Because of the bioaccumulation of penta- and tetrapolybrominated diphenyl ether (PBDE) flame retardants in biota,the environmental biotransformation of decabromodiphenyl ether (BDE-209) is of interest. BDE-209 accounts for more than 80% by mass of PBDE production and is the dominant PBDE in sediments. Most sediments are anaerobic and reports of microbial reductive dehalogenation of hydrophobic persistent organohalogen pollutants are numerous. Reductive debromination of BDE-209 in the environment could provide a significant source of lesser-brominated PBDEs to biota. Moreover, a recent study showed that BDE-209 debrominates in sewage sludge, and another demonstrated that some halorespiring bacteria will debrominate BDE-209. To determine whether reductive debromination of BDE-209 occurs in sediments, parallel experiments were conducted using anaerobic sediment microcosms and a cosolvent-enhanced biomimetic system. In the biomimetic system, reductive debromination occurred at rates corresponding to bromine substitution levels with a BDE-209 half-life of only 18 s compared with a halflife of almost 60 days for 2,2',4,4'-tetrabromodiphenyl ether. In sediment, the measured debromination half-life of BDE-209 was well over a decade and was in good agreement with the predicted value obtained from the biomimetic experiment. Product congeners were predominantly double para-substituted. BDE-209 debrominated in sediment with a corresponding increase in nona-, octa-, hepta-, and hexa-PBDEs. Nine new PBDE congeners appeared in sediment from reductive debromination. Given the very large BDE-209 burden already in sediments globally, it is important to determine whether this transformation is a significant source of lesser-brominated PBDEs to the environment.
This article describes the application of capillary electrophoresis (CE) to the analysis of compounds relevant to the Chemical Weapons Convention (CWC). CE is an analytical technique that employs narrow‐bore, fused silica capillaries to perform high‐efficiency separations of analytes based on their mobilities in an electric field. In CE, analytes are dissolved in a buffer solution and placed in a capillary to which an electric field is applied. The analytes then migrate at a rate determined by their charge and size and are detected as they migrate past a detector. CE can analyze a broad range of compounds and is particularly applicable to the analysis of water‐soluble degradation products of scheduled compounds under the CWC. Compounds typically analyzed by CE include the hydrolysis products of nerve agents such as the alkylphosphonates and hydrolytic or oxidative products of the sulfur mustards such as thiodiglycol (TDG). The alkylphosphonates require the use of indirect ultraviolet (UV) detection or other detection methods as they do not possess a suitable UV chromophore. Degradation products of the sulfur mustards have been analyzed by micellar electrokinetic chromatography (MEKC) and direct UV detection. The ability of CE to analyze anionic, cationic, zwitterionic, and neutral CWC‐related compounds, whether they be chemical warfare (CW) degradation products or scheduled starting materials, without the requirement for elaborate sample processing or labeling procedures, is an important demonstration of the utility of CE for the analysis of CWC‐related compounds. CE can be an important screening method for rapid sample processing, and capillary electrophoresis coupled with mass spectrometry (CE‐MS) can provide further analysis for unambiguous identification.
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