Scenarios of temporal and spatial evolution of hexabromocyclododecane in the North Sea.

Spatial and temporal distribution of the flame retardant hexabromocyclododecane (HBCD) in the North Sea was examined for the period from 1995 to 2005 using a pollutant transport model FANTOM. Model calculations allow conclusions on relevant sinks and fluxes in and out of the North Sea and on the time needed to establish a steady state. Calculations were performed for two additional scenarios with different rates of primary degradation ranging from fast degrading to absolute persistency. Concentrations calculated in the scenarios with degradation are in line with the monitoring data available for HBCD. Concentrations calculated in the "persistent" scenario disagree with measured data. According to our model calculations, steady state is established within months for the water and the top layer sediment with no evidence for a temporal trend, except for the "persistent" scenario, in which concentrations increase continuously in the southeastern part of the North Sea, where hydrographic and circulation characteristics produce areas of converging currents. Our model study enables a better understanding of the fate of HBCD in the North Sea, its potential for transport and overall elimination. We discuss these findings in the light of different concerns for PBT substances.

Biodegradation and product identification of [14C]hexabromocyclododecane in wastewater sludge and freshwater aquatic sediment.

In a previous study the biodegradation of hexabromocyclododecane (HBCD) was reported to occur under realistic environmental concentrations in soils and freshwater aquatic sediments with biotransformation half-lives ranging from approximately 2 days to 2 months. In this study we extend our knowledge as to the environmental behavior of HBCD with respect to the fate of the three major diastereomers of HBCD (alpha, beta, and gamma) as well as to the identification of major intermediate metabolites formed during degradation. Substantial biological transformation of the alpha-, beta-, and gamma-[14C]HBCD diastereomers was observed in wastewater (i.e., digester) sludge and in freshwater aquatic sediment microcosms prepared under aerobic and anaerobic conditions. Concomitant with the loss of [14C]HBCD in these matrixes there was a concurrent production of three [14C]products. Using a combination of high performance liquid chromatography atmospheric pressure photoionization mass spectrometry and gas chromatography electron impact ionization mass spectrometry these metabolites were identified as tetrabromocyclododecene, dibromocyclododecadiene, and cyclododecatriene. We propose that HBCD is sequentially debrominated via dihaloelimination where at each step there is the loss of two bromines from vicinal carbons with the subsequent formation of a double bond between the adjacent carbon atoms. These results demonstrate that microorganisms naturally occurring in aquatic sediments and anaerobic digester sludge mediate complete debromination of HBCD.

Acute toxicity of triorganotin compounds: different specific effects on the energy metabolism and role of pH.

Triorganotin compounds exhibit several modes of toxic action on the energy metabolism in energy-transducing membranes. The inhibition of the adenosine triphosphate (ATP) synthase and the hydroxide/chloride-antiport have been extensively investigated, but debate still exists on whether further mechanisms are relevant. In this work, two possible further effects have been investigated: inhibition of the bc1 complex and the hydroxide uniport, and in addition, the overall inhibition of the ATP synthesis was investigated in chromatophores of the photosynthetic purple bacterium Rhodobacter sphaeroides at pH = 7.5 and pH = 6.1. Experimental conditions were chosen in order to exclude the hydroxide/anion antiport as a possible effect. Inhibition of the cytochromes bc1 complex was detected, but at such high concentrations that it is not relevant for acute toxicity. Tributyltin was found to induce a decrease of the membrane potential, which can be attributed to a hydroxide uniport, whereas for triphenyltin no such activity was observed. For both compounds, inhibition of the ATP synthesis was higher at pH = 6.1 than at pH = 7.5. Also the hydroxide uniport activity of tributyltin was higher at lower pH. The contribution of the hydroxide uniport of tributyltin to the overall inhibition of the ATP synthesis cannot be quantified; however, hydroxide uniport occurred in the same concentration range as inhibition of the ATP synthesis. For triphenyltin, inhibition of the ATP synthesis can be attributed to the inhibition of the ATP synthase. It was concluded that chromatophores of R. sphaeroides are a useful system to discriminate various effects of toxicants on the energy metabolism of a cell.