Combined chemical and microbiological degradation of tetrachloroethene during the application of Carbo-Iron at a contaminated field site.

After the injection of Carbo-Iron® into an aquifer contaminated with tetrachloroethene (PCE), combined chemical and microbiological contaminant degradation processes were found in a long-term study of the field site in Lower Saxony (Germany). The applied composite material Carbo-Iron, which consists of colloidal activated carbon and embedded nanoscale zero-valent iron (ZVI) structures, functioned as intended: accumulating the pollutants and promoting their reductive dechlorination. Furthermore, the particles decreased the redox potential of the groundwater due to their reaction with oxygen and to the ZVI-corrosion-induced formation of molecular hydrogen up to 190 days after the injection, the latter promoting sulphate-reducing conditions. The emergence of cis-dichloroethene (cis-DCE), which was only found in trace quantities before the injection of Carbo-Iron, together with the presence of organisms related to Sulfospirillum multivorans, Desulfitobacterium spp. and Dehalococcoides mccartyi, indicate that Carbo-Iron is also able to support microbial degradation of PCE. However, cis-DCE did not accumulate in the present case study, although it is often observed at sites with active microbial dechlorination. The results of compound-specific isotope analysis in combination with pyrosequencing data suggested the oxidative degradation of cis-DCE by an organism related to Polaromonas sp. strain JS666. Consequently, the formation of the carcinogenic degradation intermediate vinyl chloride was circumvented. Overall, the moderate and slow change of environmental conditions mediated by Carbo-Iron not only supported organohalide-respiring bacteria, but also created the basis for a subsequent microbial oxidation step.

Dual Carbon-Bromine Stable Isotope Analysis Allows Distinguishing Transformation Pathways of Ethylene Dibromide.

The present study investigated dual carbon-bromine isotope fractionation of the common groundwater contaminant ethylene dibromide (EDB) during chemical and biological transformations, including aerobic and anaerobic biodegradation, alkaline hydrolysis, Fenton-like degradation, debromination by Zn(0) and reduced corrinoids. Significantly different correlation of carbon and bromine isotope fractionation (ΛC/Br) was observed not only for the processes following different transformation pathways, but also for abiotic and biotic processes with, the presumed, same formal chemical degradation mechanism. The studied processes resulted in a wide range of ΛC/Br values: ΛC/Br = 30.1 was observed for hydrolysis of EDB in alkaline solution; ΛC/Br between 4.2 and 5.3 were determined for dibromoelimination pathway with reduced corrinoids and Zn(0) particles; EDB biodegradation by Ancylobacter aquaticus and Sulfurospirillum multivorans resulted in ΛC/Br = 10.7 and 2.4, respectively; Fenton-like degradation resulted in carbon isotope fractionation only, leading to ΛC/Br ∞. Calculated carbon apparent kinetic isotope effects ((13)C-AKIE) fell with 1.005 to 1.035 within expected ranges according to the theoretical KIE, however, biotic transformations resulted in weaker carbon isotope effects than respective abiotic transformations. Relatively large bromine isotope effects with (81)Br-AKIE of 1.0012-1.002 and 1.0021-1.004 were observed for nucleophilic substitution and dibromoelimination, respectively, and reveal so far underestimated strong bromine isotope effects.

Origin of VC-only plumes from naturally enhanced dechlorination in a peat-rich hydrogeologic setting.

The occurrence of vinyl chloride (VC) is often a main concern at sites contaminated with chlorinated solvents due to its high degree of toxicity and carcinogenicity. VC occurrence in aquifers is most often related to the degradation of higher chlorinated ethenes or ethanes and it is generally detected in plumes along with parent contaminants. However, specific combination of stratigraphic, hydrogeologic and geochemical conditions can enhance the degradation of parents and lead to the formation of plumes almost entirely composed of VC (i.e. VC-only plumes). This paper investigates the causes of VC-only plumes in the aquifers below the city of Ferrara (northern Italy) by combining multiple lines of evidence. The City of Ferrara is located on an alluvial lowland, built by the River Po, and is made up of alternating unconsolidated sandy aquifer and silt-clay aquitard deposits of fluvial origin. This region has been strongly impacted by prior industrial activities, with the occurrence of chlorinated compounds at several sites. VC-only plumes with uncertain source location were found at two contaminated sites. The source zone of a third plume composed of chloroethenes from PCE to VC was investigated for high resolution depositional facies architecture and contaminant distribution (contaminant concentration and Compound Specific Isotope Analysis - CSIA). The investigation suggested that degradation of PCE and TCE takes place during contaminant migration through peat-rich (swamp) layers related to the Holocene transgression, which locally act as a "reactor" for stimulating degradation with the accumulation of VC in the strongly reducing environment of the peat. Regional-scale stratigraphic architecture showed the ubiquitous occurrence of swamp layers at distinct stratigraphic levels in the investigated system and their apparent linkage to the in situ creation of the VC-only plumes.

Iron oxides stimulate microbial monochlorobenzene in situ transformation in constructed wetlands and laboratory systems.

Natural wetlands are transition zones between anoxic ground and oxic surface water which may enhance the (bio)transformation potential for recalcitrant chloro-organic contaminants due to the unique geochemical conditions and gradients. Monochlorobenzene (MCB) is a frequently detected groundwater contaminant which is toxic and was thought to be persistent under anoxic conditions. Furthermore, to date, no degradation pathways for anoxic MCB removal have been proven in the field. Hence, it is important to investigate MCB biodegradation in the environment, as groundwater is an important drinking water source in many European countries. Therefore, two pilot-scale horizontal subsurface-flow constructed wetlands, planted and unplanted, were used to investigate the processes in situ contributing to the biotransformation of MCB in these gradient systems. The wetlands were fed with anoxic MCB-contaminated groundwater from a nearby aquifer in Bitterfeld, Germany. An overall MCB removal was observed in both wetlands, whereas just 10% of the original MCB inflow concentration was detected in the ponds. In particular in the gravel bed of the planted wetland, MCB removal was highest in summer season with 73 ± 9% compared to the unplanted one with 40 ± 5%. Whereas the MCB concentrations rapidly decreased in the transition zone of unplanted gravel to the pond, a significant MCB removal was already determined in the anoxic gravel bed of the planted system. The investigation of hydro-geochemical parameters revealed that iron and sulphate reduction were relevant redox processes in both wetlands. In parallel, the addition of ferric iron or nitrate stimulated the mineralisation of MCB in laboratory microcosms with anoxic groundwater from the same source, indicating that the potential for anaerobic microbial degradation of MCB is present at the field site.