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USGS2001

Effect of redox conditions on MTBE biodegradation in surface water Sediments

Microbial degradation of methyl tert-butyl ether (MTBE) was observed in surface water-sediment microcosms under anaerobic conditions. The efficiency and products of anaerobic MTBE biodegradation were dependent on the predominant terminal electron-accepting conditions. In the presence of substantial methanogenic activity, MTBE biodegradation was nominal and involved reduction of MTBE to the toxic product, tert-butyl alcohol (TBA). In the absence of significant methanogenic activity, accumulation of [14C]TBA generally decreased, and mineralization of [U-14C]MTBE to 14CO2 generally increased as the oxidative potential of the predominant terminal electron acceptor increased in the order of SO4, Fe(III), Mn(IV) < NO3 < O2. Microbial mineralization of MTBE to CO2 under Mn(IV)or SO4-reducing conditions has not been reported previously. The results of this study indicate that microorganisms inhabiting the sediments of streams and lakes can degrade MTBE effectively under a range of anaerobic terminal electron-accepting conditions. Thus, anaerobic bed sediment microbial processes may provide a significant environmental sink for MTBE in surface water systems throughout the United States.

Environmental Science & Technology↗

USGS2009

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.

Environmental Science & Technology↗

USGS1999

Denitrification in marine shales in northeastern Colorado

Parts of the South Platte River alluvial aquifer in northeastern Colorado are underlain by the Pierre Shale, a marine deposit of Late Cretaceous age that is <1000 m thick. Ground water in the aquifer is contaminated with NO 3 ‐ , and the shale contains abundant potential electron donors for denitrification in the forms of organic carbon and sulfide minerals. Nested piezometers were sampled, pore water was squeezed from cores of shale, and an injection test was conducted to determine if denitrification in the shale was a sink for alluvial NO 3 − and to measure denitrification rates in the shale. Measured values of NO 3 − , N 2 , NH 4 + , δ 15 N[NO 3 − ], δ 15 N[N 2 ], and δ 15 N[NH 4 + ] in the alluvial and shale pore water indicated that denitrification in the shale was a sink for alluvial NO 3 − . Chemical gradients, reaction rate constants, and hydraulic head data indicated that denitrification in the shale was limited by the slow rate of NO 3 − transport (possibly by diffusion) into the shale. The apparent in situ first‐order rate constant for denitrification in the shale based on diffusion calculations was of the order of 0.04–0.4 yr −1 , whereas the potential rate constant in the shale based on injection tests was of the order of 60 yr −1 . Chemical data and mass balance calculations indicate that organic carbon was the primary electron donor for denitrification in the shale during the injection test, and ferrous iron was a minor electron donor in the process. Flux calculations for the conditions encountered at the site indicate that denitrification in the shale could remove only a small fraction of the annual agricultural NO 3 ‐ input to the alluvial aquifer. However, the relatively large potential first‐order rate constant for denitrification in the shale indicated that the percentage of NO 3 − uptake by the shale could be considerably larger in areas where NO 3 − advection.

Colorado↗

USGS2002

Denitrification in the recharge area and discharge area of a transient agricultural nitrate plume in a glacial outwash sand aquifer, Minnesota

Recharge rates of nitrate (NO 3 − ) to groundwater beneath agricultural land commonly are greater than discharge rates of NO 3 − in nearby streams, but local controls of NO 3 − distribution in the subsurface generally are poorly known. Groundwater dating (CFC, 3 H) was combined with chemical (ions and gases) and stable isotope (N, S, and C) analyses to resolve the effects of land use changes, flow patterns, and water‐aquifer reactions on the distributions of O 2 , NO 3 − , SO 4 = , and other constituents in a two‐dimensional vertical section leading from upland cultivated fields to a riparian wetland and stream in a glacial outwash sand aquifer near Princeton, Minnesota. Within this section a “plume” of oxic NO 3 − ‐rich groundwater was present at shallow depths beneath the fields and part of the wetland but terminated before reaching the stream or the wetland surface. Groundwater dating and hydraulic measurements indicate travel times in the local flow system of 0 to >40 years, with stratified recharge beneath the fields, downward diversion of the shallow NO 3 − ‐bearing plume by semiconfining organic‐rich valley‐filling sediments under the wetland and upward discharge across the valley and stream bottom. The concentrations and δ 15 N values of NO 3 − and N 2 indicate that the NO 3 − plume section was bounded in three directions by a curvilinear zone of active denitrification that limited its progress; however, when recalculated to remove the effects of denitrification, the data also indicate changes in both the concentrations and δ 15 N values of NO 3 − that was recharged in the past. Isotope data and mass balance calculations indicate that FeS 2 and other ferrous Fe phases were the major electron donors for denitrification in at least two settings: (1) within the glacial‐fluvial aquifer sediments beneath the recharge and discharge areas and (2) along the bottom of the valley‐filling sediments in the discharge area. Combined results indicate that the shape and progress of the oxic NO 3 − plume termination were controlled by a combination of (1) historical and spatial variations in land use practices, (2) contrast in groundwater flow patterns between the agricultural recharge area and riparian wetland discharge area, and (3) distribution and abundance of electron donors in both the sand aquifer and valley‐filling sediments. The data are consistent with slow migration of redox zones through the aquifer in response to recharging oxic groundwater during Holocene time, then an order‐of‐magnitude increase in the flux of electron acceptors as a result of agricultural NO 3 − contamination in the late twentieth century, to which the redox zone configuration still may be adjusting. The importance of denitrification for NO 3 − movement through formerly glaciated terrains should depend on the source areas and depositional environments of the glacial sediments, as well as geomorphology and recent stream‐valley sediment history.

Water Resources Research↗

USGS2010

Characterization of microbial arsenate reduction in the anoxic bottom waters of Mono Lake, California

Dissimilatory reduction of arsenate (DAsR) occurs in the arsenic-rich, anoxic water column of Mono Lake, California, yet the microorganisms responsible for this observed in situ activity have not been identified. To gain insight as to which microorganisms mediate this phenomenon, as well as to some of the biogeochemical constraints on this activity, we conducted incubations of arsenate-enriched bottom water coupled with inhibition/amendment studies and Denaturing Gradient Gel Electrophoresis (DGGE) characterization techniques. DAsR was totally inhibited by filter-sterilization and by nitrate, partially inhibited (~50%) by selenate, but only slightly (~25%) inhibited by oxyanions that block sulfate-reduction (molybdate and tungstate). The apparent inhibition by nitrate, however, was not due to action as a preferred electron acceptor to arsenate. Rather, nitrate addition caused a rapid, microbial re-oxidation of arsenite to arsenate, which gave the overall appearance of no arsenate loss. A similar microbial oxidation of As(III) was also found with Fe(III), a fact that has implications for the recycling of As(V) in Mono Lake's anoxic bottom waters. DAsR could be slightly (10%) stimulated by substrate amendments of lactate, succinate, malate, or glucose, but not by acetate, suggesting that the DAsR microflora is not electron donor limited. DGGE analysis of amplified 16S rDNA gene fragments from incubated arsenate-enriched bottom waters revealed the presence of two bands that were not present in controls without added arsenate. The resolved sequences of these excised bands indicated the presence of members of the epsilon (Sulfurospirillum) and delta (Desulfovibrio) subgroups of the Proteobacteria, both of which have representative species that are capable of anaerobic growth using arsenate as their electron acceptor.

California↗

USGS2000

Controlled field study on the use of nitrate and oxygen for bioremediation of a gasoline source zone

Controlled releases of unleaded gasoline were utilized to evaluate the biotransformation of the soluble aromatic hydrocarbons (benzene, toluene, ethylbenzene, xylene isomers, trimethylbenzene isomers, and naphthalene) within a source zone using nitrate and oxygen as electron acceptors. Experiments were conducted within two 2 m ?? 2 m ?? 3.5 m deep sheet-piling cells. In each treatment cell, a gasoline-contaminated zone was created below the water table. Groundwater amended with electron acceptors was then flushed continuously through the cells for 174 day. Electron-acceptor utilization and hydrocarbon-metabolite formation were noted in both cells, indicating that some microbial activity had been induced in response to flushing. Relative to the cell residence time, nitrate utilization was slow and aromatic-hydrocarbon mass losses in response to microaerophilic dissolved oxygen addition were not obvious under these in situ conditions. There was relatively little biotransformation of the aromatic hydrocarbons over the 2-m flow path monitored in this experiment. A large denitrifying population capable of aromatic hydrocarbon biotransformation failed to develop within the gasoline source zone over a 14-mo period of nitrate exposure.

Bioremediation Journal↗

USGS2024

Compositional and structural mapping of Northwest Africa 15507 angrite

Angrite meteorites represent interesting sampling of planetary crustal environments. Quench-textured angrites with strong crystal zoning originated from the shallow surface region, with evidence of reducing conditions during solidification. Plutonic angrites have more coarse-grained igneous and metamorphic textures with comparatively less zoning and are interpreted as having equilibrated at greater depth. Plutonic angrites contain the minerals magnetite Fe 3 O 4 comprised of Fe 2+ and Fe 3+ , and rhönite, where Fe 3+ is required by inspection of mineral stoichiometry. NWA 15507 is a plutonic angrite with a microgabbroic texture (mean grainsize ∼1.4 mm) composed of zoned Al-Ti-augite, Ca-bearing olivine, anorthite, with accessory kirschsteinite, rhönite, hercynite, low-Ni kamacite, merrillite, Ti-free magnetite and troilite [ 1 ]. Rhönite analyzed by electron-probe microanalysis (EPMA) has the formula Ca 2.04 (Mg 0.32 Fe 2+ 4.25 Fe 3+ 0.47 Ti 0.33 Al 0.61 )(Si 3.74 Al 2.26 )O 20 , where Fe 3+ was estimated by stoichiometric analysis. During preliminary cathodoluminescence (CL) analysis, complex subgrain and oscillatory zoning was observed in the anorthite. In this study we use a combined approach of electron probe microanalysis (EPMA), cathodoluminescence (CL), electron-backscatter diffraction (EBSD), and laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) to further investigate the anorthite and distribution of Fe 3+ in NWA 15507.

Microscopy and Microanalysis↗

USGS2016

Do intracoelomic telemetry transmitters alter the post-release behaviour of migratory fish?

Electronic tags have become a common tool in fish research, enhancing our understanding of how fish interact with their environment and move among different habitats, for estimating mortality and recording internal physiological states. An often-untested assumption of electronic tagging studies is that tagged fish are representative of untagged conspecifics and thus show ‘normal’ behaviour (e.g. movement rates, swimming activity, feeding). Here, we use a unique data set for potamadromous walleye (Sander vitreus) in Lake Huron and Lake Erie tributaries to assess whether the lack of appropriate controls in electronic tagging could seriously affect behavioural data. We used fish tagged in previous years and compared their migratory behaviour during the spawning season to fish tagged in a current year at the same location. The objective of the study was to determine whether intracoelomic acoustic tag implantation altered downstream movement of walleye after spawning. Fish tagged in a given season travelled slower downstream from two river spawning sites than fish tagged in previous years. Fish tagged one or two years earlier showed no differences between each other in downstream travel time, in contrast to fish tagged in a given year. Our results support notions that standard collection and intracoelomic tagging procedures can alter short-term behaviour (i.e. days, weeks, months), and as such, researchers should use caution when interpreting data collected over such time periods. Further, whenever possible, researchers should also explicitly evaluate post-tagging effects on behaviour as part of their experimental objectives.

Maumee Bay, Saginaw Bay↗

USGS2020

Evaluating the utility of principal component analysis on EDS x-ray maps to determine bulk mineralogy

Due to advances in EDS technology, electron microscopy techniques have become an important tool to determine the relative abundance of mineral phases. However, few studies have directly compared EDS X‐ray mineralogy with traditional techniques for assessing bulk mineralogy and elemental composition. We show that analysing a limited area (~ 0.5–3.2 mm 2 ) of fine‐grained metal extraction samples using EDS X‐ray principal component analysis phase mapping yields results that agree within 10% with more traditional techniques for mineral phases present at greater than 5% m / m . Electron beam sensitive minerals, such as the carbonates, have poor correlations between EDS and X‐ray Diffraction (XRD) and/or WD‐XRF. Likewise, poor correlations between methods can be expected for particles that are smaller than the interaction volume of the electron beam (~ 1.5 µm); this strongly affected the phyllosilicates. One strength of EDS phase mapping is that it can identify phases present below the detection limit of powder XRD (< 1%). Our results demonstrate that EDS phase mapping is sufficient to estimate bulk sample mineralogy. If polished thin sections have been prepared, this approach may save time and/or money relative to the more traditional approaches of preparing separate subsamples for XRD and/or WD‐XRF.

Geostandards and Geoanalytical Research↗

USGS2013

Modeling the effects of naturally occurring organic carbon on chlorinated ethene transport to a public supply well

The vulnerability of public supply wells to chlorinated ethene (CE) contamination in part depends on the availability of naturally occurring organic carbon to consume dissolved oxygen (DO) and initiate reductive dechlorination. This was quantified by building a mass balance model of the Kirkwood-Cohansey aquifer, which is widely used for public water supply in New Jersey. This model was built by telescoping a calibrated regional three-dimensional (3D) MODFLOW model to the approximate capture zone of a single public supply well that has a history of CE contamination. This local model was then used to compute a mass balance between dissolved organic carbon (DOC), particulate organic carbon (POC), and adsorbed organic carbon (AOC) that act as electron donors and DO, CEs, ferric iron, and sulfate that act as electron acceptors (EAs) using the Sequential Electron Acceptor Model in three dimensions (SEAM3D) code. SEAM3D was constrained by varying concentrations of DO and DOC entering the aquifer via recharge, varying the bioavailable fraction of POC in aquifer sediments, and comparing observed and simulated vertical concentration profiles of DO and DOC. This procedure suggests that approximately 15% of the POC present in aquifer materials is readily bioavailable. Model simulations indicate that transport of perchloroethene (PCE) and its daughter products trichloroethene (TCE), cis -dichloroethene ( cis -DCE), and vinyl chloride (VC) to the public supply well is highly sensitive to the assumed bioavailable fraction of POC, concentrations of DO entering the aquifer with recharge, and the position of simulated PCE source areas in the flow field. The results are less sensitive to assumed concentrations of DOC in aquifer recharge. The mass balance approach used in this study also indicates that hydrodynamic processes such as advective mixing, dispersion, and sorption account for a significant amount of the observed natural attenuation in this system.

New Jersey↗

USGS2005

Measuring rates of biodegradation in a contaminated aquifer using field and laboratory methods

Rates of biodegradation were measured in a petroleum hydrocarbon-contaminated aquifer using a combination of field and laboratory methods. These methods are based on tracking concentration changes of substrates (both electron donors and acceptors) or final products of microbial metabolism over time. Ground water at the study site (Hanahan, South Carolina) is anoxic, and sulfate reduction is the predominant terminal electron accepting process. Laboratory studies conducted with sediment cored from the site showed that 14 C-toluene was mineralized to 14 CO 2 with a first-order degradation rate constant (k tol ) of -0.01 d −1 under sulfate-reducing conditions. Under nitrate-amended, Fe(III)-amended, or nonamended (methanogenic) conditions, toluene was not significantly mineralized. 14 C-Benzene was degraded at low but measurable rates (k ben = -0.003 d −1 ) under sulfate-reducing conditions whereas degradation under methanogenic conditions was negligible. These results illustrate the extreme sensitivity of laboratory-measured biodegradation rates to terminal electron-accepting conditions, and show the necessity of carefully matching experimental conditions to in situ conditions. Concentration decreases of toluene along aquifer flowpaths, when the uncertainty of ground-water flow velocities was considered, indicated k tol values ranging from -0.0075 to -0.03 d −1 . Concentration decreases of sulfate and concentration increases of dissolved inorganic carbon (DIC), when normalized for assumed stoichiometric oxidation of toluene coupled to sulfate reduction, yielded a k so4 range of -0.005 to -0.02 d −1 , and a k DIC value range of +0.00075 to +0.003 d −1 . Because both laboratory and field methods have numerous sources of uncertainty, a combination of these methods is the most appropriate procedure for evaluating biodegradation rate constants in contaminated ground-water systems.

Groundwater↗

USGS2009

Flowpath independent monitoring of reductive dechlorination potential in a fractured rock aquifer

The flowpath dependent approaches that are typically employed to assess biodegradation of chloroethene contaminants in unconsolidated aquifers are problematic in fractured rock settings, due to difficulties defining discrete groundwater flowpaths in such systems. In this study, the variation in the potential for chloroethene biodegradation with depth was evaluated in a fractured rock aquifer using two flowpath independent lines of field evidence: (1) the presence of the three biochemical prerequisites [electron donor(s), chloroethene electron acceptor(s), and chlororespiring microorganism(s)] for efficient chloroethene chlororespiration and (2) the in situ accumulation of chloroethene reductive dechlorination daughter products. The validity of this approach was assessed by comparing field results with the results of [1, 2‐ 14 C] cis ‐DCE microcosm experiments. Microcosms were prepared with depth‐specific core material, which was crushed and emplaced in discrete packer intervals for 1 year to allow colonization by the indigenous microbial community. Packer intervals characterized by significant electron donor concentrations, elevated numbers of chlororespiring microorganisms, and high reductive dechlorination product to parent contaminant ratios correlated well with the production of 14 C‐labeled reductive dechlorination products in the microcosm experiments. These results indicate that, in the absence of information on discrete groundwater flowpaths, a modified approach emphasizing flowpath independent lines of evidence can provide insight into the temporal and spatial variability of contaminant biodegradation in fractured rock systems.

Ground Water Monitoring and Remediation↗

USGS2010

The onset of metamorphism in ordinary and carbonaceous chondrites

Ordinary and carbonaceous chondrites of the lowest petrologic types were surveyed by X-ray mapping techniques. A variety of metamorphic effects were noted and subjected to detailed analysis using electron microprobe, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and cathodoluminescence (CL) methods. The distribution of Cr in FeO-rich olivine systematically changes as metamorphism increases between type 3.0 and type 3.2. Igneous zoning patterns are replaced by complex ones and Cr-rich coatings develop on all grains. Cr distributions in olivine are controlled by the exsolution of a Cr-rich phase, probably chromite. Cr in olivine may have been partly present as tetrahedrally coordinated Cr 3+ . Separation of chromite is nearly complete by petrologic type 3.2. The abundance of chondrules showing an inhomogeneous distribution of alkalis in mesostasis also increases with petrologic type. TEM shows this to be the result of crystallization of albite. Residual glass compositions systematically change during metamorphism, becoming increasingly rich in K. Glass in type I chondrules also gains alkalis during metamorphism. Both types of chondrules were open to an exchange of alkalis with opaque matrix and other chondrules. The matrix in the least metamorphosed chondrites is rich in S and Na. The S is lost from the matrix at the earliest stages of metamorphism due to coalescence of minute grains. Progressive heating also results in the loss of sulfides from chondrule rims and increases sulfide abundances in coarse matrix assemblages as well as inside chondrules. Alkalis initially leave the matrix and enter chondrules during early metamorphism. Feldspar subsequently nucleates in the matrix and Na re-enters from chondrules. These metamorphic trends can be used to refine classification schemes for chondrites. Cr distributions in olivine are a highly effective tool for assigning petrologic types to the most primitive meteorites and can be used to subdivide types 3.0 and 3.1 into types 3.00 through 3.15. On this basis, the most primitive ordinary chondrite known is Semarkona, although even this meteorite has experienced a small amount of metamorphism. Allan Hills (ALH) A77307 is the least metamorphosed CO chondrite and shares many properties with the ungrouped carbonaceous chondrite Acfer 094. Analytical problems are significant for glasses in type II chondrules, as Na is easily lost during microprobe analysis. As a result, existing schemes for chondrule classification that are based on the alkali content of glasses need to be revised.

Meteoritics and Planetary Science↗

USGS2014

Modeling long-term trends of chlorinated ethene contamination at a public supply well

A mass-balance solute-transport modeling approach was used to investigate the effects of dense nonaqueous phase liquid (DNAPL) volume, composition, and generation of daughter products on simulated and measured long-term trends of chlorinated ethene (CE) concentrations at a public supply well. The model was built by telescoping a calibrated regional three-dimensional MODFLOW model to the capture zone of a public supply well that has a history of CE contamination. The local model was then used to simulate the interactions between naturally occurring organic carbon that acts as an electron donor, and dissolved oxygen (DO), CEs, ferric iron, and sulfate that act as electron acceptors using the Sequential Electron Acceptor Model in three dimensions (SEAM3D) code. The modeling results indicate that asymmetry between rapidly rising and more gradual falling concentration trends over time suggests a DNAPL rather than a dissolved source of CEs. Peak concentrations of CEs are proportional to the volume and composition of the DNAPL source. The persistence of contamination, which can vary from a few years to centuries, is proportional to DNAPL volume, but is unaffected by DNAPL composition. These results show that monitoring CE concentrations in raw water produced by impacted public supply wells over time can provide useful information concerning the nature of contaminant sources and the likely future persistence of contamination.

New Jersey↗

USGS2000

Diversity of anaerobic halophilic microorganisms

Life in the presence of high salt concentrations is compatible with life in the absence of oxygen. Halophilic and halotolerant anaerobic prokaryotes are found both in the archaeal and in the bacterial domain, and they display a great metabolic diversity. Many of the representatives of the Halobacteriales (Archaea), which are generally considered aerobes, have the potential of anaerobic growth. Some can use alternative electron acceptors such as nitrate, fumarate, dimethylsulfoxide or trimethylamine-N-oxide Halobacterium salinarum can also grow fermentatively on L-arginine, and bacteriorhodopsin-containing cells may even grow anaerobically, energized by light. Obligatory anaerobic halophilic methanogenic Archaea also exist. The bacterial domain contains many anaerobic halophiles, including sulfate reducers. There is also a group of specialized obligatory anaerobic Bacteria, phylogenetically clustering in the low G+C branch of the Firmicutes. Most representatives of this group (order Haloanaerobiales , families Haloanaerobiaceae and Halobacteroidaceae ) are fermentative, using a variety of carbohydrates and amino acids. One species combines the potential for anaerobic growth at high salt concentrations with a preference for high temperatures. Others are homoacetogens; Acetohalobium arabaticum can grow anaerobically as a chemolithotroph, producing acetate from hydrogen and CO 2 . The Haloanaerobiales accumulate high concentrations of K + and Cl - in their cytoplasm, thereby showing a strategy of salt adaptation similar to that used by the Halobacteriales . Recently a new representative of the Haloanaerobiales was isolated from bottom sediments of the Dead Sea (strain DSSe1), which grows anaerobically by oxidation of glycerol to acetate and CO 2 while reducing selenate to selenite and elementary selenium. Other electron acceptors supporting anaerobic growth of this strain are nitrate and trimethylamine- N -oxide. The versatility of life at high salt concentrations with respect to the variety of substrates used, the types of dissimilatory metabolism, and the diversity of potential electron acceptors has important implications for the potential for life in hostile environments lacking oxygen and high in salt, implications that may also be relevant to astrobiology.

Proceedings of SPIE↗

USGS1999

Simultaneous reduction of nitrate and selenate by cell suspensions of selenium-respiring bacteria

Washed-cell suspensions of Sulfurospirillum barnesii reduced selenate [Se(VI)] when cells were cultured with nitrate, thiosulfate, arsenate, or fumarate as the electron acceptor. When the concentration of the electron donor was limiting, Se(VI) reduction in whole cells was approximately fourfold greater in Se(VI)-grown cells than was observed in nitrate-grown cells; correspondingly, nitrate reduction was ∼11-fold higher in nitrate-grown cells than in Se(VI)-grown cells. However, a simultaneous reduction of nitrate and Se(VI) was observed in both cases. At nonlimiting electron donor concentrations, nitrate-grown cells suspended with equimolar nitrate and selenate achieved a complete reductive removal of nitrogen and selenium oxyanions, with the bulk of nitrate reduction preceding that of selenate reduction. Chloramphenicol did not inhibit these reductions. The Se(VI)-respiring haloalkaliphile Bacillus arsenicoselenatis gave similar results, but its Se(VI) reductase was not constitutive in nitrate-grown cells. No reduction of Se(VI) was noted for Bacillus selenitireducens , which respires selenite. The results of kinetic experiments with cell membrane preparations of S. barnesii suggest the presence of constitutive selenate and nitrate reduction, as well as an inducible, high-affinity nitrate reductase in nitrate-grown cells which also has a low affinity for selenate. The simultaneous reduction of micromolar Se(VI) in the presence of millimolar nitrate indicates that these organisms may have a functional use in bioremediating nitrate-rich, seleniferous agricultural wastewaters. Results with 75 Se-selenate tracer show that these organisms can lower ambient Se(VI) concentrations to levels in compliance with new regulations proposed for release of selenium oxyanions into the environment.

California↗

USGS2018

Delindeite titanosilicates and lourenswalsite, two new from the Magnet Cove region, Arkansas

Delindeite and lourenswalsite are two new barium titanosilicate minerals found as microscopic crystals in miarolitic cavities in nepheline syenite in the Diamond Jo quarry, Hot Spring County, Arkansas. Delindeite is found as aggregates of flake-like crystallites in compact spherules, light pinkish grey in colour, with a resinous, pearly lustre. The flakes are biaxial positive with average n ∼ 1.813; the measured density is 3.3 g/cm 3 . Electron diffraction revealed a monoclinic unit cell in space group C 2 l m or subgroup, with a = 21.617(13), b = 6.816(5), c = 5.383(3) Å, β = 94.03(5)° (refined from X-ray powder data). The strongest X-ray lines are ( hkl , d obs , I rel ): (200, 10.80, 100); (311, 3.54, 24); (6̄01, 3.083, 28); (601, 2.888, 31); (2̄21, 2.806, 20); (910, 2.262,18). The crystals are submicroscopically twinned on (100) and also produce additional continuous diffraction streaks parallel to a *, which double the b and c axes. The formula derived from electron and ion probe analyses (H 2 O by difference), as constrained by density and molar volume data, is approximately (Na,K) 2.7 (Ba,Ca) 4 (Ti,Fe,Al) 6 Si 8 O 26 (OH) 14 , with Na > K, Ba ≫ Ca, Ti ≫ Fe,Al; Z = 1. Lourenswalsite occurs as very thin hexagonal plates in rosettes, silver grey to light brownish grey in colour. The crystals are biaxial negative with very low 2 V angle. Indices of refraction are n α = 1.815, n β ≈ n γ = 1.840; the measured density is 3.17 g/cm = 1.840; the measured density is 3.17 g/cm 3 . X-ray and electron diffraction show a sharp pseudohexagonal lattice with a = 5.244 Å, but extremely diffuse diffraction streaks normal to the hk 0 plane. In these streaks a period of 20.5 Å can be discerned. A hexagonal unit cell with a = 5.244(2) Å, c = 20.49(3) Å can be refined from the powder diffraction data but does not account for some lines, probably because of extreme layer disorder as shown by precession single-crystal patterns. The strong X-ray powder lines are (002, 10.22, 20); (-, 3.93, 20); (111, 2.608, 100); (300, 1.5145, 80); (220, 1.3111, 25). The formula given by microprobe analyses, constrained by density and molar volume data, is approximately (K,Ba) 2 (Ti,Mg,Ca,Fe) 4 (Si,Al,Fe) 6 O 14 (OH) 12 with K > Ba, Ti ≫ (Mg,Ca,Fe), Si > Al > Fe; Z = 1. These minerals are formed under oxidizing weathering conditions, and iron is assumed to be in the Fe 3+ state.

Arkansas↗

USGS2024

Changes in particle morphology during illitization: An experimental study

Smectite was reacted at several temperatures between 200°C and 500°C to produce interstratified illite/smectite (I/S) with different proportions of expandable layers. Dispersed and sedimented products were examined using a transmission electron microscope. Particle size and aspect ratio showed no systematic change as a function of reaction extent during R0 illitization. However, particles exhibited rounded edges during the early stages of the reaction, suggesting some dissolution of primary smectite. Additionally, increasing particle contrast in the electron beam suggests thickening of particles with increasing reaction extent. The thickening of particles is thought to be produced by the nucleation and precipitation of secondary illite layers on primary smectite layers. In the most extensively reacted I/S, particles have become aggregated into clumps or quasicrystals by lateral growth of illite layers. Internal uniformity of crystallographic alignment of individual growing crystals within each aggregate was reflected in the increasing frequency of 60° and 120° interfacial angles within each aggregate. In highly illitic I/S, these aggregates took on an overall euhedral form and became crystallographically contiguous, producing single crystal electron diffraction patterns.

Clays and Clay Minerals↗