Polybromattujen difenyylieettereiden (PBDE) anaerobinen brominpoisto sedimentissä

In reductive dehalogenation, halogenated compounds act as electron acceptors in respiration or cometabolic reactions. The halogen atom is removed and usually replaced with hydrogen. Polybrominated diphenyl ethers (PBDEs) are persistent and toxic compounds, which have been extensively used as flame retardants. Even after bans and use restrictions, they are released to the environment from products manufactured earlier. PBDEs have been found ubiquitously in the environment. In anaerobic conditions like in sediments, they can be degraded through reductive dehalogenation. While remediating contaminated sediments, knowledge is needed about factors affecting the degradation of PBDEs. In the present work, anaerobic debromination of two PBDEs, BDE-47 and BDE-209 in sediment was investigated in microcosms. Sediment samples were taken from the estuary of the Kymijoki River from the Baltic, and from two sites in Lake Kernaalanjärvi, one representing clean and the other contaminated sediment. In addition to sampling site, the effect of incubation temperature on the degradation rate and products was investigated with different treatments, and possible abiotic degradation was examined with autoclaved controls. The samples were analyzed with gas chromatograph with electron capture detector (GC-µECD). The amounts of Dehalococcoides and total bacteria as 16S rRNA gene copies were determined with qPCR. Hypotheses were that debromination is faster in contaminated sediments, in warmer temperature, and in the microcosms with more bacteria of the genus Dehalococcoides. The half-time of BDE-47 varied from 173 to 7701 weeks, and that of BDE-209 from 28 to 173 weeks. The debromination rate could not be explained with sampling sites or incubation temperature, but the degradation of BDE-47 was significantly slower in autoclaved microcosms. In the microcosms where BDE-47 was removed most, the main debromination product was BDE-8. In the microcosms with sediment from the clean site of Lake Kernaalanjärvi, the amount of BDE-47 did not decrease. Obviously, bacteria capable of degrading it are not abundant in sites with little or no previous contamination with organohalogens. The removal of BDE-209 in autoclaved microcosms is probably explained with abiotic degradation or adsorption so that the compound is not extractable. At the end of incubation, there were more total bacteria in the microcosms with BDE-47 than those with BDE-209. The proportion of Dehalococcoides was greater in the microcosms with BDE-209, those incubated in room temperature, and those not autoclaved. Debromination was faster in the microcosms with more total bacteria in the beginning or Dehalococcoides at the end. BDE-47 proved to be more persistent than in the literature reviewed. The hypotheses about the effect of the incubation temperature and the contamination of the sediment did not reach statistical significance, but the importance of Dehalococcoides for debromination was established according to the hypothesis.