Browsing by Author "Borch, Thomas"

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Biocides in hydraulic fracturing fluids: A critical review of their usage, mobility, degradation, and toxicity
(2015-01) Kahrilas, G. A.; Blotevogel, J.; Stewart, Philip S.; Borch, Thomas
Microbes tend to attach to available surfaces and readily form biofilms, which is problematic in healthcare settings. Biofilms are traditionally associated with wet or damp surfaces such as indwelling medical devices and tubing on medical equipment. However, microbes can survive for extended periods in a desiccated state on dry hospital surfaces, and biofilms have recently been discovered on dry hospital surfaces. Microbes attached to surfaces and in biofilms are less susceptible to biocides, antibiotics and physical stress. Thus, surface attachment and/or biofilm formation may explain how vegetative bacteria can survive on surfaces for weeks to months (or more), interfere with attempts to recover microbes through environmental sampling, and provide a mixed bacterial population for the horizontal transfer of resistance genes. The capacity of existing detergent formulations and disinfectants to disrupt biofilms may have an important and previously unrecognized role in determining their effectiveness in the field, which should be reflected in testing standards. There is a need for further research to elucidate the nature and physiology of microbes on dry hospital surfaces, specifically the prevalence and composition of biofilms. This will inform new approaches to hospital cleaning and disinfection, including novel surfaces that reduce microbial attachment and improve microbial detachment, and methods to augment the activity of biocides against surface-attached microbes such as bacteriophages and antimicrobial peptides. Future strategies to address environmental contamination on hospital surfaces should consider the presence of microbes attached to surfaces, including biofilms.
Biodegradation of chlorinated solvents in a water unsaturated topsoil
(2003-04) Borch, Thomas; Ambus, Per; Laturnus, Frank; Svensmark, Bo; Grøn, Christian
In order to investigate topsoils as potential sinks for chlorinated solvents from the atmosphere, the degradation of trichloromethane (CHCl3), 1,1,1-trichloroethane (CH3CCl3), tetrachloromethane (CCl4), trichloroethene (C2HCl3) and tetrachloroethene (C2Cl4) was studied in anoxic laboratory experiments designed to simulate denitrifying conditions in water unsaturated topsoil. Active denitrification was demonstrated by measuring the release of 15N in N2 to the headspace from added 15N labeled nitrate. The degradation of chlorinated aliphatic compounds was followed by measuring their concentrations in the headspace above the soil. The headspace concentrations of all the chlorinated solvents except CH3CCl3 were significantly (P⩽0.05) lower after 41 days in biologically active batches as compared to sterile batches. For the compounds with significantly decreasing headspace concentrations, the decline was the least for CHCl3 within the 41 days of incubation. The headspace concentrations of trichloro- and tetrachloroethene decreased more than 50% during the first 20 days with no considerable indication of abiotic transformation. While slow abiotic removal was observed, tetrachloromethane was completely biotransformed after 16 days. Based on the results in this study, we conclude that anaerobic topsoils are potential sinks for these contaminants, and that a natural attenuation potential exists, even in water unsaturated topsoils.
Catalysis of PAH biodegradation by humic acid shown in synchrotron infrared studies
(2002-03) Holman, Hoi-Ying N.; Nieman, Karl; Sorensen, Darwin L.; Miller, Charles D.; Martin, Michael C.; Borch, Thomas; McKinney, Wayne R.; Sims, R. C.
The role of humic acid (HA) in the biodegradation of toxic polycyclic aromatic hydrocarbons (PAHs) has been the subject of controversy, particularly in unsaturated environments. By utilizing an infrared spectromicroscope and a very bright, nondestructive synchrotron photon source, we monitored in situ and, over time, the influence of HA on the progression of degradation of pyrene (a model PAH) by a bacterial colony on a magnetite surface. Our results indicate that HA dramatically shortens the onset time for PAH biodegradation from 168 to 2h. In the absence of HA, it takes the bacteria about 168 h to produce sufficient glycolipids to solubilize pyrene and make it bioavailable for biodegradation. These results will have large implications for the bioremediation of contaminated soils.
Chromatographic, spectroscopic and microscopic analyses reveal the impact of iron oxides and electron shuttles on the degradation pathway of 2,4,6- trinitrotoluene (TNT) by a fermenting bacterium
(Montana State University - Bozeman, College of Agriculture, 2003) Borch, Thomas; Chairperson, Graduate Committee: William P. Inskeep and Robin Gerlach (co-chair)
Contamination of surface and subsurface environments with explosives such as 2,4,6-trinitrotoluene (TNT) is a worldwide problem. The fate and analysis of TNT were investigated in numerous artificially contaminated model systems. We developed a unique high performance liquid chromatography gradient elution method for the analysis of commonly observed TNT metabolites and EPA explosives. Column temperature was identified as the key parameter for optimal separation. Iron (hydr)oxides play an important role in the reduction, sorption and fate of TNT in soil and sediment. Consequently, characterization of the nature and properties of natural and synthetic Fe (hydr)oxides is important for determining reaction mechanisms and surface-associated chemical processes. This work thus summarizes the potential applicability of imaging and spectroscopic techniques for eliciting chemical and physical properties of iron (hydr)oxides. TNT is persistent in soils due to its low redox potential and sorption. Batch and column studies revealed some of the first results on TNT desorption behavior in two well-defined model soil systems. Biosurfactants were found to be the most promising technique for enhanced TNT desorption. Batch studies with a Cellulomonas sp. in the presence of ferrihydrite and the electron shuttle anthraquinone-2,6-disulfonate (AQDS) were conducted to reveal biotic and abiotic mechanisms contributing to the degradation of TNT. Strain ES6 was found to reduce TNT and ferrihydrite with enhanced reduction in the presence of AQDS. Ferrihydrite stimulated the formation of more reduced TNT metabolites such as 2,4-diamino-6-nitrotoluene. Interestingly, a completely different degradation pathway was observed in AQDS-amended iron-free cell suspensions, showing a rapid transformation of TNT to 2,4-dihydroxylamino-6-nitrotoluene, which transformed into unidentified polar products. The influence of iron phases (i.e. hematite, magnetite, and ferrihydrite) and secondary Fe mineral formation on the degradation of TNT was also evaluated. The initial reduction of TNT was fastest in the presence of hematite; however, the further reduction of hydroxylamino-dinitrotoluenes was fastest, in the presence of magnetite and ferrihydrite (no AQDS). The impact of AQDS was predominant in the presence of hematite resulting in the formation of 2,4,6-triaminotoluene. Ferrihydrite underwent reductive dissolution with the formation of secondary hematite. The enhanced TNT reduction in ferfihydrite-amended systems was therefore most likely due to redox-active Fe(II) rather than secondary Fe phases.
Evaluation of Characterization Techniques for Iron Pipe Corrosion Products and Iron Oxide Thin Films
(2008-10) Borch, Thomas; Camper, Anne K.; Biederman, Joel A.; Butterfield, Phillip W.; Gerlach, Robin; Amonette, James E.
A common problem faced by drinking water studies is that of properly characterizing the corrosion products (CP) in iron pipes or synthetic Fe (hydr)oxides used to simulate the iron pipe used in municipal drinking-water systems. The present work compares the relative applicability of a suite of imaging and analytical techniques for the characterization of CPs and synthetic Fe oxide thin films and provide an overview of the type of data that each instrument can provide as well as their limitations to help researchers and consultants choose the best technique for a given task. Crushed CP from a water distribution system and synthetic Fe oxide thin films formed on glass surfaces were chosen as test samples for this evaluation. The CP and synthetic Fe oxide thin films were analyzed by atomic force microscopy (AFM), scanning electron microscopy (SEM), energy-dispersive spectroscopy, time-of-flight secondary ion mass spectrometry(ToF-SIMS), X-ray powder diffractometry (XRD), grazing incident diffractometry (GID), transmission electron microscopy (TEM), selected area electron diffraction, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared, MÃ¶ssbauer spectroscopy, Brunauerâ€“Emmettâ€“Teller N2 adsorption and Fe concentration was determined by the ferrozine method. XRD and GID were found to be the most suitable techniques for identification of the mineralogical composition of CP and synthetic Fe oxide thin films, respectively. AFM and a combined ToF-SIMSâ€“AFM approach proved excellent for roughness and depth profiling analysis of synthetic Fe oxide thin films, respectively. Corrosion products were difficult to study by AFM due to their surface roughness, while synthetic Fe oxide thin films resisted most spectroscopic methods due to their limited thickness (118 nm). XPS analysis is not recommended for mixtures of Fe (hydr)oxides due to their spectral similarities. SEM and TEM provided great detail on mineralogical morphology.
Heavy metal-mineral associations in Coeur d'Alene River sediments: A synchrotron-based analysis
(2009-12) Moberly, James G.; Borch, Thomas; Sani, Rajesh K.; Spycher, Nicolas; Şengör, S. Sevinç; Ginn, Timothy R.; Peyton, Brent M.
Nearly a century of mining activities upstream have contaminated Lake Coeur d’Alene and its tributaries with Pb, Zn, and other heavy metals. Heavy metal concentrations in sediments of the Coeur d’Alene watershed have been shown to be inversely proportional to the sediment size fraction; thus, analysis on a very small scale is essential to determine the mobility and stability of heavy metals in this environment. Micron-scale synchrotron-based methods were used to determine the association of heavy metals with solid phases in sediments of the Coeur d’Alene River. Bulk X-ray diffraction (XRD), extended X-ray absorption fine structure spectroscopy, and synchrotron-based microfocused XRD combined with microfocused X-ray fluorescence mapping indicate the presence of crystalline Pb- and Zn-bearing mineral phases of dundasite [Pb2Al4(CO3)4(OH)8·3H2O], coronadite [PbMn8O16], stolzite [PbWO4], mattheddleite [Pb10(SiO4)3.5(SO4)2Cl2], bindheimite [Pb2Sb2O7], and smithsonite [ZnCO3]. Likely phases for Zn and Pb adsorption were ferrihydrite, diaspore [AlO(OH)], manganite [Mn(III)O(OH)], muscovite [KAl2(Si3Al)O10(OH,F)2], biotite [K(Fe,Mg)3AlSi3O10(F,OH)2], and montmorillonite [Na0.3(Al,Mg)2Si4O10(OH)2·8H2O]. The large predominance of Fe and Mn (hydr)oxides over other sorbent minerals suggests that the metal sorption behavior is dominated by these (hydr)oxide phases.
Impact of ferrihydrite and anthraquinone-2,6-disulfonate on the reductive transformation of 2,4,6-trinitrotoluene by a gram-positive fermenting bacterium
(2005-09) Borch, Thomas; Inskeep, William P.; Harwood, Jace A.; Gerlach, Robin
Batch studies were conducted to explore differences in the transformation pathways of 2,4,6-trinitrotoluene (TNT) reduction by a Gram-positive fermenting bacterium (Cellulomonas sp. strain ES6) in the presence and absence of ferrihydrite and the electron shuttle anthraquinone-2,6-disulfonate (AQDS). Strain ES6 was capable of TNT and ferrihydrite reduction with increased reduction rates in the presence of AQDS. Hydroxylaminodinitrotoluenes, 2,4-dihydroxylamino-6-nitrotoluene (2,4-DHANT), and tetranitroazoxytoluenes were the major metabolites observed in ferrihydrite- and AQDS-free systems in the presence of pure cell cultures. Ferrihydrite enhanced the production of amino derivatives because of reactions with microbially produced surface-associated Fe(II). The presence of AQDS in the absence of ferrihydrite promoted the fast initial formation of arylhydroxylamines such as 2,4-DHANT. However, unlike in pure cell systems, these arylhydroxylamines were transformed into several unidentified polar products. When both microbially reduced ferrihydrite and AQDS were present simultaneously, the reduction of TNT was more rapid and complete via pathways that would have been difficult to infer solely from single component studies. This study demonstrates the complexity of TNT degradation patterns in model systems where the interactions among bacteria, Fe minerals, and organic matter have a pronounced effect on the degradation pathway of TNT.
Microbial acceleration of aerobic pyrite oxidation at circumneutral pH
(2017-09) Percak-Dennett, E.; He, Shaomei; Converse, B.J.; Konishi, H.; Xu, Huifang; Corcoran, A.; Noguera, D.; Chan, C.; Bhattacharyya, A.; Borch, Thomas; Boyd, Eric S.; Roden, Eric E.
Pyrite (FeS2) is the most abundant sulfide mineral on Earth and represents a significant reservoir of reduced iron and sulfur both today and in the geologic past. In modern environments, oxidative transformations of pyrite and other metal sulfides play a key role in terrestrial element partitioning with broad impacts to contaminant mobility and the formation of acid mine drainage systems. Although the role of aerobic micro-organisms in pyrite oxidation under acidic-pH conditions is well known, to date there is very little known about the capacity for aerobic micro-organisms to oxidize pyrite at circumneutral pH. Here, we describe two enrichment cultures, obtained from pyrite-bearing subsurface sediments, that were capable of sustained cell growth linked to pyrite oxidation and sulfate generation at neutral pH. The cultures were dominated by two Rhizobiales species (Bradyrhizobium sp. and Mesorhizobium sp.) and a Ralstonia species. Shotgun metagenomic sequencing and genome reconstruction indicated the presence of Fe and S oxidation pathways in these organisms, and the presence of a complete Calvin–Benson–Bassham CO2 fixation system in the Bradyrhizobium sp. Oxidation of pyrite resulted in thin (30–50 nm) coatings of amorphous Fe(III) oxide on the pyrite surface, with no other secondary Fe or S phases detected by electron microscopy or X-ray absorption spectroscopy. Rates of microbial pyrite oxidation were approximately one order of magnitude higher than abiotic rates. These results demonstrate the ability of aerobic microbial activity to accelerate pyrite oxidation and expand the potential contribution of micro-organisms to continental sulfide mineral weathering around the time of the Great Oxidation Event to include neutral-pH environments. In addition, our findings have direct implications for the geochemistry of modern sedimentary environments, including stimulation of the early stages of acid mine drainage formation and mobilization of pyrite-associated metals.
Multiple mechanisms of uranium immobilization by Cellulomonas sp. strain ES6
(2011-02) Sivaswamy, V.; Boyanov, M. I.; Peyton, Brent M.; Viamajala, Sridhar; Gerlach, Robin; Apel, William A.; Sani, Rajesh K.; Dohnalkova, Alice; Kemner, K. M.; Borch, Thomas
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 POâ‚„Â³â ». 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
Production of eight different hydride complexes and nitrite release from 2,4,6-trinitrotoluene by Yarrowia lipolytica
(2007-10) Ziganshin, Ayrat M.; Gerlach, Robin; Borch, Thomas; Naumov, A. V.; Naumova, R. P.
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.
Resolving biogeochemical phenomena at high spatial resolution through electron microscopy
(2008-06) Geesey, Gill G.; Borch, Thomas; Reardon, Catherine L.
Our understanding of microbe-metal interactions has advanced dramatically since the mid-1970s when little was known about the reactivity of bacterial cell wall components toward metal ions in the extracellular milieu. Although certain metals such as and Pb+ were known to react with components of bacterial cell walls and used to visualize their structure by electron microscopy (Garland et al., 1975), little physicochemical data were available on the specificity and sites of interactions (Humphrey & Vincent, 1966; Heptinstall et al., 1970; Irvin et al., 1975; Lambert et al., 1975; Raymond & MacLeod, 1975). Furthermore, there were no model systems to explorethe mechanisms of these interactions. This began to change when Beveridge and Murray used isolated cell walls of Bacillus subtilis to quantify metal ion binding to wall components. Beveridge demonstrated that cell walls concentrated cations such as Mg++, Na+, K+, Cu++ and Fe+++, but not Ba++, Li+ or Al+++ (Beveridge & Murray, 1976). Since these initial studies, Beveridge and his students and collaborators have contributed greatly to our understanding of the complex interactions between microbial cell surface polymers and metals in the environment. As fellow scientists working in this research area, we have developed a deep admiration of Beveridge’s scientific insight, technical skills and collegial demeanor. Not surprisingly, Beveridge’s research has had a significant impact on our research, as well as on the research of our collaborators and colleagues, and will likely influence the work of future generations of scientists working in the field of geobiology. Some examples are cited below.
Terrestrial natural sources of trichloromethane (chloroform,chcl3) - an overview
(2002-09) Laturnus, Frank; Haselmann, Kim F.; Borch, Thomas; Gron, Christian
The widespread use of volatile chlorinated compounds like chloroform, trichloroethene and tetrachloroethene in industrialized societies causes a large annual release of these compounds into the environment. Due to their role as a source for halogen radicals involved in various catalytic atmospheric reaction cycles, including the regulation of the stratospheric and tropospheric ozone layers, these compounds also constitute a risk for drinking water resources as they can be transported to the groundwater from contaminated field sites or even from atmospheric deposition. Therefore, identification and investigation of sources and sinks of volatile chlorinated compounds are of particular interest. Chloroform, a major contributor to natural gaseous chlorine, was found to be emitted by several anthropogenic and natural sources including the oceans and terrestrial areas. The origin of chloroform in the terrestrial environment can be anthropogenic point sources, atmospheric deposition, release by vegetation and production directly in the soil. The calculated annual biogenic global chloroform emission is 700 Gg, and marine and terrestrial environments are nearly equal contributors. The estimated emissions from anthropogenic sources account for less than 10% of the estimated total emissions from all sources. Among terrestrial sources, forests have recently been identified as contributing to the release of chloroform into the environment. With the data available, annual emissions of chloroform to the atmosphere from forest sites were calculated and compared to other natural sources. At present knowledge, forests are only a minor source in the total biogenic flux of chloroform, contributing less than 1% to the annual global atmospheric input. However, it should be noted that data are available for Northern temperate forests only. The large tropical forest areas may provide a yet unknown input of chloroform.
Use of reversed-phase high-performance liquid chromatography-diode array detection for complete separation of 2,4,6-trinitrotoluene metabolites and EPA Method 8330 explosives: Influence of temperature and an ion-pair reagent
(2004-01) Borch, Thomas; Gerlach, Robin
Explosives such as 2,4,6-trinitrotoluene (TNT), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) are widely distributed environmental contaminants. Complete chromatographic separation is necessary in order to accurately determine and quantify explosives and their degradation products in environmental samples and in (bio)transformation studies. The present study describes a RP-HPLC method with diode array detection using a LC-8 guard column, a Supelcosil LC-8 chromatographic column, and a gradient elution system. This gradient method is capable of baseline separating the most commonly observed explosives and TNT transformation metabolites including 2,4,6-triaminotoluene (TAT) in a single run. The TNT metabolites separated were 2-hydroxylamino-4,6-dinitrotoluene, 4-hydroxylamino-2,6-dinitrotoluene, 2,4-dihydroxylamino-6-nitrotoluene, 4,4',6,6'-tetranitro-2,2'-azoxytoluene, 2,2',6,6'-tetranitro-4,4'-azoxytoluene, 4,4',6,6'-tetranitro-2,2'-azotoluene, 2,2',6,6'-tetranitro-4,4'-azotoluene, 2-amino-4,6-dinitrotoluene, 4-amino-2,6-dinitrotoluene, 2,6-diamino-4-nitrotoluene, 2,4-diamino-6-nitrotoluene, and TAT. The same gradient method at a different column temperature can also be used to baseline separate the explosives targeted in the Environmental Protection Agency (EPA) Method 8330 with approximately 22% reduction in total run time and 48% decrease in solvent consumption compared to previously published methods. Good separation was also obtained when all TNT metabolites and EPA Method 8330 compounds (a total of 23 compounds) were analyzed together; only 2,6-DANT and HMX co-eluted in this case. The influence of temperature (35B55 C) and the use of an ion-pair reagent on the chromatographic resolution and retention were investigated. Temperature was identified as the key parameter for optimal baseline separation. Increased temperature resulted in shorter retention times and better peak resolution especially for the aminoaromatics investigated. The use of an ion-pair reagent (octanesulfonic acid) generally resulted in longer retention times for compounds containing amine functional groups, more baseline noise, and decreased peak resolution.