Atmospheric concentrations reported as total toxic equivalents (TEQs), 2378-substituted (∑17PCDD/F) and 4-8 homologous groups (∑4-8PCDD/F) were highly variable and significantly correlated to urban scale. The rural average (3.0±2.7fgTEQm-3) was thirty times less than metropolitan values (90±51fgTEQm-3), with urban cluster (5.4±4.0fgTEQm-3) and urbanized area (33±50fgTEQm-3) in an intermediate position. A rural outlier exhibited the highest TEQ values (295-296fgTEQm-3) suggesting a local source. Principal component analyses (PCA) performed for ∑17PCDD/F and ∑4-8PCDD/F to identify source contributions showed more significant results for homologue groups compared to 17 congeners (83 and 45% of total variability explained, respectively) pointing to dominant diesel emissions enriched in TeCDF in rural areas, and open burning and industrial sources characterized by TeCDD, PeCDD contributing most in urbanized and metropolitan areas. Homologue group PCA also performed better clustering samples according to sources and TEQ concentrations. The PCDD/Fs profile of the rural outlier dominated by HxCDF and HpCDD/F showed a typical municipal incineration signature confirming the presence of local source.

Bioaccumulation of dioxin-like PCBs and PBDEs by detritus-feeding fish in the Rio de la Plata estuary, Argentina.

A comparative analysis of bioaccumulation behavior of dioxin-like polychlorinated biphenyls (dlPCBs) and polybrominated biphenyl ethers (PBDEs) was conducted involving simultaneous measurements in settling particles and a detritivorous fish (Sabalo, Prochilodus linneatus) collected in the sewage impacted Buenos Aires coastal area. Focalization of dlPCBs and PBDEs along the detritus food chain is reflected by a 30-40-fold increase of dry weight PBDE and dlPCB concentrations from settling particles to fish (1.8 ± 1.0 to 58 ± 31 and 6.8 ± 3.9 to 281 ± 155 ng g(-1) dry weight (dw), respectively). In this transference, dlPCB congeners presented more conservative patterns than those of PBDEs, basically due to debromination of BDE 99 and 153 to BDE 47 in fish. Lipid/organic carbon-based biota-sediment accumulation factors (BSAFs) ranged between 5 and 20 (7.3 ± 3.0 and 16 ± 8.0 for PBDEs and dlPCBs). Congener-specific BSAF of dlPCBs suggested a lower bioavailability of more planar non-ortho-PCB versus mono-ortho-PCB suggesting higher affinity to organic matter. BSAFs of PBDEs differed markedly among bromine homolog groups, supporting the biotransformation-formation from higher brominated to lighter congeners. The log BSAFs-log K OW relationship of dlPCBs and PBDEs presented a parabolic pattern maximizing at log K OW 6-7, but PBDE curve differs reflecting biotransformation processes.

Behavior of dioxin like PCBs and PBDEs during early diagenesis of organic matter in settling material and bottom sediments from the sewage impacted Buenos Aires' coastal area, Argentina.

Settling particles (SPs) and sediments collected in the Buenos Aires sewer area were analyzed for dioxin like polychlorinated biphenyls (dlPCBs) and polybrominated diphenyl ethers (PBDEs) to follow early diagenetic changes during transport and deposition of organic matter. SP showed a temporal trend of higher total organic carbon (TOC) and fresher dlPCBs and PBDEs signatures during warm-rainy months related to more efficient washout of residues. TOC-normalized sediment trap concentrations suggest a diagenetic magnification of dlPCBs during cold-dry months due to enhanced decomposition of TOC, whereas most labile PBDEs appear to follow TOC decay. The diagenetic behavior of individual congeners along seasonal changes (cold/warm) and during deposition (bottom sediment/SP) shows the selective preservation of heavier, more persistent congeners with a positive relationship with sediment half-lives. The 3-4 times diagenetic magnification of heavier congeners observed in bottom sediments would be a prevailing long-term pathway for dlPCBs and PBDEs bioaccumulation in detritus feeding organisms.

Migratory behaviour of a dominant detritivorous fish Prochilodus lineatus evaluated by multivariate biochemical and pollutant data.

This paper studies the migration pathways and ranges of a dominant detritivorous fish Prochilodus lineatus along pollution gradients in the Río de la Plata basin using multivariate analysis of biochemical and pollutant data. Biochemical composition (water, ash, lipids, proteins, carbohydrates, neutral lipids classes and fatty acids), aliphatic hydrocarbons (ALI), polychlorinated biphenyls (PCB), linear alkylbenzenes (LAB) and organochlorine pesticides (OClP) were determined in muscle samples of P. lineatus collected in Metropolitan Buenos Aires, the lower Paraná River (Paraná: 200-1000 km from Buenos Aires) and the middle Paraná and Paraguay Rivers (North: 1000-1400 km north). Biochemical variables and pollutants exhibited large variability [Lipids 1.1-89.5% wet mass; ALI 1.4-413; LABs not detectable (n.d.)-115.2; PCBs n.d.-27.9; OClPs n.d.-11.8 µg g(-1) dry mass], due to the contrast of Buenos Aires with North fish. Fish from Buenos Aires were fatty (lipids 24.7 ± 12.3% wet mass), enriched in 18 carbon fatty acids and severely contaminated (ALI 152.4 ± 72.3; LABs 65.1 ± 26.4; PCBs 15.2 ± 6.8; OClPs 1.8 ± 1.9 µg g(-1) dry mass mean ±S.D.). In contrast, fish from North were lean (4.1 ± 3.1% wet mass), enriched in long chain (>20 carbons) polyunsaturated fatty acids, with average one to two orders of magnitude lower pollutant levels (ALI 41.2 ± 51.9; PCBs 2.2 ± 3.5; LABs 8.8 ± 21.1; OClPs 0.67 ± 0.75 µg g(-1) dry mass mean ±S.D.). Paraná showed intermediate values in all variables, denoting the mixing of different fish stocks. Based on principal component analysis, 14 outliers from 60 North and Paraná samples (representing 26 from 108 individual fish) were identified as pertaining to the Buenos Aires group with very similar lipid and pollutant levels. Data suggest that P. lineatus migrates a highly variable distance, exceeding 800-1000 km in multiple spatial and temporal overlapping ranges. Chemometric analysis of biochemical and pollutant data effectively discriminates fish according to the chemical signature acquired by detritus feeding in pristine and contaminated urban or industrial areas.

Risk ranking of multiple-POPs in detritivorous fish from the Río de la Plata.

To evaluate the bioaccumulation and the risk associated to consumption of lipid-rich detritivorous fish, a comprehensive set of organic pollutants (n=213) including polychlorinated biphenyls (PCBs), dioxin like PCBs (dlPCBs), chlorinated pesticides (CHLPs), chlorobenzenes (CBzs), polybrominated diphenyl ethers (PBDEs), polychlorinated dibenzo dioxins and furans (PCDD/F), resolved (ALI) and unresolved aliphatic hydrocarbons (UCM) and linear alkyl benzenes (LABs) were analyzed in Sábalo fish (Prochilodus lineatus) collected in the polluted Metropolitan Buenos Aires coast and in migrating specimens. Fatty fish muscles (lipids: 74±9.3% dry weight) contained homogeneous (24-51% variability) and very high-concentrations of organic pollutants ranging from 60 to 1,300 µg g(-1) fresh weight (fw) ALI+UCM; 10-40 µg g(-1) fw LABs and PCBs; 0.1-1 µg g(-1) fw dlPCBs, DDTs, chlordanes, CBzs and PBDEs; 0.01-0.1 µg g(-1) fw mirex, endosulfans, aldrin, dieldrin, endrin and 0.07-0.2 ng g(-1) PCDD/F. Total toxicity equivalents (TEQs) ranged from 60 to 395 pg g(-1) fw (34±17 and 213±124 pg g(-1) TEQs for PCDD/F and dlPCBs respectively). These are among the highest concentrations reported for fish and point out the remarkable ability of Sábalo to feed on anthropogenic organic-enriched particles and tolerate a high pollutant load. Contaminant signatures show partial alteration with still abundant lower molecular weight components indicating that fish feeds directly in the outfalls. Consumption limits based on reference doses ranged from 0.1 (PCBs) to >1,2000 g d(-1) (endosulfan) allowing a comprehensive risk-based ranking of contaminants in this long-range migrating, detritivorous fish.

Bioaccumulation of anthropogenic contaminants by detritivorous fish in the Río de la Plata estuary: 2-Polychlorinated biphenyls.

The temporal variability and bioaccumulation dynamics of individual PCBs were studied in a detritivorous fish (Sábalo: Prochilodus lineatus) collected from 1999 to 2005 in the polluted Buenos Aires coastal area. Fish muscles contain high concentrations of total PCBs (11+/-7.2, 4.6+/-3.4 or 19+/-13 microg g(-1), dry, fresh and lipid weight, respectively) reflecting chronic bioaccumulation from sewage-industrial particulates. On a temporal basis, lipid normalized PCBs concentrations peaked by the end of 2001-2002 coincident with the rainiest period over the last four decades and shortly after PCB prohibition in the country, reflecting massive discharges to the coastal ecosystem. PCB composition in fish muscles show a prevailing contribution of hexachlorobiphenyls (35+/-4.2%), followed by hepta (23+/-3.0%), penta (20+/-3.6%), tri-tetra (16+/-4.8%) and minor proportions of octa-decachlorobiphenyls (5.7+/-3.1%) similar to an Aroclor 1242-1254-1260 1:2:4 mixture. During 2001-2002 maxima fish showed an enrichment in tri-tetrachlorobiphenyls ( approximately 1242-1254-1260 1:1:1 mixture) denoting a fresher signature. Fish/settling material lipid-organic carbon accumulation factors (BSAFs: 2.4-46, average: 21+/-10) plotted against kow showed a parabolic trend (BSAFs=-0.38 log kow2 + 5.16 log kow -15.85; R2=0.46) maximizing at hexa, hepta and octachlorobiphenyl 203 with reduced bioaccumulation of a few hepta (170, 191) and most octa-decachlorobihenyls suggesting limited intestinal absorption.

Bioaccumulation of anthropogenic contaminants by detritivorous fish in the Río de la Plata estuary: 1-aliphatic hydrocarbons.

The temporal variability and bioaccumulation dynamics of C(12-25)n-alkanes, isoprenoids and unresolved aliphatic hydrocarbons (UCM) were studied in a detritivorous fish (Sábalo: Prochilodus lineatus) collected from 1999 to 2005 in the sewage impacted Buenos Aires coastal area. Fish muscles contain huge amounts of n-C(12-25) (165+/-93, 70+/-48 or 280+/-134 microg g(-1), dry, fresh and lipid weight, respectively) and UCM (931+/-560, 399+/-288 and 1,567+/-802 microg g(-1)) reflecting the chronic bioaccumulation of fossil fuels from sewage particulates. On a temporal basis, lipid normalized aliphatic concentrations peaked by the end of 2001-2002 during the rainiest period over the last four decades (1,750 vs. 1,083+/-4.6mm in 1999, 2004 and 2005), reflecting an enhanced exposition due to massive anthropogenic fluxes from Metropolitan Buenos Aires in wet years. The hydrocarbon composition in fish muscles is enriched in n-C(15-17) and isoprenoids relative to a fresh crude oil and settling particulates, with fresher signatures during the 2001-2002 maxima. Fish/settling material bioaccumulation factors (BAFs: 0.4-6.4 dry weight or 0.07-0.94 lipid-organic carbon) plotted against K(ow) showed a parabolic pattern maximizing at n-C(14-18) and isoprenoids. The optimal bioaccumulation window corresponds to highly hydrophobic (log K(ow): 7.2-9.9), intermediate-size C(14-18)n-alkanes and C(15-20) isoprenoids (MW: 198-282; length: 17.9 to 25.4A) with melting points ranging from -19.8 to 28 degrees C. The uptake efficiency is inversely correlated to melting points and increased from 75% for n-C(25) to above 90% for n-C(14-15) and isoprenoids.

Sources, vertical fluxes, and equivalent toxicity of aromatic hydrocarbons in coastal sediments of the Río de la Plata Estuary, Argentina.

Settling particles and bottom sediments collected at 1, 2.5, and 4 km off the metropolitan Buenos Aires coast in the Río de la Plata were analyzed to evaluate the sources and toxicity of resolved (PAHs) and unresolved (AROUCM) aromatic hydrocarbons. PAHs (0003-2.1 microg g(-1)) and AROUCM (0.01-78 microg g(-1)) presented the highest concentrations nearthe Buenos Aires port and sewer and decreasing values up- and downstream and along on- and offshore gradients. Sediment traps deployed in the Central area revealed large aromatic fluxes (1.3 +/- 1.5 and 31 +/- 47 mg m(-2) day(-1) for PAHs and AROUCM). The composition of sedimentary PAHs was dominated by uniformly distributed high molecular weight pyrogenic PAHs (53 +/- 11% fluoranthene, pyrene, and heavier PAHs), followed by diagenetically derived perylene more abundant in less polluted sites (29 +/- 15%) and lower molecular weight petrogenic PAHs (18 +/- 7.1% phenanthrene, anthracene, and methylated compounds), which covaried inversely with perylene. PAH diagnostic ratios indicated a stronger influence of petrogenic discharges close to the shore and the prevalence of combustion of fossil fuels and vehicle emissions over wood in offshore sediments. Sediment cores showed sustained hydrocarbon levels with decreasing proportion of petrogenic PAHs and relative enrichment of pyrogenic components and perylene down to 20-cm depth. PAH toxicity assessment by sediment quality guidelines (SQG) and dioxin-equivalent factors (PAH TEQ: 0.08-395 pg g(-1) dw) identified 1-2.5 km sediments close to the port and sewer as the most affected area. According to SQG, dibenz[a,h]anthracene and pyrene were the most critical PAHs, followed by benzo[a]pyrene, benz[a]anthracene, and chrysene. In contrast, PAH TEQs were dominated by indeno[1,2,3-cd]pyrene, benzo[k]fluoranthene, benzo[a]pyrene, perylene, and benz[a]anthracene which accounted for an average 86 +/- 5.7% of total TEQs.

Sources, vertical fluxes, and accumulation of aliphatic hydrocarbons in coastal sediments of the Río de la Plata Estuary, Argentina.

Settling particles and underlying sediments collected at 1, 2.5 and 4 km off the metropolitan Buenos Aires coast were analyzed to evaluate the sources and accumulation of resolved (RES), unresolved (UCM), and biomarker aliphatic hydrocarbons. Sedimentary aliphatic concentrations (RES 0.11-14 microg x g(-1); UCM 0.1-800 microg x g(-1)) included variability associated with north-south gradients and an exponential offshore reduction. Highest concentrations were registered close to Buenos Aires port and sewer, compared to cleaner northern stations and southward sites affected by a seaward residue transport. Sediment traps deployed in the sewer area revealed large hydrocarbon (38 and 319 mg x m(-2) x day(-1), RES and UCM) and total organic carbon fluxes (29 +/- 26 g x m(-2) x day(-1). The composition of RES and hopanes evaluated by principal component analysis indicated a consistent offshore gradient defined bythe relative contribution of lower vs higher molecular weight components. Distant sites showed decreasing proportions of petrogenic n-C(17-26) alkanes, isoprenoids, and C(20-27) terpanes and relative enrichment of n-C(27,29,31,33) terrestrial plant alkanes and C(31-33) homohopanes. Sediment hydrocarbon profiles showed an average 2-fold reduction down to 20 cm depth with preferential removal of lower molecular weight components and enrichment of n-C(23-35) alkanes and hopanes. Sediment inventories and trap depositional fluxes indicate the accumulation of 5800-9700 tons of aliphatic hydrocarbons in the top 0-5 cm sediments with a strong interfacial alteration and selective preservation of refractory components: n-C(13-22) (1.0%) < isoprenoids (3.2%) < n-C(23-35) (6.1%) < hopanes (47%) approximately UCM (50%), compared to intermediate stability of organic carbon (12%) and quantitative preservation of polychlorinated biphenyls (PCBs) (91%).

Vertical fluxes and accumulation of PCBs in coastal sediments of the Río de la Plata estuary, Argentina.

Settling particles and underlying sediments collected at 1, 2.5 and 4 km along offshore transects in the urbanized sector of the Río de la Plata were analyzed to evaluate the sources and accumulation of PCBs. Total PCB concentrations range from <0.1 to 100 ng g(-1) and include variability associated to North-South and offshore gradients reflecting the impact of coastal discharges. Highest concentrations were recorded in the industrialized Central area close to Buenos Aires (61+/-37 ng g(-1) at 1 km) relative to cleaner northern stations (3.6+/-2.2 ng g(-1)) and southward sites (37+/-2.8 ng g(-1)), affected by transport of particulate PCBs by coastal currents. Sediment traps deployed in the Central area revealed large depositional fluxes of total matter (361+/-124 gm(-2)day(-1)) and PCBs (26+/-19 microg m(-2)day(-1)) and high sedimentation rates (5.0+/-1.7 cm yr(-1)). Uniform PCB concentrations (66-89 ng g(-1)) down to 20 cm in sediment cores suggest continued PCB discharges during the last 4 years. PCB composition was dominated by hexa (43+/-6.4%), hepta (23+/-5.1%) and pentachlorobiphenyls (21+/-5.5%) with lower proportions tri-tetra (7.4+/-5.4%) and higher chlorinated congeners (5.1+/-3.3%). A consistent weathering pattern with loss of 3-5 chlorobiphenyls and enrichment in higher chlorinated PCBs corresponding to a shift from a 1:1 to a 1:3 1254:1260 Aroclor mixture, was observed offshore. A principal component analysis performed with the relative contribution of PCB congener classes confirmed the offshore weathering pattern indicating that transformer oils containing Aroclor 1254-1260 are the most probable sources. Sediment inventories, sediment trap fluxes and Fugacity II calculations indicate an accumulation approximately 500-800 kg PCB in superficial sediments of this coastal environment.

Oil spill in the Rio de la Plata estuary, Argentina: 2-hydrocarbon disappearance rates in sediments and soils.

The 6-month assessment of the oil spill impact in the Rio de la Plata described in the preceding paper [Colombo, J.C., Barreda, A., Bilos, C., Cappelletti, N., Demichelis, S., Lombardi, P., Migoya, M.C., Skorupka, C., Suarez, G., 2004. Oil spill in the Rio de la Plata estuary, Argentina: 1 - biogeochemical assessment of waters, sediments, soils and biota. Environmental Pollution] was followed by a 13- and 42-month campaigns to evaluate the progress of hydrocarbon decay. Average sediment hydrocarbon concentrations in each sampling include high variability (85-260%) due to contrasting site conditions, but reflect a significant overall decrease after 3 years of the spill: 17 +/- 27, 18 +/- 39 to 0.54 +/- 1.4 microg g(-1) for aliphatics; 0.44 +/- 0.49, 0.99 +/- 1.6 to 0.04 +/- 0.03 microg g(-1) for aromatics at 6, 13 and 42 months, respectively. Average soil hydrocarbon levels are 100-1000 times higher and less variable (61-169%) than sediment values, but display a clear attenuation: 3678 +/- 2369, 1880 +/- 1141 to 6.0 +/- 10 microg g(-1) for aliphatics and 38 +/- 26, 49 +/- 32 to 0.06 +/- 0.04 microg g(-1) for aromatics. Hydrocarbon concentrations modeled to first-order rate equations yield average rate constants of total loss (biotic+abiotic) twice as higher in soils (k = 0.18-0.19 month(-1)) relative to sediments (0.08-0.10 month(-1)). Individual aliphatic rate constants decrease with increasing molecular weight from 0.21 +/- 0.07 month(-1) for isoprenoids and n-C27, similar to hopanes (0.10 +/- 0.05 month(-1)). Aromatics disappearance rates were more homogeneous with higher values for methylated relative to unsubstituted species (0.17 +/- 0.05 vs. 0.12 +/- 0.05 months(-1)). Continued hydrocarbon inputs, either from biogenic (algal n-C15,17; vascular plant n-C27,29) or combustion related sources (fluoranthene and pyrene), appear to contribute to reduced disappearance rate. According to the different loss rates, hydrocarbons showed clear compositional changes from 6-13 to 42 months. Aliphatics disappearance rates and compositional changes support an essentially microbiologically-mediated recovery of coastal sediments to pre-spill conditions in a 3-4 year period. The lower rates and more subtle compositional changes deduced for aromatic components, suggest a stronger incidence of physical removal processes.

Oil spill in the Rio de la Plata estuary, Argentina: 1. Biogeochemical assessment of waters, sediments, soils and biota.

Aliphatic (ALI) and aromatic (ARO) hydrocarbon concentrations, composition and sources were evaluated in waters, sediments, soils and biota to assess the impact of approximately 1000 tons of oil spilled in Rio de la Plata coastal waters. Total ALI levels ranged from 0.4-262 microg/l in waters, 0.01-87 microg/g in sediments, 5-39 microg/g in bivalves, 12-323 microg/g in macrophytes to 948-5187 microg/g in soils. ARO varied from non-detected 10 microg/l, 0.01-1.3 mug/g, 1.0-16 microg/g, 0.5-6.9 microg/g to 22-67 microg/g, respectively. Offshore (1, 5, 15 km) waters and sediments were little affected and contained low background hydrocarbon levels reflecting an effective wind-driven transport of the slick to the coast. Six months after the spill, coastal waters, sediments, soils and biota still presented very high levels exceeding baseline concentrations by 1-3 orders of magnitude. UCM/resolved aliphatic ratio showed a clear trend of increasing decay: coastal waters (3.3) < macrophytes (6.7) < soils (9.4) < offshore sediments (13) < coastal sediments (17) < clams (52). All environmental compartments consistently indicated that the most impacted area was the central sector close to Magdalena city, specially low-energy stream embouchures and bays which acted as efficient oil traps. The evaluation of hydrocarbon composition by principal component analysis indicated the predominance of biogenic (algae, vascular plant cuticular waxes), background anthropic, pyrogenic and diagenetic hydrocarbons, offshore and in non-impacted coastal sites. In contrast, polluted stations presented petrogenic signatures characterized by the abundance of isoprenoids, low molecular weight n-alkanes and methylated aromatics in different stages of alteration. The petrogenic/biogenic ratio ( n-C23) and petrogenic/pyrogenic relationship (methylated/unsubstitued PAH) discriminated the samples according to the different degree of impact. The following paper present the results of the study of the progress of hydrocarbon disappearance in sediments and soils 13 and 42 months after the spill.