Thomas Borch

Biogeochemical Redox Processes and their Impact on Contaminant Dynamics

Life and element cycling on Earth is directly related to electron transfer (or redox) reactions. An understanding of biogeochemical redox processes is crucial for predicting and protecting environmental health and can provide new opportunities for engineered remediation strategies. Energy can be released and stored by means of redox reactions via the oxidation of labile organic carbon or inorganic compounds (electron donors) by microorganisms coupled to the reduction of electron acceptors including humic substances, iron-bearing minerals, transition metals, metalloids, and actinides. Environmental redox processes play key roles in the formation and dissolution of mineral phases. Redox cycling of naturally occurring trace elements and their host minerals often controls the release or sequestration of inorganic contaminants. Redox processes control the chemical speciation, bioavailability, toxicity, and mobility of many major and trace elements including Fe, Mn, C, P, N, S, Cr, Cu, Co, As, Sb, Se, Hg, Tc, and U. Redox-active humic substances and mineral surfaces can catalyze the redox transformation and degradation of organic contaminants. In this review article, we highlight recent advances in our understanding of biogeochemical redox processes and their impact on contaminant fate and transport, including future research needs.

Redox Transformation of Arsenic by Fe(II)Activated Goethite (α-FeOOH)

The redox state and speciation of the metalloid arsenic (As) determine its environmental fate and toxicity. Knowledge about biogeochemical processes influencing arsenic redox state is therefore necessary to understand and predict its environmental behavior. Here we quantified arsenic redox changes by pH-neutral goethite [alpha-Fe(III)OOH] mineral suspensions amended with Fe(II) using wet-chemical and synchrotron X-ray absorption (XANES) analysis. Goethite itself did not oxidize As(III) and, in contrast to thermodynamic predictions, Fe(II)-goethite systems did not reduce As(V). However, we observed rapid oxidation of As(III) to As(V) in Fe(II)-goethite systems. Mössbauer spectroscopy showed initial formation of (57)Fe-goethite after (57)Fe(II) addition plus a so far unidentified additional Fe(II) phase. No other Fe(III) phase could be detected by Mössbauer, EXAFS, SEM, XRD, or HR-TEM. This suggests that reactive Fe(III) species form as an intermediate Fe(III) phase upon Fe(II) addition and electron transfer into bulk goethite but before crystallization of the newly formed Fe(III) as goethite. In summary this study indicates that in the simultaneous presence of Fe(III) oxyhydroxides and Fe(II), as commonly observed in environments inhabited by iron-reducing microorganisms, As(III) oxidation can occur. This potentially explains the presence of As(V) in reduced groundwater aquifers.

Artificial Sweetener Sucralose in U.S. Drinking Water Systems

The artificial sweetener sucralose has recently been shown to be a widespread of contaminant of wastewater, surface water, and groundwater. In order to understand its occurrence in drinking water systems, water samples from 19 United States (U.S.) drinking water treatment plants (DWTPs) serving more than 28 million people were analyzed for sucralose using liquid chromatography tandem mass spectrometry (LC-MS/MS). Sucralose was found to be present in source water of 15 out of 19 DWTPs (47-2900 ng/L), finished water of 13 out of 17 DWTPs (49-2400 ng/L) and distribution system water of 8 out of the 12 DWTPs (48-2400 ng/L) tested. Sucralose was only found to be present in source waters with known wastewater influence and/or recreational usage, and displayed low removal (12% average) in the DWTPs where finished water was sampled. Further, in the subset of DWTPs with distribution system water sampled, the compound was found to persist regardless of the presence of residual chlorine or chloramines. In order to understand intra-DWTP consistency, sucralose was monitored at one drinking water treatment plant over an 11 month period from March 2010 through January 2011, and averaged 440 ng/L in the source water and 350 ng/L in the finished water. The results of this study confirm that sucralose will function well as an indicator compound for anthropogenic influence on source, finished drinking and distribution system (i.e., tap) water, as well as an indicator compound for the presence of other recalcitrant compounds in finished drinking water in the U.S.

Terrestrial natural sources of trichloromethane (chloroform, CHCl3) - An overview

The widespread use of volatile chlorinatedcompounds like chloroform, trichloroethene andtetrachloroethene in industrialized societiescauses a large annual release of thesecompounds into the environment. Due to theirrole as a source for halogen radicals involvedin various catalytic atmospheric reactioncycles, including the regulation of thestratospheric and tropospheric ozone layers,these compounds also constitute a risk fordrinking water resources as they can betransported to the groundwater fromcontaminated field sites or even fromatmospheric deposition. Therefore,identification and investigation of sources andsinks of volatile chlorinated compounds are ofparticular interest. Chloroform, a majorcontributor to natural gaseous chlorine, wasfound to be emitted by several anthropogenicand natural sources including the oceans andterrestrial areas. The origin of chloroform inthe terrestrial environment can beanthropogenic point sources, atmosphericdeposition, release by vegetation andproduction directly in the soil. The calculatedannual biogenic global chloroform emission is700 Gg, and marine and terrestrial environmentsare nearly equal contributors. The estimatedemissions from anthropogenic sources accountfor less than 10% of the estimated totalemissions from all sources. Among terrestrialsources, forests have recently been identifiedas contributing to the release of chloroform intothe environment. With the data available,annual emissions of chloroform to theatmosphere from forest sites were calculatedand compared to other natural sources. Atpresent knowledge, forests are only a minorsource in the total biogenic flux ofchloroform, contributing less than 1% to theannual global atmospheric input. However, itshould be noted that data are available forNorthern temperate forests only. The largetropical forest areas may provide a yet unknowninput of chloroform.

Multiple Mechanisms of Uranium Immobilization by Cellulomonas sp. strain ES6

Removal of hexavalent uranium (U(VI)) from aqueous solution was studied using a Gram‐positive facultative anaerobe, Cellulomonas sp. strain ES6, under anaerobic, non‐growth conditions in bicarbonate and PIPES buffers. Inorganic phosphate was released by cells during the experiments providing ligands for formation of insoluble U(VI) phosphates. Phosphate release was most probably the result of anaerobic hydrolysis of intracellular polyphosphates accumulated by ES6 during aerobic growth. Microbial reduction of U(VI) to U(IV) was also observed. However, the relative magnitudes of U(VI) removal by abiotic (phosphate‐based) precipitation and microbial reduction depended on the buffer chemistry. In bicarbonate buffer, X‐ray absorption fine structure (XAFS) spectroscopy showed that U in the solid phase was present primarily as a non‐uraninite U(IV) phase, whereas in PIPES buffer, U precipitates consisted primarily of U(VI)‐phosphate. In both bicarbonate and PIPES buffer, net release of cellular phosphate was measured to be lower than that observed in U‐free controls suggesting simultaneous precipitation of U and PO  43− . In PIPES, U(VI) phosphates formed a significant portion of U precipitates and mass balance estimates of U and P along with XAFS data corroborate this hypothesis. High‐resolution transmission electron microscopy (HR‐TEM) and energy dispersive X‐ray spectroscopy (EDS) of samples from PIPES treatments indeed showed both extracellular and intracellular accumulation of U solids with nanometer sized lath structures that contained U and P. In bicarbonate, however, more phosphate was removed than required to stoichiometrically balance the U(VI)/U(IV) fraction determined by XAFS, suggesting that U(IV) precipitated together with phosphate in this system. When anthraquinone‐2,6‐disulfonate (AQDS), a known electron shuttle, was added to the experimental reactors, the dominant removal mechanism in both buffers was reduction to a non‐uraninite U(IV) phase. Uranium immobilization by abiotic precipitation or microbial reduction has been extensively reported; however, the present work suggests that strain ES6 can remove U(VI) from solution simultaneously through precipitation with phosphate ligands and microbial reduction, depending on the environmental conditions. Cellulomonadaceae are environmentally relevant subsurface bacteria and here, for the first time, the presence of multiple U immobilization mechanisms within one organism is reported using Cellulomonas sp. strain ES6. Biotechnol. Bioeng. 2011;108: 264–276.

Microbial Iron Cycling in Acidic Geothermal Springs of Yellowstone National Park: Integrating Molecular Surveys, Geochemical Processes, and Isolation of Novel Fe-Active Microorganisms

Geochemical, molecular, and physiological analyses of microbial isolates were combined to study the geomicrobiology of acidic iron oxide mats in Yellowstone National Park. Nineteen sampling locations from 11 geothermal springs were studied ranging in temperature from 53 to 88°C and pH 2.4 to 3.6. All iron oxide mats exhibited high diversity of crenarchaeal sequences from the Sulfolobales, Thermoproteales, and Desulfurococcales. The predominant Sulfolobales sequences were highly similar to Metallosphaera yellowstonensis str. MK1, previously isolated from one of these sites. Other groups of archaea were consistently associated with different types of iron oxide mats, including undescribed members of the phyla Thaumarchaeota and Euryarchaeota. Bacterial sequences were dominated by relatives of Hydrogenobaculum spp. above 65–70°C, but increased in diversity below 60°C. Cultivation of relevant iron-oxidizing and iron-reducing microbial isolates included Sulfolobus str. MK3, Sulfobacillus str. MK2, Acidicaldus str. MK6, and a new candidate genus in the Sulfolobales referred to as Sulfolobales str. MK5. Strains MK3 and MK5 are capable of oxidizing ferrous iron autotrophically, while strain MK2 oxidizes iron mixotrophically. Similar rates of iron oxidation were measured for M. yellowstonensis str. MK1 and Sulfolobales str. MK5. Biomineralized phases of ferric iron varied among cultures and field sites, and included ferric oxyhydroxides, K-jarosite, goethite, hematite, and scorodite depending on geochemical conditions. Strains MK5 and MK6 are capable of reducing ferric iron under anaerobic conditions with complex carbon sources. The combination of geochemical and molecular data as well as physiological observations of isolates suggests that the community structure of acidic Fe mats is linked with Fe cycling across temperatures ranging from 53 to 88°C.

Dissimilatory Reduction and Transformation of Ferrihydrite-Humic Acid Coprecipitates

Organic matter (OM) is present in most terrestrial environments and is often found coprecipitated with ferrihydrite (Fh). Sorption or coprecipitation of OM with Fe oxides has been proposed to be an important mechanism for long-term C preservation. However, little is known about the impact of coprecipitated OM on reductive dissolution and transformation of Fe(III) (oxyhydr)oxides. Thus, we study the effect of humic acid (HA) coprecipitation on Fh reduction and secondary mineral formation by the dissimilatory Fe(III)-reducing bacterium Shewanella putrefaciens strain CN32. Despite similar crystal structure for all coprecipitates investigated, resembling 2-line Fh, the presence of coprecipitated HA resulted in lower specific surface areas. In terms of reactivity, coprecipitated HA resulted in slower Fh bioreduction rates at low C/Fe ratios (i.e., C/Fe ≤ 0.8), while high C/Fe ratios (i.e., C/Fe ≥ 1.8) enhanced the extent of bioreduction compared to pure Fh. The coprecipitated HA also altered the secondary Fe mineralization pathway by inhibiting goethite formation, reducing the amount of magnetite formation, and increasing the formation of a green rust-like phase. This study indicates that coprecipitated OM may influence the rates, pathway, and mineralogy of biogeochemical Fe cycling and anaerobic Fe respiration within soils.

Steroid hormone runoff from agricultural test plots applied with municipal biosolids

The potential presence of steroid hormones in runoff from sites where biosolids have been used as agricultural fertilizers is an environmental concern. A study was conducted to assess the potential for runoff of seventeen different hormones and two sterols, including androgens, estrogens, and progestogens from agricultural test plots. The field containing the test plots had been applied with biosolids for the first time immediately prior to this study. Target compounds were isolated by solid-phase extraction (water samples) and pressurized solvent extraction (solid samples), derivatized, and analyzed by gas chromatography-tandem mass spectrometry. Runoff samples collected prior to biosolids application had low concentrations of two hormones (estrone <0.8 to 2.23 ng L(-1) and androstenedione <0.8 to 1.54 ng L(-1)) and cholesterol (22.5 ± 3.8 μg L(-1)). In contrast, significantly higher concentrations of multiple estrogens (<0.8 to 25.0 ng L(-1)), androgens (<2 to 216 ng L(-1)), and progesterone (<8 to 98.9 ng L(-1)) were observed in runoff samples taken 1, 8, and 35 days after biosolids application. A significant positive correlation was observed between antecedent rainfall amount and hormone mass loads (runoff). Hormones in runoff were primarily present in the dissolved phase (<0.7-μm GF filter), and, to a lesser extent bound to the suspended-particle phase. Overall, these results indicate that rainfall can mobilize hormones from biosolids-amended agricultural fields, directly to surface waters or redistributed to terrestrial sites away from the point of application via runoff. Although concentrations decrease over time, 35 days is insufficient for complete degradation of hormones in soil at this site.

Spills of Hydraulic Fracturing Chemicals on Agricultural Topsoil: Biodegradation, Sorption, and Co-contaminant Interactions

Hydraulic fracturing frequently occurs on agricultural land. Yet the extent of sorption, transformation, and interactions among the numerous organic frac fluid and oil and gas wastewater constituents upon environmental release is hardly known. Thus, this study aims to advance our current understanding of processes that control the environmental fate and toxicity of commonly used hydraulic fracturing chemicals. Poly(ethylene glycol) surfactants were completely biodegraded in agricultural topsoil within 42-71 days, but their transformation was impeded in the presence of the biocide glutaraldehyde and was completely inhibited by salt at concentrations typical for oil and gas wastewater. At the same time, aqueous glutaraldehyde concentrations decreased due to sorption to soil and were completely biodegraded within 33-57 days. While no aqueous removal of polyacrylamide friction reducer was observed over a period of 6 months, it cross-linked with glutaraldehyde, further lowering the biocides aqueous concentration. These findings highlight the necessity to consider co-contaminant effects when we evaluate the risk of frac fluid additives and oil and gas wastewater constituents in agricultural soils in order to fully understand their human health impacts, likelihood for crop uptake, and potential for groundwater contamination.

Production of Eight Different Hydride Complexes and Nitrite Release from 2,4,6-Trinitrotoluene by Yarrowia lipolytica

ABSTRACT 2,4,6-Trinitrotoluene (TNT) transformation by the yeast strain Yarrowia lipolytica AN-L15 was shown to occur via two different pathways. Direct aromatic ring reduction was the predominant mechanism of TNT transformation, while nitro group reduction was observed to be a minor pathway. Although growth of Y. lipolytica AN-L15 was inhibited initially in the presence of TNT, TNT transformation was observed, indicating that the enzymes necessary for TNT reduction were present initially. Aromatic ring reduction resulted in the transient accumulation of eight different TNT-hydride complexes, which were characterized using high-performance liquid chromatography, UV-visible diode array detection, and negative-mode atmospheric pressure chemical ionization mass spectrometry (APCI-MS). APCI-MS analysis revealed three different groups of TNT-hydride complexes with molecular ions at m/z 227, 228, and 230, which correspond to TNT-mono- and dihydride complexes and protonated dihydride isomers, respectively. One of the three protonated dihydride complex isomers detected appears to release nitrite in the presence of strain AN-L15. This release of nitrite is of particular interest since it can provide a pathway towards complete degradation and detoxification of TNT.