Distribution and source apportionment of hydrocarbons in sediments of oil-producing continental margin: a fuzzy logic approach.

Investigation were carried out targeting distribution and source apportioning of hydrocarbons in surface sediments from shallow to deep waters in the Campos Basin, one of the most important oil-producing provinces in Brazil. The observed levels of aliphatic (≤ 124 µg g-1) and polycyclic aromatic hydrocarbons (PAHs ≤ 599 ng g-1) are lower than those considered relevant for environmental risk to the benthic habitats. Higher median concentrations of aliphatic hydrocarbons (8.49 µg g-1) and PAHs (84.8 ng g-1) in the middle slope sediments (700-1000-m water depths) showed the influence of hydrodynamics upon hydrocarbon accumulation in the sediments. Diagnostic ratios and conventional statistical analysis applied to hydrocarbon data produced insufficient information on the contribution of different sources. These traditional approaches do not consider the potential changes affecting source assignment and therefore cannot deal with the uncertainties. The fuzzy logic applied as an alternative method for data treatment successfully incorporated the uncertainties in the differentiation between petrogenic and pyrolytic sources, including those due to degradation. Moreover, by using fuzzy logic, it was possible to identify that water circulation patterns, mass transport, deposition, and degradation processes are more relevant factors in determining hydrocarbon composition than source proximity.

Marine sponges as bioindicators of oil and combustion derived PAH in coastal waters.

The present study evaluates the potential of Hymeniacidon heliophila as bioindicator of PAH contamination. For this, concentration of 33 PAH was determined in organisms from sites with different contamination level including the heavily polluted Guanabara Bay, Rio de Janeiro, and less impacted coastal areas. PAH concentration and typology were determined in sponges collected from different depths and in two different seasons. The brown mussel broadly studied as bioindicator was also sampled from the same sites for comparison. Both species provided similar information on total PAH concentration which is related to site contamination level. Sponges, however, revealed slight tendency to accumulation of combustion-derived PAH in relation to petrogenic compounds. Differences in PAH typology between species may derive from the interspecific variation in particle size ingestion. Different hydrocarbon typologies were observed in sponges from dry and wet season and PAH concentration varied with depth. H. heliophila may be used as an alternative approach to investigate the presence and sources of PAH in estuarine areas.

Formation and identification of PAHs metabolites in marine organisms.

In this study, the development of the technique APCI(+) LC/MS/MS allowed the detection of phenanthrene, pyrene and metabolites of alkyl homologs in fish bile (in situ) and in urine of crabs. Laboratory experiments were carried out exposing crabs from an unpolluted mangrove (Barra de Guaratiba) to phenanthrene, and to the alkylated homologs 1-methyl phenanthrene and 2,6,9-trimethyl phenanthrene. Urine samples were collected at 0, 24, 48, 72, and 96 h. Fishes were captured from strategic sites from Guanabara Bay. Hydroxylated metabolites of phenanthrene, epoxides, orthoquinone and glucoside conjugates were identified in both samples. The method APCI(+) LC/MS/MS showed to be effective in a preliminary assessment of phenanthrene metabolite formation, although the low concentrations of 1-methyl phenanthene and 2,6,9-trimethyl phenanthrene did not allow a systematic evaluation of data. The method, however, proved to be excellent tool for studies of PAHs metabolites due to the high selectivity, sensitivity and separation attained.

Hydrocarbons in sediments of a chronically contaminated bay: the challenge of source assignment.

Aliphatic hydrocarbons and 39 PAH (parental and alkylated homologs) determined in ca. 100 sediment samples from the Guanabara Bay, Rio de Janeiro, were evaluated for source discrimination using new approaches. Concentrations of total PAH were in the range of 96-135,000 µg kg(-1) similar to other coastal urbanized embayment. Traditional diagnostic ratios were not as efficient PAH source indicators, e.g. biomass combustion was assigned as the major source of the pyrolytic PAH although the hydrographic basin is highly industrialized and urbanized. It is proved petrogenic imprint cannot be detected if only the 16 USEPA PAH are determined. The high production in the eutrophic system is not apparent in the aliphatic fraction dominated by land derived n-alkanes due to the effectiveness of microbial degradation. The present work demonstrates the complexity of hydrocarbon forensics when applied to chronically contaminated environments.

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

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

Biomarkers of PAHs exposure in crabs Ucides cordatus: laboratory assay and field study.

Pyrene metabolites in urine and micronucleus in haemocytes of crabs (Ucides cordatus) were tested as biomarkers of exposure to oil derived PAHs in mangrove sediments. The goal was to verify how well pyrene metabolites in urine represent levels of oil contamination in mangroves and whether the micronuclei assay indicates exposure. For this, bioassays were performed using crabs from clean and contaminated areas, and field studies were conducted in four mangroves. Results of the bioassay show that U. cordatus assimilates, metabolises, and excretes pyrene in urine as pyrene-1-glucoside, pyrene-sulphate and pyrene-conjugate. OH-pyrene-sulphate was the major metabolite produced/excreted over 120 h of observation by crabs from the clean mangrove. The production/excretion of pyrene-1-glucoside in this case increased linearly with time at a rate of 2.3 x 10(-10)mol L(-1)day(-1). The number of micronuclei in haemocytes also increased with the time after pyrene inoculation, indicating that exposure to pyrene triggers genotoxic and mutagenic response. In crabs from a heavily oil-contaminated mangrove pyrene-1-glucoside was the major metabolite, an indication that production/excretion of a certain metabolite varies depending on adaptation of the animal to the environment. A highly significant correlation was found between the concentration of pyrene metabolites in urine of field crabs expressed as OH-pyrene equivalents and the sum of 38 PAHs determined in hepatopancreas/sediments (r=0.825, n=23, p<0.05). The response of these crabs to the micronuclei assay was not significantly related to concentration of individual or total PAHs. Nevertheless, metabolite results prove U. cordatus as excellent bioindicator for evaluating environmental quality in mangrove areas as related to PAHs and oil contamination.

Stramonita haemastoma as a bioindicator for organotin contamination in coastal environments.

Stramonita haemastoma was investigated as a suitable bioindicator of TBT and TPhT contamination in the tropical Atlantic Ocean by: 1. Imposex induction in healthy females after inoculation with TBT and TPhT in the laboratory; and 2. Determining incidence of imposex in S. haemastoma collected from areas with various levels of tributyltin (TBT) and triphenyltin (TPhT) and determining the concentrations of these chemical in its tissues and that of its prey, the mussell Perna pernas. Imposex intensities and organotin concentrations in tissues showed good correlation, indicating S. haemastoma as a reliable bioindicator of TBT and TPhT contamination in coastal waters. Body burden threshold of TBT and TPhT for imposex induction was estimated to be 10-20 ng g(-1).