Use of CAH-degrading bacteria as test-organisms for evaluating the impact of fine zerovalent iron particles on the anaerobic subsurface environment.

The release of fine zerovalent iron (ZVI) particles in the environment after being introduced for in-situ treatment of compounds like chlorinated aliphatic hydrocarbons (CAHs) may raise questions toward environmental safety, especially for nanoscale materials. Classical single-species ecotoxicity tests do focus on aerobic conditions and are only relevant for the scenario when ZVI-particles reach surface water. Herein, we present an alternative approach where a CAH-degrading mixed bacterial culture was used as test-organisms relevant for the anaerobic subsurface. The impact of different ZVI particles on the bacterial culture was evaluated mainly by quantifying ATP, a reporter molecule giving a general indication of the microbial activity. These lab-scale batch tests were performed in liquid medium, without protecting and buffering aquifer material, as such representing worst-case scenario. The activity of the bacterial culture was negatively influenced by nanoscale zerovalent iron at doses as low as 0.05 g L(-1). On the other hand, concentrations up to 2 g L(-1) of several different types of microscale zerovalent iron (mZVI) particles stimulated the activity. However, very high doses of 15-30 g L(-1) of mZVI showed an inhibiting effect on the bacterial community. Negative effects of ZVIs were confirmed by H2 accumulation in the batch reactors and the absence of lactate consumption. Observed inhibition also corresponded to a pH increase above 7.5, explicable by ZVI corrosion that was found to be dose-dependent. The obtained results suggest that low doses of mZVIs will not show severe inhibition effects on the microbial community once used for in-situ treatment of CAHs.

Corrosion rate estimations of microscale zerovalent iron particles via direct hydrogen production measurements.

In this study, the aging behavior of microscale zerovalent iron (mZVI) particles was investigated by quantifying the hydrogen gas generated by anaerobic mZVI corrosion in batch degradation experiments. Granular iron and nanoscale zerovalent iron (nZVI) particles were included in this study as controls. Firstly, experiments in liquid medium (without aquifer material) were performed and revealed that mZVI particles have approximately a 10-30 times lower corrosion rate than nZVI particles. A good correlation was found between surface area normalized corrosion rate (RSA) and reaction rate constants (kSA) of PCE, TCE, cDCE and 1,1,1-TCA. Generally, particles with higher degradation rates also have faster corrosion rates, but exceptions do exists. In a second phase, the hydrogen evolution was also monitored during batch tests in the presence of aquifer material and real groundwater. A 4-9 times higher corrosion rate of mZVI particles was observed under the natural environment in comparison with the aquifer free artificial condition, which can be attributed to the low pH of the aquifer and its buffer capacity. A corrosion model was calibrated on the batch experiments to take into account the inhibitory effects of the corrosion products (dissolved iron, hydrogen and OH(-)) on the iron corrosion rate.

Guar gum coupled microscale ZVI for in situ treatment of CAHs: continuous-flow column study.

A column study was performed under in situ conditions to evaluate to which extend the inactivation of the microscale zerovalent iron (mZVI) by guar gum occurs under continuous flow conditions. Five aquifer containing columns were set up under different conditions. Efficient removal of trichloroethene was observed for the column amended by mZVI. Stabilization of the mZVI with guar gum led to slightly reduced activity. More reduced reactivity was observed in the poisoned column containing guar gum stabilized mZVI. This confirms that soil microorganisms can degrade guar gum and that subsequent removal of the oligosaccharides by the groundwater flow (flushing effect) can reactivate the mZVI. After more than six months of continuous operation the columns were dismantled. DNA-based qPCR analysis revealed that mZVI does not significantly affect the bacterial community, while guar gum stabilized mZVI particles can even induce bacterial growth. Overall, this study suggests that the temporarily decreased mZVI reactivity due to guar gum, has a rather limited impact on the performance of in situ reactive zones. The presence of guar gum slightly reduced the reactivity of iron, but also slowed down the iron corrosion rate which prolongs the life time of reactive zone.

Impact of carbon, oxygen and sulfur content of microscale zerovalent iron particles on its reactivity towards chlorinated aliphatic hydrocarbons.

Zerovalent iron (ZVI) abiotically degrades several chlorinated aliphatic hydrocarbons (CAHs) via reductive dechlorination, which offers perspectives for in situ groundwater remediation applications. The difference in reactivity between ZVI particles is often linked with their specific surface area. However, other parameters may influence the reactivity as well. Earlier, we reported for a set of microscale zerovalent iron (mZVI) particles the disappearance kinetic of different CAHs which were collected under consistent experimental conditions. In the present study, these kinetic data were correlated with the carbon, oxygen and sulfur content of mZVI particles. It was confirmed that not only the specific surface area affects the disappearance kinetic of CAHs, but also the chemical composition of the mZVI particles. The chemical composition, in addition, influences CAHs removal mechanism inducing sorption onto mZVI particles instead of dechlorination. Generally, high disappearance kinetic of CAHs was observed for particles containing less oxygen. A high carbon content, on the other hand, induced nonreactive sorption of the contaminants on the mZVI particles. To obtain efficient remediation of CAHs by mZVI particles, this study suggested that the carbon and oxygen content should not exceed 0.5% and 1% respectively. Finally, the efficiency of the mZVI particles may be improved to some extent by enriching them with sulfur. However, the impact of sulfur content on the reactivity of mZVI particles is less pronounced than that of the carbon and oxygen content.

Reactivity screening of microscale zerovalent irons and iron sulfides towards different CAHs under standardized experimental conditions.

A standardized batch test procedure was developed and used to evaluate the reactivity of twelve newly designed microscale zerovalent iron (mZVI) particles and two biogenic iron sulfides towards a mixture of chlorinated aliphatic hydrocarbons (CAHs) and their breakdown products. For comparison, commercially available mZVIs, nanoscale zerovalent irons (nZVIs), iron sulfides (FeS) and granular zerovalent iron were also tested. Reactivity of the particles was based on observed (kobs) and mass normalized (kM) pseudo-first-order degradation rate constants, as well as specific surface area normalized reaction rate constants (kSA). Sorption characteristics of the particles were based on mass balance data. Among the new mZVIs, significant differences in reactivity were observed and the most reactive particles were identified. Based on kM data, nZVI degraded the examined contaminants one to two orders of magnitude faster than the mZVIs. kM values for biogenic iron sulfides were similar to the least reactive mZVIs. On the other hand, comparison of kSA data revealed that the reactivity of some newly designed mZVIs was similar to highly reactive nZVIs, and even up to one order of magnitude higher. kSA values for biogenic iron sulfides were one to two orders of magnitude lower than those reported for reactive mZVIs.

Reactivity recovery of guar gum coupled mZVI by means of enzymatic breakdown and rinsing.

Microscale zerovalent iron (mZVI) reduces chlorinated aliphatic hydrocarbons (CAHs) to harmless compounds, but the sedimentation of the mZVI particles in the injection fluid limits the injectability of the particles during field applications. In this study, mZVI particles in suspension were stabilized by green polymer guar gum, which had a positive impact on mZVI stability, but decreased the reactivity of the particles towards CAHs by 1 to 8 times. Guar gum (GG) was found to adsorb onto the mZVI surface, inhibiting contact between the chlorinated compounds and the reactive iron surface. Indications were found for intermolecular hydrogen bonding between mZVI and the guar gum. Subsequent addition of commercially available enzymes resulted in the cleavage of the polysaccharide guar gum into lower molecular fragments, but not in improved reactivity. The reactivity recovery of guar gum coupled mZVI was recovered after intensive rinsing of the iron particles, removing the guar gum fragments from the particles. Overall, this study shows that CAHs can be treated efficiently by guar gum stabilized mZVI after reactivation by means of enzymatic breakdown and rinsing.