X-ray absorption spectroscopy identifies calcium-uranyl-carbonate complexes at environmental concentrations

Current research on bioremediation of uranium-contaminated groundwater focuses on supplying indigenous metal-reducing bacteria with the appropriate metabolic requirements to induce microbiological reduction of soluble uranium(VI) to poorly soluble uranium(IV). Recent studies of uranium(VI) bioreduction in the presence of environmentally relevant levels of calcium revealed limited and slowed uranium(VI) reduction and the formation of a Ca-UO₂-CO₃ complex. However, the stoichiometry of the complex is poorly defined and may be complicated by the presence of a Na-UO₂-CO₃ complex. Such a complex might exist even at high calcium concentrations, as some UO₂-CO₃ complexes will still be present. The number of calcium and/or sodium atoms coordinated to a uranyl carbonate complex will determine the net charge of the complex. Such a change in aqueous speciation of uranium(VI) in calcareous groundwater may affect the fate and transport properties of uranium. In this paper, we present the results from X-ray absorption fine structure (XAFS) measurements of a series of solutions containing 50 μM uranium(VI) and 30 mM sodium bicarbonate, with various calcium concentrations of 0-5 mM. Use of the data series reduces the uncertainty in the number of calcium atoms bound to the UO₂-CO₃ complex to approximately 0.6 and enables spectroscopic identification of the Na-UO₂-CO₃ complex. At nearly neutral pH values, the numbers of sodium and calcium atoms bound to the uranyl triscarbonate species are found to depend on the calcium concentration, as predicted by speciation calculations.     

High- and low-affinity binding sites for Cd on the bacterial cell walls of Bacillus subtilis and Shewanella oneidensis

Bulk Cd adsorption isotherm experiments, thermodynamic equilibrium modeling, and Cd K edge EXAFS were used to constrain the mechanisms of proton and Cd adsorption to bacterial cells of the commonly occurring Gram-positive and Gram-negative bacteria, Bacillus subtilis and Shewanella oneidensis, respectively. Potentiometric titrations were used to characterize the functional group reactivity of the S. oneidensis cells, and we model the titration data using the same type of non-electrostatic surface complexation approach as was applied to titrations of B. subtilis suspensions by Fein et al. (2005). Similar to the results for B. subtilis, the S. oneidensis cells exhibit buffering behavior from approximately pH 3-9 that requires the presence of four distinct sites, with pK_a values of 3.3 ± 0.2, 4.8 ± 0.2, 6.7 ± 0.4, and 9.4 ± 0.5, and site concentrations of 8.9(±2.6) × 10⁻⁵, 1.3(±0.2) × 10⁻⁴, 5.9(±3.3) × 10⁻⁵, and 1.1(±0.6) × 10⁻⁴ moles/g bacteria (wet mass), respectively. The bulk Cd isotherm adsorption data for both species, conducted at pH 5.9 as a function of Cd concentration at a fixed biomass concentration, were best modeled by reactions with a Cd:site stoichiometry of 1:1. EXAFS data were collected for both bacterial species as a function of Cd concentration at pH 5.9 and 10 g/L bacteria. The EXAFS results show that the same types of binding sites are responsible for Cd sorption to both bacterial species at all Cd loadings tested (1-200 ppm). Carboxyl sites are responsible for the binding at intermediate Cd loadings. Phosphoryl ligands are more important than carboxyl ligands for Cd binding at high Cd loadings. For the lowest Cd loadings studied here, a sulfhydryl site was found to dominate the bound Cd budgets for both species, in addition to the carboxyl and phosphoryl sites that dominate the higher loadings. The EXAFS results suggest that both Gram-positive and Gram-negative bacterial cell walls have a low concentration of very high-affinity sulfhydryl sites which become masked by the more abundant carboxyl and phosphoryl sites at higher metal:bacteria ratios. This study demonstrates that metal loading plays a vital role in determining the important metal-binding reactions that occur on bacterial cell walls, and that high affinity, low-density sites can be revealed by spectroscopy of biomass samples. Such sites may control the fate and transport of metals in realistic geologic settings, where metal concentrations are low.     

Depth-related influences on biodegradation rates of phenanthrene in polluted marine sediments of Puget Sound, WA

A whole-core injection method was used to determine depth-related rates of microbial mineralization of (14)C-phenanthrene added to both contaminated and clean marine sediments of Puget Sound, WA. For 26-day incubations under micro-aerobic conditions, conversions of (14)C-phenanthrene to (14)CO(2) in heavily PAH-contaminated sediments from two sites in Eagle Harbor were much higher (up to 30%) than those in clean sediments from nearby Blakely Harbor (<3%). The averaged (14)C-phenanthrene degradation rates in the surface sediment horizons (0-3 cm) were more rapid (2-3 times) than in the deeper sediment horizons examined (>6 cm), especially in the most PAH polluted EH9 site. Differences in mineralization were associated with properties of the sediments as a function of sediment depth, including grain-size distribution, PAH concentration, total organic matter and total bacterial abundance. When strictly anaerobic incubations (in N(2)/H(2)/CO(2) atmosphere) were used, the phenanthrene biodegradation rates at all sediment depths were two times slower than under micro-aerobic conditions, with methanogenesis observed after 24 days. The main rate-limiting factor for phenanthrene degradation under anaerobic conditions appeared to be the availability of suitable electron acceptors. Addition of calcium sulfate enhanced the first order rate coefficient (k(1) increased from 0.003 to 0.006 day(-1)), whereas addition of soluble nitrate, even at very low concentration (<0.5 mM), inhibited mineralization. Long-term storage of heavily polluted Eagle Harbor sediment as intact cores under micro-aerobic conditions also appeared to enhance anaerobic biodegradation rates (k(1) up to 0.11 day(-1)).     

Plastic ingestion by planktivorous fishes in the North Pacific Central Gyre

A significant amount of marine debris has accumulated in the North Pacific Central Gyre (NPCG). The effects on larger marine organisms have been documented through cases of entanglement and ingestion; however, little is known about the effects on lower trophic level marine organisms. This study is the first to document ingestion and quantify the amount of plastic found in the gut of common planktivorous fish in the NPCG. From February 11 to 14, 2008, 11 neuston samples were collected by manta trawl in the NPCG. Plastic from each trawl and fish stomach was counted and weighed and categorized by type, size class and color. Approximately 35% of the fish studied had ingested plastic, averaging 2.1 pieces per fish. Additional studies are needed to determine the residence time of ingested plastics and their effects on fish health and the food chain implications.     

Characterization of uraninite nanoparticles produced by Shewanella oneidensis MR-1

The reduction of uranium(VI) by Shewanella oneidensis MR-1 was studied to examine the effects of bioreduction kinetics and background electrolyte on the physical properties and reactivity to re-oxidation of the biogenic uraninite, UO_2(s). Bioreduction experiments were conducted with uranyl acetate as the electron acceptor and sodium lactate as the electron donor under resting cell conditions in a 30 mM NaHCO₃ buffer, and in a PIPES-buffered artificial groundwater (PBAGW). MR-1 was cultured in batch mode in a defined minimal medium with a specified air-to-medium volume ratio such that electron acceptor (O₂) limiting conditions were reached just when cells were harvested for subsequent experiments. The rate of U(VI) bioreduction was manipulated by varying the cell density and the incubation temperature (1.0 × 10⁸ cell ml⁻¹ at 20 °C or 2.0 × 10⁸ cell ml⁻¹ at 37 °C) to generate U(IV) solids at “fast” and “slow” rates in the two different buffers. The presence of Ca in PBAGW buffer altered U(VI) speciation and solubility, and significantly decreased U(VI) bioreduction kinetics. High resolution transmission electron microscopy was used to measure uraninite particle size distributions produced under the four different conditions. The most common primary particle size was 2.9-3.0 nm regardless of U(VI) bioreduction rate or background electrolyte. Extended X-ray absorption fine-structure spectroscopy was also used to estimate uraninite particle size and was consistent with TEM results. The reactivity of the biogenic uraninite products with dissolved oxygen was tested, and neither U(VI) bioreduction rate nor background electrolyte had any statistical effect on oxidation rates. With MR-1, uraninite particle size was not controlled by the bioreduction rate of U(VI) or the background electrolyte. These results for MR-1, where U(VI) bioreduction rate had no discernible effect on uraninite particle size or oxidation rate, contrast with our recent research with Shewanella putrefaciens CN32, where U(VI) bioreduction rate strongly influenced both uraninite particle size and oxidation rate. These two studies with Shewanella species can be viewed as consistent if one assumes that particle size controls oxidation rates, so the similar uraninite particle sizes produced by MR-1 regardless of U(VI) bioreduction rate would result in similar oxidation rates. Factors that might explain why U(VI) bioreduction rate was an important control on uraninite particle size for CN32 but not for MR-1 are discussed.     

Developing a sediment budget for a small drainage basin in Australia

A sediment budget was developed for the 1.7 km² Maluna Creek drainage basin located in the Hunter Valley, New South Wales, Australia, for the period 1971-86. the impact of viticulture, which commenced at Maluna in 1971, was studied using erosion plots, with caesium-137 as an indicator of both soil erosion and sedimentation. Two methods were used to estimate vineyard soil losses from caesium-137 measurements. Sediment output from the catchment was measured for three years, and extrapolated from readings taken at a nearby long-term stream flow gauging station for the remaining 13 years. Relative amounts of soil loss from forest (60 per cent basin area), grazing land (30 per cent) and vineyards (10 per cent) were calculated. Soil losses by rain splash detachment were ten times greater from bare/cultivated sufaces than from the forest. Erosion plots of area 2 m² showed no significant differences in soil loss between forest and grassland but, under bare soil, losses were 100 times greater. the ¹³⁷Cs method was employed to calculate net soil loss from all vineyard blocks using both a previously established calibration curve and a proportional model. the latter method gave estimates of soil loss which were 3-9 times greater than by the calibration curve, and indicated that average soil losses from the vineyard were equivalent to 62 t ha^?1 y^?1 (1971-86). It was estimated that the forest contributed 1-8 per cent, the grazing land 1.6 per cent, and the vineyard 96.6 per cent of the total soil loss during that period. Sediment storages within the fluvial system adjacent to the vineyard ws 9460 t for the period, whereas sediment output was equivalent to 215 t km^?1 y^?1. Independent measurements of soil erosion, storage, and output showed that 56 per cent of the eroded sediment remained in the catchment, and 34 per cent was transported out by Maluna Creek. the budget was able to be balanced to within 10 per cent.     

Microbial reduction of iron(III)-rich nontronite and uranium(VI)

To assess the dynamics of microbially mediated U-clay redox reactions, we examined the reduction of iron(III)-rich nontronite NAu-2 and uranium(VI) by Shewanella oneidensis MR-1. Bioreduction experiments were conducted with combinations and varied concentrations of MR-1, nontronite, U(VI) and the electron shuttle anthraquinone-2,6-disulfonate (AQDS). Abiotic experiments were conducted to quantify U(VI) sorption to NAu-2, the reduction of U(VI) by chemically-reduced nontronite-Fe(II), and the oxidation of uraninite, U^(IV)O_2(s), by nontronite-Fe(III). When we incubated S. oneidensis MR-1 at lower concentration (0.5 × 10⁸ cell mL⁻¹) with nontronite (5.0 g L⁻¹) and U(VI) (1.0 mM), little U(VI) reduction occurred compared to nontronite-free incubations, despite the production of abundant Fe(II). The addition of AQDS to U(VI)- and nontronite-containing incubations enhanced both U(VI) and nontronite-Fe(III) reduction. While U(VI) was completely reduced by S. oneidensis MR-1 at higher concentration (1.0 × 10⁸ cell mL⁻¹) in the presence of nontronite, increasing concentrations of nontronite led to progressively slower rates of U(VI) reduction. U(VI) enhanced nontronite-Fe(III) reduction and uraninite was oxidized by nontronite-Fe(III), demonstrating that U served as an effective electron shuttle from S. oneidensis MR-1 to nontronite-Fe(III). The electron-shuttling activity of U can explain the lack or delay of U(VI) reduction observed in the bulk solution. Little U(VI) reduction was observed in incubations that contained chemically-reduced nontronite-Fe(II), suggesting that biologic U(VI) reduction drove U valence cycling in these systems. Under the conditions used in these experiments, we demonstrate that iron-rich smectite may inhibit or delay U(VI) bioreduction.     

Historical analysis (2000-2005) of the coastal water quality in San Andrés Island, SeaFlower Biosphere Reserve, Caribbean Colombia

To understand the coastal water quality of San Andrès Island, and provide tools for the management of its marine resources, we present the historical analysis of the island monitoring, which includes ammonia, nitrites, nitrate, phosphates, fecal and total coliforms. The anthropogenic pressure on the coastal system is heavy, with water nutrification, posing at risk seagrass and coral ecosystems. During dry season, biologically available nitrogen is 3-9 times higher than the maximum recommended for coral reefs, while during wet season values are 2-6.4 times the maximum. Biologically available phosphorous is also high, 1-8 times the maximum during dry season, 2-13 times during wet season. In some sites the concentration of pathogenic bacteria is above the limits set by law for primary and secondary contact. It is urgent to improve the management of sewage discharge, the main polluting source of San Andres coastal waters.     

A DENDROGEOMORPHOLOGICAL ANALYSIS OF SNOW AVALANCHES IN THE COLORADO FRONT RANGE,USA

Despite the growing risk of avalanche-related death and property damage associated with the burgeoning tourist industry in the Colorado Front Range, no dendro-geomorphological studies have been conducted to assess avalanche history in this region. In this study, dendrogeomorphological techniques are used to develop avalanche event chronologies and to reconstruct past slide magnitude at two sites located near Loveland Pass. At Mount Bethel, historical data compiled by the Colorado Department of Transportation (CDOT) and the Westwide Data Network for the period between 1974 and 1996 corroborate four of eight dendrochronologically dated event years. At Grizzly Peak, four of five dendrochronologically determined event years occurring between 1981 and 1996 are supported by historical data kept by CDOT, the Westwide Data Network and the Arapaho Basin Ski Patrol. Avalanche path reconstruction and the examination of vegetative indicator species reveal periodic fluctuations in slide magnitude at both sites, suggesting that larger avalanches have run outside the present tracks multiple times. The chronicling and assessment of each path's slide history informs of past occurrences and alerts us to future risks. [Key words: avalanche, dendrogeomorphology, Colorado Front Range.]     

搭建地震方法和大地测量方法所检测的慢地震之间的桥梁

最近观测到的异常地震事件——深部低频地震和颤动、甚低频地震及慢滑动事件——形成了慢震群,而这个慢震群受控于不同于普通地震的标定律。根据这个标定律,我们在日本西部的纪伊半岛下方观测到了之前未知的事件,其震源持续时间约20-200s,矩震级为3～4级。这些地震在2～8Hz的频带范围内辐射能量,直接与其地震矩率成比例,但这个比例常数比一般地震小4～5个数量级。这个地区的慢地震可能是由大量的剪切滑动事件组成的,从地震方法上看,总体上会呈现为颤动或长达200s持续时间的较长独立事件,从大地测量方法上看,是慢滑动事件。