Bioaccumulation Study of Produced Water Discharges from Southeastern Brazilian Offshore Petroleum Industry Using Feral Fishes.

The main effluent of oil and gas production is the discharge of produced water (PW). Despite the potential environmental impact, the structure of oil and gas platforms can act as artificial reefs. Two species of fish, Caranx crysos and Tylosurus acus, were captured under two discharging platforms at Campos Basin, P19 and P40. A nondischarging platform, P25, was taken as reference. The highest median concentration of PAH in muscle tissue was observed for C. Crysos at P40 (219.38 ng g-1) followed by P19 (68.26 ng g-1). For T. acus, the highest median concentrations were 40.07 and 42.21 ng g-1 from P19 and P40 respectively. P25 presented the smallest recorded concentrations. The results of PAH in the muscle tissue of C. crysos enabled to distinguish the platforms with PW discharge from the platform without discharge. Trace elements concentrations reflected the background levels and were not influenced by the PW release.

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.

Validation of Ucides cordatus as a bioindicator of oil contamination and bioavailability in mangroves by evaluating sediment and crab PAH records.

This study is aimed at verifying the relevance of Ucides cordatus as a bioindicator of oil contamination and PAH bioavailability in mangrove sediments. For this, crabs and sediment cores were sampled from five mangroves, including an area suspected of contamination derived from an MF380 oil spillage, and analyzed for the 16 PAH in the USEPA priority list as well as for the five series of alkylated homologues. Concentrations in sediments varied from 35 microg kg-1 in the lower core layer of the control area to 33,000 microg kg-1 in the upper layer of the most contaminated area. Total PAH contents in crabs varied from 206 to 62,000 microg kg-1 and were closely correlated to that in sediments. In general, individual PAH profiles in both matrices were in good agreement. Phenanthrenes, however, were more predominant in crabs making up to 30-46% of the Total PAH. Accumulation factors found in the range of 0.7 to 35 were highly variable even after normalizing concentrations for organic carbon and lipid content. Survival in highly contaminated environment and reliable record of environmental contamination in the tissue provide evidence that U. cordatus is an excellent bioindicator for oil in mangroves.

Monitoring of polycyclic aromatic hydrocarbons in a produced water disposal area in the Potiguar Basin, Brazilian equatorial margin.

The Potiguar Basin has oil and gas production fields offshore and onshore. All treated produced water (PW) from these fields is discharged through submarine outfalls. Although polycyclic aromatic hydrocarbons (PAHs) are minor constituents of PW, their input into the marine ecosystem is environmentally critical due to potential ecological hazards. A 2-year monitoring program was conducted in the vicinity of the outfalls to evaluate PAH bioaccumulation in marine life from PW discharges. The study was performed using transplanted bivalves Crassostrea brasiliana and semipermeable membrane devices (SPMDs) to measure PAH concentrations via bioaccumulation and in seawater. The bioaccumulation of PAH in transplanted bivalves reached up to 1105 ng g(-1) in the vicinity of the monitored outfall. Significantly lower PAH concentrations were found in the reference area in comparison to the studied area around the outfalls. Time-integrated PAH concentrations in seawater ranged from 38 to 0.3 ng L(-1) near the outfalls and from 10 ng L(-1) to not detected in the reference area. Both measurement techniques were found to be effective for determining a gradient of descending PAH concentrations from the outfalls. In addition, this study also evaluated the bioavailability of PAH for local marine biota and provided information about the influence of PW discharges on the water quality of marine ecosystems.

Measurements of labile Cd, Cu, Ni, Pb, and Zn levels at a northeastern Brazilian coastal area under the influence of oil production with diffusive gradients in thin films technique (DGT).

In this work, the ability of the diffusive gradients in thin films technique (DGT) was evaluated for monitoring the concentrations, and estimating the availability, of metals at a northeastern Brazilian coastal area under the influence of oil production. Three sites with an average distance between 0m (EM-1), 100 m (EM-2), and 1,000 m (EM-3) of a submarine outfall-I (Guamaré-RN, Brazil) and another site (GA-1) with an average distance of 12,000 m east of Outfall I, near the city of Galinhos, were studied. DGT units were deployed at the same sites in three campaigns from July, 2010 to June, 2011. Effects on the accuracy of analytical results regarding the deployment time, gel porosity, and thickness were evaluated. There was no difference between the measurements obtained with two sets of DGT devices, those assembled with open or restrictive pore gel, respectively, showing that organic metallic species are not present near the submarine outlet. After 21 day deployments in a region (near Submarine Outfall I) that receives produced waters that have been treated, there was evidence of biofilm formation on DGT membranes. However, it was demonstrated that the biofilm interference with DGT measurements was negligible. Data found in this work show that total concentrations of Cd, Cu, Pb, Ni, and Zn in seawater samples collected at sites GA-1 and EM-1 in two campaigns were below 0.33, 1.67, 0.47, 0.70, 2.86 ng mL(-1) respectively. For the first time, labile levels of Cd, Cu, Pb, Ni, and Zn in an area under the influence of oil production were determined. DGT measurements allowed the verification of the effects of temporal variation on levels of Zn and Ni. There were no effects of spatial variations on levels of Cd, Cu, Ni, Pb, and Zn at the four studied sites, suggesting no contamination of these metals at the northeastern Brazilian coastal area investigated in this work.

Urinary PAH metabolites as biomarkers of exposure in aquatic environments.

While immunoassays have been extensively applied to evaluate environmental contamination, to date they have rarely been used for the analysis of biological fluids outside of human medicine. These media are important because pollutants such as polycyclic aromatic hydrocarbons (PAHs) and their metabolites become concentrated in tissues, body fluids, and excreta, thereby offering a measure of exposure to biologically available contaminants. Such analyses also provide a nondestructive tool for monitoring exposure. Crabs (Carcinus maenas) were exposed to phenanthrene and pyrene (separately) at concentrations ranging from 0 to 200 microg L(-1). After 48 h, urine samples were taken and analyzed by immunoassay and UV-fluorescence spectrophotometry. Urinary levels (calibrated against hydroxylated metabolites) proved to be dose dependent for both compounds, and good agreementwas demonstrated between the immunoassay and the fluorescence techniques. The cross reactivity of the immunochemical technique (ELISA) for pyrene and hydroxy-metabolites was lower than for phenanthrene. HPLC analyses demonstrated that urine from the crabs exposed to pyrene contained mainly conjugate PAH metabolites whose concentrations (the sum of the four main pyrene metabolites/conjugates) showed very good agreement with the ELISA (r2 > 0.94) and fluorescence (r2 > 0.91) data. Environmental samples were also analyzed by ELISA and UV-fluorescence, and both techniques detected PAH (mainly petrogenic) contamination in the urine samples from a polluted harbor. These data demonstrate the potential of urine analyses by ELISA and UV-fluorescence to measure exposure of crabs to PAH.