Method development and application to sediments for multi-residue analysis of organic contaminants using gas chromatography-tandem mass spectrometry.

A method for the determination of four classes of potentially toxic substances (PTSs) was developed and applied in marine sediments, including (i) polycyclic aromatic hydrocarbons (PAHs), (ii) polychlorinated biphenyls (PCBs), (iii) polybrominated diphenyl ethers (PBDEs), and (iv) organochlorinated pesticides (OCPs). The method is based on ultrasonic extraction with a mixture of dichloromethane:methanol (9:1 v/v) and gas chromatography coupled with tandem mass spectrometry analysis (GC-MS/MS) in multiple reaction monitoring (MRM) mode. A total of 89 compounds were identified using two precursor-product ion standards for each analyte. The method detection limit (MDL; 0.001-0.055 ng g-1 dw) and method quantification limit (MQL; 0.002-0.184 ng g-1 dw) are below the usual thresholds of pollution adopted by international sediment quality guidelines. The method proved to be selective, sensitive, accurate, and linear, with the advantage of reducing sample handling time and consumable expenses (solvent, adsorbents). The developed method was successfully applied to surface sediments of Sepetiba Bay, Rio de Janeiro State, Brazil. Total concentrations of PAH (29.20-209.5 ng g-1 dw), PCB (0.06-2.16 ng g-1 dw), OCP (0.03-0.33 ng g-1 dw), and PBDE (0.06-0.21 ng g-1 dw) represent a baseline for these compounds and revealed mild to low levels of contamination in comparison to other coastal bays in SE Brazil. By using the proposed method, we expect this preliminary dataset can be expanded and include other similar coastal systems from developing countries marked by scarcity of information about levels, risk assessment, and specific sediment quality guidelines encompassing multiple classes of regulated and emerging organic contaminants.

A novel approach for characterization of polycyclic aromatic hydrocarbon (PAH) pollution patterns in sediments from Guanabara Bay, Rio de Janeiro, Brazil.

A novel multivariate method based on principal component analysis of pre-processed sections of chromatograms is used to characterize the complex PAH pollution patterns in sediments from Guanabara Bay, Brazil. Five distinct sources of 3- to 6-ring PAHs could be revealed. The harbour is the most contaminated site in the bay, its plume stretches in a South West to North East direction and the chemical profile indicates mainly pyrogenic sources mixed with a fraction of high-molecular-weight petrogenic PAHs. Rio São João de Meriti is the second largest source of PAHs, and introduces mainly a fraction of low-molecular-weight petrogenic PAHs from the western region of Rio de Janeiro. The sites close to the ruptured pipeline at the Duque de Caxias Refinery show a distinctive pollution pattern indicating a heavy petroleum fraction. The method also led to the identification of new potential indicator ratios also involving coeluting peaks (e.g., triphenylene and chrysene).

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.