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.

Optimization and comparison of HPLC and RRLC conditions for the analysis of carbonyl-DNPH derivatives.

Analytical conditions for the analysis of 15 carbonyl-DNPH derivatives were optimized and compared by high performance liquid chromatography (HPLC) and rapid resolution liquid chromatography (RRLC). Binary, ternary and quaternary mixtures of acetonitrile, isopropanol, methanol, tetrahydrofuran and water were evaluated under RRLC conditions employing a Zorbax Eclipse Plus C18 (50 mm x 4.6 mm x 1.8 microm) column and a Zorbax Eclipse Plus C18 (50 mm x 2.1 mm x 1.8 microm) column. The optimized conditions obtained employing the two RRLC columns were compared with those obtained using a Supelcosil C18 (250 mm x 4.6 mm x 5 microm; Supelco) that is designed for HPLC separation of DNPH derivatives. Chromatograms run with a Zorbax Eclipse Plus C18 (50 mm x 2.1 mm x 1.8 microm) column and a mobile phase composed of isopropanol, methanol, tetrahydrofuran and water led to the best separation conditions considering reduced analysis time (approximately 6 min per run), solvent consumption rate (approximately 2 mL per run) and resolution of propanone, acrolein and propionaldehyde hydrazones. Quantification limits and linear ranges were adequate for direct application of EPA TO-11 conditions in all sets of RRLC and HPLC conditions. The analytical method was applied in the determination of carbonyl compounds (CCs) in Niterói City, RJ, Brazil in samples that were collected during periods of 2h. Formaldehyde (8.22-9.78 ppbv) predominated in all periods followed by acetaldehyde (1.77-3.99ppbv) and propanone (1.89-3.26 ppbv). Heavy CCs such as butyraldehyde and benzaldehyde were also detected in most samples. Total CCs varied along the studied day. The obtained results showed that RRLC can be applied to CCs determination without any change in the conditions of sample preparation of the Method EPA TO-11.

Effect aeration on biodegradation of petroleum waste

Large amaounts of oily sludge are generated as residues by the oil industry, representing a real problem for refineries. This work studied the technical viability of treating oily aludge biologically, through stimulation of native microorganisms, at bench scale. Such microorganisms were able to grow in a medium containing oily sludge as the only carbon and energy source. Two oily sludge concentrations were studied, 5(per cent) (v/v) and 10 (per cent) (v/v), with a C:N ratio of 100:1. Higher microbial populations were observed in the first case. Substrate inhibition and/or toxic effect took place in the second case. The importance of aeration on the microbial activity and on the biodegradation of the residue was ascertained. In terms of n-paraffins, pristane and phytane consumption, maximum global efficiency of the genus "Pseudomonas sp." predominated. Two yeast species were also identified and two filamentous fungi were isolated.