Synergistic effects of microbial anaerobic dechlorination of perchloroethene and nano zero-valent iron (nZVI) - A lysimeter experiment.

Perchloroethene (PCE) is a hazardous and persistent groundwater pollutant. Both treatment with nanoscaled zero-valent iron (nZVI) and biological degradation by bacteria have downsides. Distribution of nZVI underground is difficult and a high percentage of injected nZVI is consumed by anaerobic corrosion, forming H2 rather than being available for PCE dechlorination. On the other hand, microbial PCE degradation can suffer from the absence of H2. This can cause the accumulation of the hazardous metabolites cis-1,2-dichloroethene (DCE) or vinylchloride (VC). The combination of chemical and biological PCE degradation is a promising approach to overcome the disadvantages of each method alone. In this lysimeter study, artificial aquifers were created to test the influence of nZVI on anaerobic microbial PCE dechlorination by a commercially available culture containing Dehalococcoides spp. under field-like conditions. The effect of the combined treatment was investigated with molasses as an additional electron source and after cessation of molasses addition. The combination of nZVI and the Dehalococcoides spp. containing culture led to a PCE discharge in the lysimeter outflow that was 4.7 times smaller than that with nZVI and 1.6 times smaller than with bacterial treatment. Moreover, fully dechlorinated end-products showed an 11-fold increase compared to nZVI and a 4.2-fold increase compared to the microbial culture. The addition of nZVI to the microbial culture also decreased the accumulation of hazardous metabolites by 1.7 (cis-DCE) and 1.2 fold (VC). The stimulatory effect of nZVI on microbial degradation was most obvious after the addition of molasses was stopped.

Inhibition and stimulation of two perchloroethene degrading bacterial cultures by nano- and micro-scaled zero-valent iron particles.

The pollutant perchloroethene (PCE) can often be found at urban contaminated sites. Thus in-situ clean-up methods, like remediation using zero valent iron (ZVI) or bacterial dechlorination, are preferred. During the remediation with ZVI particles anaerobic corrosion occurs as an unwanted, particle consuming side reaction with water. However, in this reaction H2 is formed, which is usually scarce during anaerobic microbial dechlorination. Dehalococcoides needs H2 for cell growth using it as an electron donor to dechlorinate chlorinated hydrocarbons. Combining application of ZVI with bacterial dechlorination can turn ZVI in a H2 donor leading to a more controllable bacterial dechlorination, a smaller amount of ZVI suspension and decreased remediation costs. In this study nano- and micro scaled ZVI particles (nZVI, mZVI) were combined in microcosms with two dechlorinating bacterial cultures. The two cultures showed different dechlorination behaviors with ethene and cis-DCE as final products. Phospholipid fatty acids (PLFA) associated with Dehalococcoides (18:1w7, 18:1w7c, 10:Me16:0) and Geobacteriaceae (16,1w7c; 15:0; 16:0) have been found in both bacterial cultures, slight differences in their abundance could explain the different dechlorinating behaviors. The combination of both bacterial cultures with mZVI led to a stimulated dechlorination process leading to about two times higher kobs for PCE dechlorination (0.01-0.05 h-1). In the otherwise cis-DCE accumulating culture complete dechlorination to ethene was achieved. While addition of nZVI inhibited both cultures. Combined with nZVI the completely dechlorinating culture produced lower amounts of dechlorinated products (3.2 µmol) as compared to the single biotic treatment (5.1 µmol). Combining the incompletely dechlorinating culture with nZVI significantly reduced the kobs,PCE (single: 8 × 10-3 ± 3 × 10-4 h-1; combination: 5 × 10-3 ± 2 × 10-4 h-1). H2 produced by nZVI and mZVI was utilized by both bacterial cultures. The particle size, resulting specific surface areas, agglomeration tendencies and reactivity appears to be crucial for the effect on microbial cells.