Influence of ferric iron on complete dechlorination of trichloroethylene (TCE) to ethene: Fe(III) reduction does not always inhibit complete dechlorination

The effects of Fe(III) reduction on TCE, cis-DCE, and VC dechlorination were studied in both contaminated aquifer material and enrichment cultures. The results from sediment batch experiments demonstrated that Fe(III) reduction did not inhibit complete dechlorination. TCE was reduced concurrently with Fe(III) in the first 40 days of the incubations. While all incubations (plus and minus Fe(III)) generated approximately the same mass of ethene within the experimental time frame, Fe(III) speciation (ferrihydrite versus Fe(III)-NTA) had an impact on daughter product distribution and dechlorination kinetics. 16S rRNA gene clone library sequencing identified Dehalococcoides and Geobacteraceae as dominant populations, which included G. lovleyi like organisms. Quantitative PCR targeting 16S rRNA genes and Reductive Dehalogenase genes (tceA, bvcA, vcrA) indicated that Dehalococcoides and Geobacteraceae were enriched concurrently in the TCE-degrading, Fe(III)-reducing sediments. Enrichment cultures demonstrated that soluble Fe(III) had a greater impact on cis-DCE and VC reduction than solid-phase Fe(III). Geobacteraceae and Dehalococcoides were also coenriched in the liquid cultures, and the Dehalococcoides abundance in the presence of Fe(III) was not significantly different from those in the cultures without Fe(III). Hydrogen reached steady-state concentrations most amenable to complete dechlorination very quickly when Fe(III) was present in the culture, suggesting that Fe(III) reduction may actually help dechlorination. This was contrasted to hydrogen levels in nitrate-amended enrichments, in which hydrogen concentration was too low for any chlororespiration.     

Reductive dechlorination pathways of tetrachloroethylene and trichloroethylene and subsequent transformation of their dechlorination products by mackinawite (FeS) in the presence of metals

Because of frequent co-occurrence of metals with chlorinated organic pollutants, Fe(II), Co(II), Ni(II), and Hg(II) were evaluated for their impact on the dechlorination pathways of PCE and TCE and the subsequent transformation of the initial dechlorination products by FeS. PCE transforms to acetylene via beta-elimination, TCE via hydrogenolysis, and 1,1-DCE via alpha-elimination, while TCE transforms to acetylene via beta-elimination and cis-DCE and 1,1-DCE via hydrogenolysis. Acetylene subsequently transforms in FeS batches, but little transformation of cis-DCE and 1,1-DCE was observed. Branching ratio calculations indicate that the added metals decrease the reductive transformation of PCE and TCE via beta-elimination relative to hydrogenolysis, resulting in a higher production of the toxic DCE byproducts. Nonetheless, acetylene is generally the dominant product. Production of highly water-soluble compound(s) is suspected as a significant source for incomplete mass recoveries. In the transformation of PCE and TCE, the formation of unidentified product(s) is most significant in Co(II)-added FeS batches. Although nearly complete mass recoveries were observed in the other FeS batches, the subsequent transformation of acetylene would lead to the formation of unidentified product(s) over long time periods.     

Reductive dechlorination of tetrachloroethylene and trichloroethylene by mackinawite (FeS) in the presence of metals: reaction rates

Reductive dechlorination by mackinawite (FeS) is an important transformation pathway for chloroethylenes in anoxic environments. Yet, the impact of metals on reductive dechlorination is not well understood, despite their frequent cooccurrence with chloroethylenes. Fe(II), Co(II), Ni(II), and Hg(II) were evaluated for their impact on the dechlorination rates of PCE and TCE by FeS. Compared with unamended FeS batches, the dechlorination rates of both chloroethylenes decreased by addition of 0.01 M Fe(II). Relative to 0.01 M Fe(II)-added FeS batches, the dechlorination rates increased in FeS batches amended with 0.01 M of Co(II) and Hg(II), whereas the rates decreased in 0.01 M Ni(II)-added batches. While significantly impacting the dechlorination rates, the amended metals were quantitatively sequestered by FeS mainly because of formation of metal sulfides. Comparison of the dechlorination rates between metal-added FeS batches and metal sulfide batches suggests that discrete metal sulfides do not form in metal-added FeS batches. The observed exceptionally high reactivity of CoS suggests that it may be useful in reactive permeable barrier applications because of its stability in anoxic waters. The dechlorination rates of PCE and TCE significantly varied with Fe(ll) amendment concentrations (Fe(II)0), indicating the presence of different types of solid-bound Fe phases with Fe(II)o.     

Abiotic reductive dechlorination of chlorinated ethylenes by iron-bearing soil minerals. 1. Pyrite and magnetite

Abiotic reductive dechlorination of chlorinated ethylenes (tetrachloroethylene (PCE), trichloroethylene (TCE), cis-dichloroethylene (cis-DCE), and vinyl chloride (VC)) by pyrite and magnetite was characterized in a batch reactor system. Dechlorination kinetics was adequately described by a modified Langmuir-Hinshelwood model that includes the effect of a decreasing reductive capacity of soil mineral. The kinetic rate constant for the reductive dechlorination of target organics at reactive sites of soil minerals was in the range of 0.185 (+/- 0.023) to 1.71 (+/- 0.06) day(-1). The calculated specific reductive capacity of soil minerals for target organics was in the range of 0.33 (+/- 0.02) to 2.26 (+/- 0.06) microM/g and sorption coefficient was in the range of 0.181 (+/- 0.006) to 0.7 (+/- 0.022) mM(-1). Surface area-normalized pseudo-first-order initial rate constants for target organics by pyrite were found to be 23.5 to 40.3 times greater than those by magnetite. Target organics were mainly transformed to acetylene and small amount of chlorinated intermediates, which suggests that beta-elimination was the main dechlorination pathway. The dechlorination of VC followed a hydrogenolysis pathway to produce ethylene and ethane. The addition of Fe(II) increased the dechlorination rate of cis-DCE and VC in magnetite suspension by nearly a factor of 10. The results obtained in this research provide basic knowledge to better predict the fate of chlorinated ethylenes and to understand the potential of abiotic processes in natural attenuation.     

Green rust and iron oxide formation influences metolachlor dechlorination during zerovalent iron treatment

Electron transfer from zerovalent iron (Fe0) to targeted contaminants is affected by initial Fe0 composition, the oxides formed during corrosion, and surrounding electrolytes. We previously observed enhanced metolachlor destruction by Fe0 when iron or aluminum salts were present in the aqueous matrix and Eh/pH conditions favored formation of green rusts. To understand these enhanced destruction rates, we characterized changes in Fe0 composition during treatment of metolachlor with and without iron and aluminum salts. Raman microspectroscopy and X-ray diffraction (XRD) indicated that the iron source was initially coated with a thin layer of magnetite (Fe3O4), maghemite (gamma-Fe2O3), and wüstite (FeO). Time-resolved analysis indicated that akaganeite (beta-FeOOH) was the dominant oxide formed during Fe0 treatment of metolachlor. Goethite (alpha-FeOOH) and some lepidocrocite (gamma-FeOOH) formed when Al2(SO4)3 was present, while goethite and magnetite (Fe3O4) were identified in Fe0 treatments containing FeSO4. Although conditions favoring formation of sulfate green rust (GR(II); Fe6(OH)12SO4) facilitated Fe0-mediated dechlorination of metolachlor, only adsorption was observed when GR(II) was synthesized (without Fe0) in the presence of metolachlor and Eh/pH changed to favor Fe(III)oxyhydroxide or magnetite formation. In contrast, dechlorination occurred when magnetite or natural goethite was amended with Fe(II) (as FeSO4) at pH 8 and continued as long as additional Fe(II) was provided. While metolachlor was not dechlorinated by GR(II) itself during a 48-h incubation, the GR(II) provided a source of Fe(II) and produced magnetite (and other oxide surfaces) that coordinated Fe(II), which then facilitated dechlorination.     

Experimental evaluation and mathematical modeling of microbially enhanced tetrachloroethene (PCE) dissolution

Experiments to assess metabolic reductive dechlorination (chlororespiration) at high concentration levels consistent with the presence of free-phase tetrachloroethene (PCE) were performed using three PCE-to-cis-1,2-dichloroethene (cis-DCE) dechlorinating pure cultures (Sulfurospirillum multivorans, Desulfuromonas michiganensis strain BB1, and Geobacter lovleyi strain SZ) and Desulfitobacterium sp. strain Viet1, a PCE-to-trichloroethene (TCE) dechlorinating isolate. Despite recent evidence suggesting bacterial PCE-to-cis-DCE dechlorination occurs at or near PCE saturation (0.9-1.2 mM), all cultures tested ceased dechlorinating at approximately 0.54 mM PCE. In the presence of PCE dense nonaqueous phase liquid (DNAPL), strains BB1 and SZ initially dechlorinated, but TCE and cis-DCE production ceased when aqueous PCE concentrations reached inhibitory levels. For S. multivorans, dechlorination proceeded at a rate sufficient to maintain PCE concentrations below inhibitory levels, resulting in continuous cis-DCE production and complete dissolution of the PCE DNAPL. A novel mathematical model, which accounts for loss of dechlorinating activity at inhibitory PCE concentrations, was developed to simultaneously describe PCE-DNAPL dissolution and reductive dechlorination kinetics. The model predicted that conditions corresponding to a bioavailability number (Bn) less than 1.25 x 10(-2) will lead to dissolution enhancement with the tested cultures, while conditions corresponding to a Bn greater than this threshold value can result in accumulation of PCE to inhibitory dissolved-phase levels, limiting PCE transformation and dissolution enhancement. These results suggest that microorganisms incapable of dechlorinating at high PCE concentrations can enhance the dissolution and transformation of PCE from free-phase DNAPL.     

Synergistic effect of copper ion on the reductive dechlorination of carbon tetrachloride by surface-bound Fe(II) associated with goethite

The dechlorination of carbon tetrachloride (CT) by Fe(II) associated with goethite in the presence of transition metal ions was investigated. X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (XRPD) were used to characterize the chemical states and crystal phases of transition metals on solid phases, respectively. CT was dechlorinated to chloroform (CF) by 3 mM Fe(II) in 10 mM goethite (25.6 m2 L(-1)) suspensions. The dechlorination followed pseudo-first-order kinetics, and a rate constant (k(obs)) of 0.036 h(-1) was observed. Transition metal ions have different effects on CT dechlorination. The addition of Ni(II), Co(II), and Zn(II) lowered the k(obs) for CT dechlorination, whereas the amendment of 0.5 mM Cu(II) into the Fe(II)-Fe(III) system significantly enhanced the efficiency and the rate of CT dechlorination. The k(obs) for CT dechlorination with 0.5 mM Cu(II) was 1.175 h(-1), which was 33 times greater than that without Cu(II). Also, the dechlorination of CT by surface-bound iron species is pH-dependent, and the rate constants increased from 0.008 h(-1) at pH 4.0 to 1.175 h(-1) at pH 7.0. When the solution contained Cu(II) and Fe(II) without goethite, a reddish-yellow precipitate was formed, and the concentration of Fe(ll) decreased with the increase in Cu(II) concentration. XPS and XRPD analyses suggested the possible presence of Cu2O and ferrihydrite in the precipitate. Small amounts of aqueous Cu(I) were also detected, reflecting the fact that Cu(II) was reduced to Cu(I) by Fe(II). A linear relationship between k(obs) for CT dechlorination and the concentration of Cu(II) was observed when the amended Cu(II) concentration was lower than 0.5 mM. Moreover, the k(obs) for CT dechlorination was dependent on the Fe(II) concentration in the 0.5 mM Cu(II)-amended goethite system and followed a Langmuir-Hinshelwood relationship. These results clearly indicate that Fe(II) serves as the bulk reductant to reduce both CT and Cu(II). The resulting Cull) can further act as a catalyst to enhance the dechlorination rate of chlorinated hydrocarbons in iron-reducing environments.     

Reductive dechlorination of carbon tetrachloride in aqueous solutions containing ferrous and copper ions

Fe(II) associated with iron-containing minerals has been shown to be a potential reductant in natural subsurface environments. While it is known that the surface-bound iron species has the capacity to dechlorinate various chlorinated compounds, the role of transition metals to act as catalysts with these iron species is of importance. We previously observed that the reduction of Cu(II) by Fe(II) associated with goethite enhanced the dechlorination efficiency of chlorinated compound. In this study, the reductive dechlorination of carbon tetrachloride (CCl4) by dissolved Fe(II) in the presence of Cu(II) ions was investigated to understand the synergistic effect of Fe(II) and Cu(II) on the dechlorination processes in homogeneous aqueous solutions. The dechlorination efficiency of CCl4 by Fe(II) increased with increasing Cu(II) concentrations over the range of 0.2-0.5 mM and then decreased at high Cu(II) concentrations. The efficiency and rate of CCl4 dechlorination also increased with increasing dissolved Fe(II) concentration in the presence of 0.5 mM Cu(II) at neutral pH. When the Fe(II)/Cu(II) ratio varied between 1 and 10, the pseudo-first-order rate constant (k(obs)) increased 250-fold from 0.007 h(-1) at 0.5 mM Fe(II) to 1.754 h(-1) at 5 mM Fe(II). X-ray powder diffraction and scanning electron microscopy analyses showed that Cu(II) can react with Fe(II) to produce different morphologies of ferric oxides and subsequently accelerate the dechlorination rate of CCl4 at a high Fe(II) concentration. Amorphous ferrihydrite was observed when the stoichiometric Fe(II)/Cu(II) ratio was 1, while green rust, goethite, and magnetite were formed when the molar ratios of Fe(II)/Cu(II) reached 4-6. In addition, the dechlorination of CCl4 by dissolved Fe(II) is pH dependent. CCl4 can be dechlorinated by Fe(II) over a wide range of pH values in the Cu(II)-amended solutions, and the k(obs) increased from 0.0057 h(-1) at pH 4.3 to 0.856 h(-1) at pH 8.5, which was 9-25 times greater than that in the absence of Cu(II) at pH 7-8.5. The high reactivity of dissolved Fe(II) on the dechlorination of CCl4 in the presence of Cu(II) under anoxic conditions may enhance our understanding of the role of Fe(II) and the long-term reactivity of the zerovalent iron system in the dechlorination processes for chlorinated organic contaminants.     

Reductive dechlorination of cis-1,2-dichloroethene and vinyl chloride by "Dehalococcoides ethenogenes"

cis-Dichloroethene (DCE) and vinyl chloride (VC) often accumulate in contaminated aquifers in which tetrachloroethene (PCE) or trichloroethene (TCE) undergo reductive dechlorination. "Dehalococcoides ethenogenes" strain 195 is the first isolate capable of dechlorinating chloroethenes past cis-DCE. Strain 195 could utilize commercially synthesized cis-DCE as an electron acceptor, but doses greater than 0.2 mmol/L were inhibitory, especially to PCE utilization. To test whether the cis-DCE itself was toxic, or whether the toxicity was due to impurities in the commercial preparation (97% nominal purity), we produced cis-DCE biologically from PCE using a Desulfitobacterium sp. culture. The biogenic cis-DCE was readily utilized at high concentrations by strain 195 indicating that cis-DCE was not intrinsically inhibitory. Analysis of the commercially synthesized cis-DCE by GC/mass spectrometry indicated the presence of approximately 0.4% mol/mol chloroform. Chloroform was found to be inhibitory to chloroethene utilization by strain 195 and at least partially accounts for the inhibitory activity of the synthetic cis-DCE. VC, a human carcinogen that accumulates to a large extent in cultures of strain 195, was not utilized as a growth substrate, and cultures inoculated into medium with VC required a growth substrate, such as PCE, for substantial VC dechlorination. However, high concentrations of PCE or TCE inhibited VC dechlorination. Use of a hexadecane phase to keep the aqueous PCE concentration low in cultures allowed simultaneous utilization of PCE and VC. At contaminated sites in which "D. ethenogenes" or similar organisms are present, biogenic cis-DCE should be readily dechlorinated, chloroform as a co-contaminant may be inhibitory, and concentrations of PCE and TCE, except perhaps those near the source zone, should allow substantial VC dechlorination.     

Reoxidation behavior of technetium, iron, and sulfur in estuarine sediments

Technetium is a redox active radionuclide, which is present as a contaminant at a number of sites where nuclear fuel cycle operations have been carried out. Recent studies suggest that Tc(VII), which is soluble under oxic conditions, will be retained in sediments as Fe(III)-reducing conditions develop, due to reductive scavenging as hydrous TcO2. However, the behavior of technetium during subsequent reoxidation of sediments remains poorly characterized. Here, we describe a microcosm-based approach to investigate the reoxidation behavior of reduced, technetium-contaminated sediments. In reoxidation experiments, the behavior of Tc was strongly dependent on the nature of the oxidant. With air, reoxidation of Fe(II) and, in sulfate-reducing sediments, sulfide occurred accompanied by approximately 50% remobilization of Tc to solution as TcO4-. With nitrate, reoxidation of Fe(II) and, in sulfate-reducing sediments, sulfide only occurred in microbially active experiments where Fe(II) and sulfide oxidation coupled to nitrate reduction was occurring. Here, Tc was recalcitrant to remobilization with <10% Tc remobilized to solution even when extensive Fe(II) and sulfide reoxidation had occurred. X-ray absorption spectroscopy on reoxidized sediments suggested that 15-50% of Tc bound to sediments was present as Tc(VII). Overall, these results suggest that Tc reoxidation behavior is not directly coupled to Fe or S oxidation and that the extent of Tc remobilization is dependent on the nature of the oxidant.     

Efficient dechlorination of tetrachloroethylene in soil slurry by combined use of an anaerobic Desulfitobacterium sp. strain Y-51 and zero-valent iron

A laboratory test was conducted to examine the combined effect of bioaugmentation of an anaerobic bacterial Desulfitobacterium sp. strain Y-51 and addition of zero-valent iron (Fe0) on the reductive dechlorination of tetrachloroethylene (PCE) in a non-sterile soil slurry. Introduction of a strain Y-51 culture in soil (3 mg vss (volatile suspended solids)/kg soil) containing PCE (at 60 micromol/kg soil) led to complete conversion of PCE to cis-1,2-dichloroethylene (cis-DCE) within 40 d. Treatments of the same soil slurry with Fe0 (0.1-1.0%) resulted in extended PCE dechlorination to ethylene (ETH) and ethane (ETA). The combined use of a strain Y-51 culture and Fe0 showed effective dechlorination of PCE than did the individual use. The cis-DCE produced from biological PCE dechlorination by strain Y-51 was totally converted to non-chlorinated end products by the following chemical reduction by Fe0. Furthermore, anaerobic corrosion of Fe0 was found to stimulate the biological reductive dechlorination of PCE by keeping proper levels of pH and oxidation-reduction potential (ORP) and by producing cathodic hydrogen, which might be used as an electron donor for respiratory PCE dechlorination. These findings suggest that the combined use of bacterial strain Y-51 and Fe0 is effective for practical treatment of PCE and other chlorinated ethylenes in contaminated sites.     

The effects of reaction-product formation on the reductive dissolution of MnO2 by Fe(II)

We conducted batch-reactor experiments to measure the reductive dissolution of pyrolusite-coated (beta-MnO2) quartz by Fe(II) under conditions representative of an acid mine-drainage subsurface plume. The results reveal that reductive dissolution rates were initially rapid but declined considerably as Fe(III)(aq), a product of the reductive-dissolution reaction, was removed from solution by heterogeneous precipitation. The inhibition of reductive-dissolution was attributed to blocking of the beta-MnO2 surface sites by the Fe(III)(s) precipitate. Calculations of a simple model that accounts for the effects of Fe(III)(s) precipitate formation on reductive dissolution rates closely match temporal changes in Mn(II), Fe(II), and Fe(II) concentrations measured in 10 experiments, distinguished on the basis of the initial Fe(II)-to-Mn(IV) mole ratio and the initial Fe(III)(aq) concentration. The model-data comparisons reveal that the initial reaction rate on a clean beta-MnO2 surface exceeds the long-term reaction rate by 3 orders of magnitude, highlighting the importance of linking Fe(III) precipitation with the reductive dissolution of beta-MnO2 by Fe(II).     

Effects of the nonionic surfactant tween 80 on microbial reductive dechlorination of chlorinated ethenes

Recent field studies have indicated synergistic effects of coupling microbial reductive dechlorination with physicochemical remediation (e.g., surfactant flushing) of dense nonaqueous phase liquid (DNAPL) source zones. This study explored chlorinated ethene (e.g., tetrachloroethene [PCE]) dechlorination in the presence of 50-5000 mg/L Tween 80, a nonionic surfactant employed in source zone remediation. Tween 80 did not inhibit dechlorination by four pure PCE-to-cis-1,2-dichloroethene (cis-DCE) or PCE-to-trichloroethene (TCE) dechlorinating cultures. In contrast, cis-DCE-dechlorinating Dehalococcoides isolates (strain BAV1 and strain FL2) failed to dechlorinate in the presence of Tween 80. Bio-Dechlor INOCULUM (BDI), a PCE-to-ethene dechlorinating consortium, produced cis-DCE in the presence of Tween 80, further suggesting that Tween 80 inhibits dechlorination by Dehalococcoides organisms. Quantitative real-time PCR analysis applied to BDI revealed that the number of Dehalococcoides cells decayed exponentially (R(2) = 0.85) according to the Chick-Watson disinfection model (pseudo first-order decay rate of 0.13+/-0.02 day(-1)) from an initial value of 6.6 +/-1.5 x 10(8) to 1.3+/-0.8 x 10(5) per mL of culture after 58 days of exposure to 250 mg/L Tween 80. Although Tween 80 exposure prevented ethene formation and reduced Dehalococcoides cell numbers, Dehalococcoides organisms remained viable, and dechlorination activity pist cis-DCE was recovered following the removal of Tween 80. These findings suggest that sequential Tween 80 flushing followed by microbial reductive dechlorination is a promising strategy for remediation of chlorinated ethene-impacted source zones.     

Microbial diversity and changes in the distribution of dehalogenase genes during dechlorination with different concentrations of cis-DCE

A dechlorinating consortium (designated as TES-1 culture) able to convert trichloroethene (TCE) to ethene was established from TCE-contaminated groundwater. This culture had the ability of complete dechlorination of TCE within about one month. From the clone library analysis of 16S rRNA gene, this culture was mainly composed of fermentation bacteria, such as Clostridium spp., and Desulfitobacterium spp. known as facultative dechlorinator. PCR using specific primers for Dehalococcoides spp. and the dehalogenase genes confirmed that the culture contained the Dehalococcoides spp. 16S rRNA gene and three dehalogenase genes, tceA, vcrA and bvcA. Dechlorination experiments using cis-dichloroethene (cis-DCE) at concentrations of 37-146 μM, revealed that the gene copy numbers of tceA, vcrA, and bvcA increased up to 10? copy/mL, indicating that Dehalococcoides spp. containing these three dehalogenase genes were involved in cis-DCE dechlorination. However, in the culture to which 292 μM of cis-DCE was added, only the tceA gene and the Dehalococcoides spp. 16S rRNA gene increased up to 10? copy/mL. The culture containing 292 μM of cis-DCE also exhibited about one tenth slower ethene production rate compared to the other cultures.     

Kinetics and modeling of the Fe(III)/H2O2 system in the presence of sulfate in acidic aqueous solutions

This work examined the effect of sulfate ions on the rate of decomposition of H2O2 by Fe(III) in homogeneous aqueous solutions. Experiments were carried out at 25 degrees C, pH < or = 3 and the concentrations of sulfate ranged from 0 to 200 mM ([Fe(III)]0 = 0.2 or 1 mM, [H2O2]0 = 10 or 50 mM). The spectrophometric study shows that addition of sulfate decreased the formation of iron(III)-peroxo complexes and that H2O2 does not form complexes with iron(III)-sulfato complexes. The rates of decomposition of H2O2 markedly decreased in the presence of sulfate. The measured rates were accurately predicted by a kinetic model based on reactions previously validated in NaClO4/HClO4 solutions and on additional reactions involving sulfate ions and sulfate radicals. At a fixed pH, the pseudo-first-order rate constants were found to decrease linearly with the molar fraction of Fe(II) complexed with sulfate. The model was also able to predict the rate of oxidation of a probe compound (atrazine) by Fe(III)/H2O2. Computer simulations indicate that the decrease of the rate of oxidation of organic solutes by Fe(III)/H2O2 can be mainly attributed to the complexation of Fe(III) by sulfate ions, while sulfate radicals play a minor role on the overall reaction rates.     

Acetate versus hydrogen as direct electron donors to stimulate the microbial reductive dechlorination process at chloroethene-contaminated sites

A study to evaluate the dechlorination end points and the most promising electron donors to stimulate the reductive dechlorination process at the chloroethene-contaminated Bachman Road site in Oscoda, MI, was conducted. Aquifer materials were collected from inside the plume and used to establish microcosms under a variety of electron donor conditions using chlorinated ethenes as electron acceptors. All microcosms that received an electron donor showed dechlorination activity, but the end points depended on the sampling location, indicating a heterogeneous distribution of the dechlorinating populations in the aquifer. Interestingly, several microcosms that received acetate as the only electron donor completely dechlorinated PCE to ethene. All acetate-amended microcosms rapidly converted PCE to cis-DCE, whereas PCE dechlorination in H2-fed microcosms only occurred after a pronounced lag time and after acetate had accumulated by H2/CO2 acetogenic activity. The microcosm experiments were corroborated by defined co-culture experiments, which demonstrated that H2 sustained PCE to cis-DCE dechlorination by acetotrophic populations in the presence of H2/CO2 acetogens. In sediment-free nonmethanogenic enrichment cultures derived from ethene-producing microcosms, acetate alone supported complete reductive dechlorination of chloroethenes to ethene, although the addition of H2 resulted in higher cis-DCE and VC dechlorination rates. Measurements of H2 production and consumption suggested that syntrophic acetate-oxidizing population(s) were active in the enrichment cultures. These findings demonstrated that either acetate or H2 alone can be sufficient to promote complete     

Dechlorination of tetrachloroethylene in aqueous solutions using metal-modified zerovalent silicon

The combination of zerovalent metal with a catalytic second metal ion (bimetallic materials) to enhance the dechlorination efficiency and rate of chlorinated compounds has received much attention. Bimetallic materials not only enhance the dechlorination process but also alter the reduction pathway and product distribution. In this study, the efficiency and rate of tetrachloroethylene (PCE) dechlorination by metal-modified zerovalent silicon was investigated as a potential reductant for chlorinated hydrocarbons under anoxic conditions. The X-ray photoelectron spectroscopic (XPS) results showed that metal ions including Ni(II), Cu(II), and Fe(II) could be reduced to their zerovalent forms on the Si surface. The dechlorination of PCE obeyed the pseudo-first-order kinetics, and the pseudo-first-order rate constants (k(obs)) for PCE dechlorination followed the order Ni/Si > Fe/Si > Cu/Si. Addition of Cu(II) lowered the dechlorination efficiency and rate of PCE by Si, while the k(obs) values for PCE dechlorination in the presence of 0.1 mM Fe(II) and Ni(II) were 1.5-3.8 times higher than that by Si alone. In addition, the efficiency and rate of PCE dechlorination increased upon increasing the mass loading of Ni(II) ranging between 0.05 and 0.5 mM and then decreased when the Ni(II) loading was further increased to 1 mM. The scanning electron microscopic (SEM) images and electron probe microanalytical (EPMA) maps showed that the Ni nanoparticles deposited on the Si surface and aggregated to a large particle at 1 mM Ni(II), which clearly depicts that the Ni(II) loading of 0.5 mM is the optimal value to enhance the efficiency and rate of PCE dechlorination by Si. Also, the reaction pathways for PCE dechlorination changed from hydrogenolysis in the absence of Ni(II) to hydrodechlorination when Ni(II) concentrations were higher than 0.05 mM. Results obtained in this study reveal that the metal-deposited zerovalent silicon can serve as an environmentally friendly reductant for the enhanced degradation of chlorinated hydrocarbons for long-term performance.     

Anaerobic degradation of cis-1,2-dichloroethylene and vinyl chloride by Clostridium sp. strain DC1 isolated from landfill leachate sediment

The bacterial community structure of anaerobic enrichment cultures that are capable of degrading both cis-1,2-dichloroethylene (cis-DCE) and vinyl chloride (VC) and isolation of the organism responsible for the degradation were investigated. Denaturing gradient gel electrophoresis (DGGE) of a PCR-amplified 16S rRNA gene from the cultures showed the possible predominance of Clostridium species. One isolate, designated strain DC1, was closely related to members of Clostridiaceae, based on 16S rRNA gene analysis, and the highest sequence similarity (98.9%) was obtained for Clostridium saccarobutylicum. In culture experiments, strain DC1 was shown to degrade cis-DCE and VC during the stationary phase of growth without accumulation of VC and/or ethene. The bacterial growth was not linked to the degradation of cis-DCE and VC. Stoichiometric analysis revealed that two moles of chloride ions as released from one mole of cis-DCE during the incubation period, indicating that cis-DCE was fully dechlorinated. The results appear consistent with the presence of a mechanism of oxidative dechlorination rather than respiratory reductive dechlorination; the latter is accompanied by transient formation of dechlorinated ethenes from cis-DCE and VC.     

Effects of progressive anoxia on the solubility of technetium in sediments

Technetium is a significant radioactive contaminant from nuclear fuel cycle operations. It is highly mobile in its oxic form (as Tc(VII)O4-) but is scavenged to sediments in its reduced forms (predominantly Tc(IV)). Here we examine the behavior of Tc at low concentrations and as microbial anoxia develops in sediment microcosms. A cascade of stable-element terminal-electron-accepting processes developed in microcosms due to indigenous microbial activity. TcO4- removal from solution occurred during active microbial Fe(III) reduction, which generated Fe(II) in the sediments and was complete before sulfate reduction began. Microbial community analysis revealed a similar and complex microbial population at all three sample sites. At the intermediate salinity site, PauII, a broad range of NO3-, Mn(IV), Fe(III), and SO4(2-) reducers were present in sediments including microbes with the potential to reduce Fe(III) to Fe(II), although no differences in the microbial population were discerned as anoxia developed. When sterilized sediments were incubated with pure cultures of NO3(-)-, Fe(III)-, and sulfate-reducing bacteria, TcO4- removal occurred during active Fe(III) reduction. X-ray absorption spectroscopy confirmed that TcO4- removal was due to reduction to hydrous Tc(IV)O2 in Fe(III)- and sulfate-reducing estuarine sediments.     

Microbial reduction of Fe(III) and sorption/precipitation of Fe(II) on Shewanella putrefaciens strain CN32

The influence of Fe(II) on the dissimilatory bacterial reduction of an Fe(III) aqueous complex (Fe(III)-citrate(aq)) was investigated using Shewanella putrefaciens strain CN32. The sorption of Fe(II) on CN32 followed a Langmuir isotherm. Least-squares fitting gave a maximum sorption capacity of Qmax = 4.19 x 10(-3) mol/10(12) cells (1.19 mmol/m2 of cell surface area) and an affinity coefficient of log K = 3.29. The growth yield of CN32 with respect to Fe(III)aq reduction showed a linear trend with an average value of 5.24 (+/-0.12) x 10(9) cells/mmol of Fe(III). The reduction of Fe(III)aq by CN32 was described by Monod kinetics with respect to the electron acceptor concentration, Fe(III)aq, with a half-saturation constant (Ks) of 29 (+/-3) mM and maximum growth rate (micromax) of 0.32 (+/-0.02) h(-1). However, the pretreatment of CN32 with Fe(II)aq significantly inhibited the reduction of Fe(III)aq, resulting in a lag phase of about 3-30 h depending on initial cell concentrations. Lower initial cell concentration led to longer lag phase duration, and higher cell concentration led to a shorter one. Transmission electron microscopy and energy dispersive spectroscopy revealed that many cells carried surface precipitates of Fe mineral phases (valence unspecified) during the lag phase. These precipitates disappeared after the cells recovered from the lag phase. The cell inhibition and recovery mechanisms from Fe(II)-induced mineral precipitation were not identified by this study, but several alternatives were discussed. A modified Monod model incorporating a lag phase, Fe(II) adsorption, and aqueous complexation reactions was able to describe the experimental results of microbial Fe(III)aq reduction and cell growth when cells were pretreated with Fe(II)aq.