Fish as biomonitors of polybrominated diphenyl ethers and hexabromocyclododecane in Czech aquatic ecosystems: pollution of the Elbe River basin.

BACKGROUND: Brominated flame retardants (BFRs)--polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD)--belong to the group of relatively "new" environmental contaminants. The occurrence of these compounds in the Czech aquatic ecosystem was for the first time documented within the 3-year monitoring study initiated in 2001. In 2002-2003 HBCD and the major PBDE congeners (28, 47, 49, 66, 85, 99, 100, 153, 154, and 183) were found in 136 freshwater fish samples collected from several sampling sites located at three Czech rivers (Vltava, Elbe, Tichá Orlice). Chub (Leuciscus cephalus), barbel (Barbus barbus), bream (Abramis brama), perch (Perca fluviatilis), and trout (Salmo trutta), representing the most common fish species, were examined by gas chromatography coupled with negative chemical ionization mass spectrometry. RESULTS: The presence of PBDE congeners and HBCD was detected in all analyzed samples (limits of detection for target analyts ranged from 0.015 to 0.1 ng/g lipid weight). Without exception the dominating congener was BDE-47. The most pronounced extent of fish contamination was found in the Vltava river at Klecany, downstream from the industrial agglomeration of Prague. As for fish species, the highest concentrations of PBDEs (sum of congeners) were measured in benthic species, represented by bream and barbel, up to 19.6 ng/g wet weight and 16.5 ng/g wet weight, respectively. The lowest accumulation occurred in predator fish (perch and trout). The highest levels of HBCD were detected in barbel from Srnojedy on the Elbe River (15.6 ng/g wet weight), downstream.

Fast isolation of hydrophobic organic environmental contaminants from exposed semipermeable membrane devices (SPMDs) prior to GC analysis.

Semipermeable membrane devices (SPMD) represent a passive sampling technology that is becoming widely used for monitoring of surface waters pollution. While "classic" procedures employ dialysis to recover target compounds from exposed SPMDs, in the present study analytes were isolated from cut membrane together with sequestering medium (triolein) using hexane as an extraction solvent. This approach allowed us to reduce the time needed for accomplishment of isolation step from 48 h to only 1 h. Automated gel permeation chromatography (GPC) clean-up is employed in the following step to separate triolein from analytes fraction. Musk compounds (MCs), polychlorinated biphenyls (PCBs), brominated flame retardants (BFRs) and several other persistent organochlorine compounds (OCs) were determined in the respective fraction by GC method employing selective detectors (MSD, ECD). As shown in a series of analyses of SPMDs deployed in various aquatic ecosystems, high recoveries and good repeatability of results together with a possibility to obtain the information on the pollution of sampling site at the day of sample arrival to laboratory make this newly implemented procedure an interesting alternative to time consuming dialysis.

Challenges of gas chromatography-high-resolution time-of-flight mass spectrometry for simultaneous analysis of polybrominated diphenyl ethers and other halogenated persistent organic pollutants in environmental samples.

The potential of a gas chromatographic method employing high-resolution time-of-flight (TOF) mass spectrometry was evaluated for detection of polybrominated diphenyl ethers (PBDEs) in the environmental matrices represented by fish and river sediment. Two ionisation techniques, viz. electron ionisation (EI) and negative ion chemical ionisation (NICI), the latter with methane as a reagent gas, were used in this study. While the instrumental lowest calibration levels (LCLs) obtained in El were in the range from 1 to 5 pg, their values ranged between 10 to 250 fg in NICI mode. This enhancement in detectability of target analytes enabled identification/quantification of even minor PBDE congeners, and consequently, improved characterisation of particular sample contamination patterns. In addition, this method allowed estimation of the PCB levels in examined samples. CB 153 was used as a contamination marker in this study.