Fubo Luan

Bioreduction of Nitrobenzene, Natural Organic Matter, and Hematite by Shewanella putrefaciens CN32

We examined the reduction of nitrobenzene by Shewanella putrefaciens CN32 in the presence of natural organic matter (NOM) and hematite. Bioreduction experiments were conducted with combinations and varied concentrations of nitrobenzene, soil humic acid, Georgetown NOM, hematite, and CN32. Abiotic experiments were conducted to quantify nitrobenzene reduction by biogenic Fe(II) and by bioreduced NOMs. We show that S. putrefaciens CN32 can directly reduce nitrobenzene. Both NOMs enhanced nitrobenzene reduction and the degree of enhancement depended on properties of the NOMs (aromaticity, organic radical content). Hematite enhanced nitrobenzene reduction by indirect reaction with biogenic-Fe(II), however, enhancement was dependent on the availability of excess electron donor. Under electron donor-limiting conditions, reducing equivalents diverted to hematite were not all transferred to nitrobenzene. In systems that contained both NOM and hematite we conclude that NOM-mediated reduction of nitrobenzene was more important than Fe(II)-mediated reduction.

Iron(III)-Bearing Clay Minerals Enhance Bioreduction of Nitrobenzene by Shewanella putrefaciens CN32

Iron-bearing clay minerals are ubiquitous in the environment, and the clay-Fe(II)/Fe(III) redox couple plays important roles in abiotic reduction of several classes of environmental contaminants. We investigated the role of Fe-bearing clay minerals on the bioreduction of nitrobenzene. In experiments with Shewanella putrefaciens CN32 and excess electron donor, we found that the Fe-bearing clay minerals montmorillonite SWy-2 and nontronite NAu-2 enhanced nitrobenzene bioreduction. On short time scales (<50 h), nitrobenzene reduction was primarily biologically driven, but at later time points, nitrobenzene reduction by biologically formed structural Fe(II) in the clay minerals became increasingly important. We found that chemically reduced (dithionite) iron-bearing clay minerals reduced nitrobenzene more rapidly than biologically reduced iron-bearing clay minerals despite the minerals having similar structural Fe(II) concentrations. We also found that chemically reduced NAu-2 reduced nitrobenzene faster as compared to chemically reduced SWy-2. The different reactivity of SWy-2 versus NAu-2 toward nitrobenzene was caused by different forms of structural clay-Fe(II) in the clay minerals and different reduction potentials (Eh) of the clay minerals. Because most contaminated aquifers become reduced via biological activity, the reactivity of biogenic clay-Fe(II) toward reducible contaminants is particularly important.

Abiotic reduction of nitroaromatic compounds by Fe(II) associated with iron oxides and humic acid

Experiments were conducted to examine the reduction of nitroaromatic compounds (NACs) by Fe(II) associated with iron oxides (goethite, hematite and magnetite) and humic acid. The reduction rate of nitrobenzene decreased in the order of Fe(II) associated with magnetite>Fe(II) associated with goethite>Fe(II) associated with hematite. We proposed a four-step model (adsorption, electron transfer to conduction band, electron transfer to nitrobenzene and electron transfer to crystal lattice) for nitrobenzene reduction by Fe(II) associated with iron oxides. Fe(II)-humic acid complexes did not present reduction capability of nitrobenzene. Furthermore, Humic acid significantly inhibited nitrobenzene reduction by Fe(II) associated with iron oxides. The inhibitory effect of humic acid toward the reduction of nitrobenzene decreased in the order of magnetite>goethite>hematite.

Linear Free Energy Relationships for the Biotic and Abiotic Reduction of Nitroaromatic Compounds

Nitroaromatic compounds (NACs) are ubiquitous environmental contaminants that are susceptible to biological and abiotic reduction. Prior works have found that for the abiotic reduction of NACs, the logarithm of the NACs’ rate constants correlate with one-electron reduction potential values of the NACs (EH,NAC1) according to linear free energy relationships (LFERs). Here, we extend the application of LFERs to the bioreduction of NACs and to the abiotic reduction of NACs by bioreduced (and pasteurized) iron-bearing clay minerals. A linear correlation (R2=0.96) was found between the NACs’ bioreduction rate constants (kobs) and EH,NAC1 values. The LFER slope of log kobs versus EH,NAC1/(2.303RT/F) was close to one (0.97), which implied that the first electron transfer to the NAC was the rate-limiting step of bioreduction. LFERs were also established between NAC abiotic reduction rate constants by bioreduced iron-bearing clay minerals (montmorillonite SWy-2 and nontronite NAu-2). The second-order NAC reduction rate constants (k) by bioreduced SWy-2 and NAu-2 were well correlated to EH,NAC1 (R2=0.97 for both minerals), consistent with bioreduction results. However, the LFER slopes of log k versus EH,NAC1/(2.303RT/F) were significantly less than one (0.48–0.50) for both minerals, indicating that the first electron transfer to the NAC was not the rate-limiting step of abiotic reduction. Finally, we demonstrate that the rate of 4-acetylnitrobenzene reduction by bioreduced SWy-2 and NAu-2 correlated to the reduction potential of the clay (EH,clay, R2=0.95 for both minerals), indicating that the clay reduction potential also influences its reactivity.

Reduction of nitrobenzene by steel convert slag with Fe(II) system: the role of calcium in steel slag.

Experiments were conducted to examine of nitrobenzene reduction by steel convert slag (SCS) with Fe(II) system. The results showed SCS with Fe(II) was an effective reductant for nitrobenzene at pH 5.5-6.5. Further analysis suggested Fe(II) was adsorbed by SCS through ion replacement with SCS-bound Ca(II). More than 81% of the total Ca(II) in SCS was replaced with dissolved Fe(II), indicating a high adsorption capacity for Fe(II) (more than 5.82 mmol Fe(II)/g SCS). A three step mechanism (replacement process, conversion process and electron transfer process) was proposed for nitrobenzene reduction by SCS with Fe(II) system. The amount of Ca(II) in SCS determined the adsorption capacity for Fe(II) and further determined the reduction capacity of SCS with Fe(II) system.

Effects of supplemental organic carbon on long-term reduction and reoxidation of uranium

Bioreduction of mobile uranyl(VI) (UO22+) to sparingly soluble uraninite (U(IV)O2(s)) is a strategy that has been proposed for in situ remediation of uranium contaminated aquifers. That strategy faces the challenge of reoxidation of uraninite, with consequent release of soluble uranyl when the stimulation of U(VI) bioreduction is terminated. We tested the effects of supplemental organic carbon (ethanol) addition on the long-term reduction and subsequent reoxidation of uranium. In 620 days (31 pore volumes) flow-through bioreduction experiments with 1 or 10 mM ethanol, no obvious difference was observed in effluent U(VI), effluent nitrate, and effluent sulfate. However, a higher concentration of ethanol (10 mM) supported more extensive sulfate reduction to sulfide compared to lower ethanol (1 mM). Upon completion of bioreduction experiments, U(IV) in both 1 and 10 mM ethanol-fed columns was resistant to reoxidation upon addition of oxygenated water to the columns for 110 days (182 pore volumes). Columns that received a higher concentration of ethanol (10 mM) exhibited less U(IV) reoxidation in the presence of nitrate compared to 1 mM ethanol-fed column sediments, and similar results were observed in batch reoxidation experiments in which O2 was used as an oxidant. Our results demonstrate that supplemental organic carbon could protect biogenic U(IV) from remobilization upon intrusion of oxidants.

Iron(III) minerals and anthraquinone-2,6-disulfonate (AQDS) synergistically enhance bioreduction of hexavalent chromium by Shewanella oneidensis MR-1

Bioreduction of hexavalent chromium (Cr(VI)) to sparingly soluble trivalent chromium (Cr(III)) is a strategy for the remediation of Cr(VI) contaminated sites. However, its application is limited due to the slow bioreduction process. Here we explored the potential synergistic enhancement of iron(III) minerals (nontronite NAu-2, ferrihydrite, and goethite) and electron shuttle anthraquinone-2,6-disulfonate (AQDS) on the bioreduction of Cr(VI) by Shewanella oneidensis MR-1. AQDS alone increased the bioreduction rate of Cr(VI) by accelerating electron transfer from MR-1 to Cr(VI). Iron minerals alone did not increase the bioreduction rate of Cr(VI), where the electron transfer from MR-1 to Fe(III) minerals was inhibited due to the toxicity of Cr(VI) to MR-1. AQDS plus NAu-2 or ferrihydrite significantly enhanced the bioreduction rate of Cr(VI) as compared to AQDS or NAu-2/ferrihydrite alone, demonstrating that AQDS plus NAu-2/ferrihydrite had the synergistic effect on bioreduction of Cr(VI). Synergy factor (kcells+Fe+AQDS/(kcells+Fe + kcells+AQDS)) was used to quantify the synergistic effect of AQDS and iron minerals on the bioreduction of Cr(VI). The synergy factors of AQDS plus NAu-2 were 2.09-4.63 (three Cr(VI) spikes), and the synergy factors of AQDS plus ferrihydrite were 1.89-4.61 (two Cr(VI) spikes). In the presence of Cr(VI), AQDS served as the electron shuttle between MR-1 and iron minerals, facilitating the reduction of Fe(III) minerals to Fe(II). The synergistic enhancement of AQDS and NAu-2/ferrihydrite was attributed to the generated Fe(II), which could quickly reduce Cr(VI) to Cr(III). Our results provide an attractive strategy to strengthen the bio-immobilization of Cr(VI) at iron-rich contaminated sites through the synergistic enhancement of iron(III) minerals and electron shuttle.