Uranium speciation and stability after reductive immobilization in aquifer sediments

It has generally been assumed that the bioreduction of hexavalent uranium in groundwater systems will result in the precipitation of immobile uraninite (UO₂). In order to explore the form and stability of uranium immobilized under these conditions, we introduced lactate (15 mM for 3 months) into flow-through columns containing sediments derived from a former uranium-processing site at Old Rifle, CO. This resulted in metal-reducing conditions as evidenced by concurrent uranium uptake and iron release. Despite initial augmentation with Shewanella oneidensis, bacteria belonging to the phylum Firmicutes dominated the biostimulated columns. The immobilization of uranium (∼1 mmol U per kg sediment) enabled analysis by X-ray absorption spectroscopy (XAS). Tetravalent uranium associated with these sediments did not have spectroscopic signatures representative of U-U shells or crystalline UO₂. Analysis by microfocused XAS revealed concentrated micrometer regions of solid U(IV) that had spectroscopic signatures consistent with bulk analyses and a poor proximal correlation (μm scale resolution) between U and Fe. A plausible explanation, supported by biogeochemical conditions and spectral interpretations, is uranium association with phosphoryl moieties found in biomass; hence implicating direct enzymatic uranium reduction. After the immobilization phase, two months of in situ exposure to oxic influent did not result in substantial uranium remobilization. Ex situ flow-through experiments demonstrated more rapid uranium mobilization than observed in column oxidation studies and indicated that sediment-associated U(IV) is more mobile than biogenic UO₂. This work suggests that in situ uranium bioimmobilization studies and subsurface modeling parameters should be expanded to account for non-uraninite U(IV) species associated with biomass.     

Molecular and isotopic partitioning of low-molecular-weight hydrocarbons during migration and gas hydrate precipitation in deposits of a high-flux seepage site

Detailed knowledge of the extent of post-genetic modifications affecting shallow submarine hydrocarbons fueled from the deep subsurface is fundamental for evaluating source and reservoir properties. We investigated gases from a submarine high-flux seepage site in the anoxic Eastern Black Sea in order to elucidate molecular and isotopic alterations of low-molecular-weight hydrocarbons (LMWHC) associated with upward migration through the sediment and precipitation of shallow gas hydrates. For this, near-surface sediment pressure cores and free gas venting from the seafloor were collected using autoclave technology at the Batumi seep area at 845 m water depth within the gas hydrate stability zone.Vent gas, gas from pressure core degassing, and from hydrate dissociation were strongly dominated by methane (> 99.85 mol.% of ∑[C₁–C₄, CO₂]). Molecular ratios of LMWHC (C₁/[C₂ + C₃] > 1000) and stable isotopic compositions of methane (δ¹³C = ? 53.5‰ V-PDB; D/H around ? 175‰ SMOW) indicated predominant microbial methane formation. C₁/C₂₊ ratios and stable isotopic compositions of LMWHC distinguished three gas types prevailing in the seepage area. Vent gas discharged into bottom waters was depleted in methane by > 0.03 mol.% (∑[C₁–C₄, CO₂]) relative to the other gas types and the virtual lack of ¹⁴C–CH₄ indicated a negligible input of methane from degradation of fresh organic matter. Of all gas types analyzed, vent gas was least affected by molecular fractionation, thus, its origin from the deep subsurface rather than from decomposing hydrates in near-surface sediments is likely.As a result of the anaerobic oxidation of methane, LMWHC in pressure cores in top sediments included smaller methane fractions [0.03 mol.% ∑(C₁–C₄, CO₂)] than gas released from pressure cores of more deeply buried sediments, where the fraction of methane was maximal due to its preferential incorporation in hydrate lattices. No indications for stable carbon isotopic fractionations of methane during hydrate crystallization from vent gas were found. Enrichments of ¹⁴C–CH₄ (1.4 pMC) in short cores relative to lower abundances (max. 0.6 pMC) in gas from long cores and gas hydrates substantiates recent methanogenesis utilizing modern organic matter deposited in top sediments of this high-flux hydrocarbon seep area.     

Modelling the Shimokita deep coalbed biosphere over deep geological time: Starvation,stimulation, material balance and population models

Basin models can simulate geological, geochemical and geophysical processes and potentially also the deep biosphere, starting from a burial curve, assuming a thermal history and utilizing other experimentally obtained data. Here, we apply basin modelling techniques to model cell abundances within the deep coalbed biosphere off Shimokita Peninsula, Japan, drilled during Integrated Ocean Drilling Program Expedition 337. Two approaches were used to simulate the deep coalbed biosphere: (a) In the first approach, the deep biosphere was modelled using a material balance approach that treats the deep biosphere as a carbon reservoir, in which fluxes are governed by temperature-controlled metabolic processes that retain carbon via cell-growth and cell-repair and pass it back via cell-damaging reactions. (b) In the second approach, the deep biosphere was modelled as a microbial community with a temperature-controlled growth ratio and carrying capacity (a limit on the size of the deep biosphere) modulated by diagenetic-processes. In all cases, the biosphere in the coalbeds and adjacent habitat are best modelled as a carbon-limited community undergoing starvation because labile sedimentary organic matter is no longer present and petroleum generation is yet to occur. This state of starvation was represented by the conversion of organic carbon to authigenic carbonate and the formation of kerogen. The potential for the biosphere to be stimulated by the generation of carbon-dioxide from the coal during its transition from brown to sub-bituminous coal was evaluated and a net thickness of 20 m of lignite was found sufficient to support an order of magnitude greater number of cells within a low-total organic carbon (TOC) horizon. By comparison, the stimulation of microbial populations in a coalbed or high-TOC horizon would be harder to detect because the increase in population size would be proportionally very small.     

Stable carbon isotopic compositions of intact polar lipids reveal complex carbon flow patterns among hydrocarbon degrading microbial communities at the Chapopote asphalt volcano

Seepage of asphalt forms the basis of a cold seep system at 3000 m water depth at the Chapopote Knoll in the southern Gulf of Mexico. Anaerobic microbial communities are stimulated in the oil-impregnated sediments as evidenced by the presence of intact polar membrane lipids (IPLs) derived from archaea and Bacteria at depths up to 7 m below the seafloor. Detailed investigation of stable carbon isotope composition (δ¹³C) of alkyl and acyl moieties derived from a range of IPL precursors with distinct polar head groups resolved the complexity of carbon metabolisms and utilization of diverse carbon sources by uncultured microbial communities. In surface sediments most of the polar lipid-derived fatty acids with phosphatidylethanolamine (PE), phosphatidylglycerol (PG) and diphosphatidylglycerol (DPG) head groups could be tentatively assigned to autotrophic sulfate-reducing bacteria, with a relatively small proportion involved in the anaerobic oxidation of methane. Derivatives of phosphatidyl-(N)-methylethanolamine (PME) were abundant and could be predominantly assigned to heterotrophic oil-degrading bacteria. Archaeal IPLs with phosphate-based hydroxyarchaeols and diglycosidic glyceroldibiphytanylglyceroltetraethers (GDGTs) were assigned to methanotrophic archaea of the ANME-2 and ANME-1 cluster, respectively, whereas δ¹³C values of phosphate-based archaeols and mixed phosphate-based and diglycosidic GDGTs point to methanogenic archaea. At a 7 m deep sulfate-methane transition zone that is linked to the upward movement of gas-laden petroleum, a distinct increase in abundance of archaeal IPLs such as phosphate-based hydroxyarchaeols and diglycosidic archaeol and GDGTs is observed; their δ¹³C values are consistent with their origin from both methanotrophic and methanogenic archaea. This study reveals previously hidden, highly complex patterns in the carbon-flow of versatile microbial communities involved in the degradation of heavy oil including hydrocarbon gases that would not have been evident from classical compound-specific isotope analyses of either bulk IPL or apolar lipid derivatives.     

Comparative dissolution kinetics of biogenic and chemogenic uraninite under oxidizing conditions in the presence of carbonate

The long-term stability of biogenic uraninite with respect to oxidative dissolution is pivotal to the success of in situ bioreduction strategies for the subsurface remediation of uranium legacies. Batch and flow-through dissolution experiments were conducted along with spectroscopic analyses to compare biogenic uraninite nanoparticles obtained from Shewanella oneidensis MR-1 and chemogenic UO_2.00 with respect to their equilibrium solubility, dissolution mechanisms, and dissolution kinetics in water of varied oxygen and carbonate concentrations. Both materials exhibited a similar intrinsic solubility of ∼10⁻⁸ M under reducing conditions. The two materials had comparable dissolution rates under anoxic as well as oxidizing conditions, consistent with structural bulk homology of biogenic and stoichiometric uraninite. Carbonate reversibly promoted uraninite dissolution under both moderately oxidizing and reducing conditions, and the biogenic material yielded higher surface area-normalized dissolution rates than the chemogenic. This difference is in accordance with the higher proportion of U(V) detected on the biogenic uraninite surface by means of X-ray photoelectron spectroscopy. Reasonable sources of a stable U(V)-bearing intermediate phase are discussed. The observed increase of the dissolution rates can be explained by carbonate complexation of U(V) facilitating the detachment of U(V) from the uraninite surface. The fraction of surface-associated U(VI) increased with dissolved oxygen concentration. Simultaneously, X-ray absorption spectra showed conversion of the bulk from UO_2.0 to UO_2+x. In equilibrium with air, combined spectroscopic results support the formation of a near-surface layer of approximate composition UO_2.25 (U₄O₉) coated by an outer layer of U(VI). This result is in accordance with flow-through dissolution experiments that indicate control of the dissolution rate of surface-oxidized uraninite by the solubility of metaschoepite under the tested conditions. Although U(V) has been observed in electrochemical studies on the dissolution of spent nuclear fuel, this is the first investigation that demonstrates the formation of a stable U(V) intermediate phase on the surface of submicron-sized uraninite particles suspended in aqueous solutions.     

Reconstruction of past methane availability in an Arctic Alaska wetland indicates climate influenced methane release during the past ~12,000?years

Atmospheric contributions of methane from Arctic wetlands during the Holocene are dynamic and linked to climate oscillations. However, long-term records linking climate variability to methane availability in Arctic wetlands are lacking. We present a multi-proxy ~12,000?year paleoecological reconstruction of intermittent methane availability from a radiocarbon-dated sediment core (LQ-West) taken from a shallow tundra lake (Qalluuraq Lake) in Arctic Alaska. Specifically, stable carbon isotopic values of photosynthetic biomarkers and methane are utilized to estimate the proportional contribution of methane-derived carbon to lake-sediment-preserved benthic (chironomids) and pelagic (cladocerans) components over the last ~12,000?years. These results were compared to temperature, hydrologic, and habitat reconstructions from the same site using chironomid assemblage data, oxygen isotopes of chironomid head capsules, and radiocarbon ages of plant macrofossils. Cladoceran ephippia from ~4,000?cal?year BP sediments have ??¹³C values that range from ~?39 to ?31??, suggesting peak methane carbon assimilation at that time. These low ??¹³C values coincide with an apparent decrease in effective moisture and development of a wetland that included Sphagnum subsecundum. Incorporation of methane-derived carbon by chironomids and cladocerans decreased from ~2,500 to 1,500?cal?year BP, coinciding with a temperature decrease. Live-collected chironomids with a radiocarbon age of 1,640?cal?year BP, and fossil chironomids from 1,500?cal?year BP in the core illustrate that ??old?? carbon has also contributed to the development of the aquatic ecosystem since ~1,500?cal?year BP. The relatively low ??¹³C values of aquatic invertebrates (as low as ?40.5??) provide evidence of methane incorporation by lake invertebrates, and suggest intermittent climate-linked methane release from the lake throughout the Holocene.     

A simple guideline to apply excitation-emission matrix spectroscopy (EEMs) for the characterization of dissolved organic matter (DOM) in anoxic marine sediments

Marine sediments represent a major carbon reservoir on Earth. Dissolved organic matter(DOM) in pore waters accumulates products and intermediates of carbon cycling in sediments. The application of excitation-emission matrix spectroscopy(EEMs) in the analysis of subseafloor DOM samples is largely unexplored due to the redoxsensitive matrix of anoxic pore water. Therefore, this study aims to investigate the interference caused by the matrix on EEMs and propose a guideline to prepare pore water sam...     

Molecular characterization of uranium(VI) sorption complexes on iron(III)-rich acid mine water colloids

A mixing of metal-loaded acid mine drainage with shallow groundwater or surface waters usually initiates oxidation and/or hydrolysis of dissolved metals such as iron (Fe) and aluminum (Al). Colloidal particles may appear and agglomerate with increasing pH. Likewise chemical conditions may occur while flooding abandoned uranium mines. Here, the risk assessment of hazards requires reliable knowledge on the mobility of uranium (U). A flooding process was simulated at mesocosm scale by mixing U-contaminated acid mine water with near-neutral groundwater under oxic conditions. The mechanism of U-uptake by fresh precipitates and the molecular structure of U bonding were determined to estimate the mobility of U(VI). Analytical and spectroscopic methods such as Extended X-ray Absorption Fine-Structure (EXAFS) spectroscopy at the Fe K-edge and the U L_III-edge, and Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy were employed. The freshly formed precipitate was identified as colloidal two-line ferrihydrite. It removed U(VI) from solution by sorption processes, while surface precipitation or structural incorporation of U was not observed. EXAFS data suggest a mononuclear inner-sphere, edge-sharing complex of U(VI) with ferrihydrite in the absence of dissolved carbonate. By employing a novel EXAFS analysis method, Monte Carlo Target Transformation Factor Analysis, we could for the first time ascertain a 3-D configuration of this sorption complex without the necessity to invoke formation of a ternary complex. The configuration suggests a slightly tilted position of the adsorbed unit relative to the edge-sharing Fe(O, OH)₆ octahedra. In the presence of dissolved carbonate and at pH ∼8.0, a distal carbonate O-atom at ∼4.3 Å supports formation of ternary U(VI)-carbonato surface complexes. The occurrence of these complexes was also confirmed by ATR-FTIR. However, in slightly acidic conditions (pH 5-6) in equilibrium with atmospheric CO₂, the U(VI) sorption on ferrihydrite was dominated by the binary complex species Fe(O)₂UO₂, whereas ternary U(VI)-carbonato surface complexes were of minor relevance. While sulfate and silicate were also present in the mine water, they had no detectable influence on U(VI) surface complexation. Our experiments demonstrate that U(VI) forms stable inner-sphere sorption complexes even in the presence of carbonate and at slightly alkaline pH, conditions which previously have been assumed to greatly accelerate the mobility of U(VI) in aqueous environments. Depending on the concentrations of U(VI) and carbonate, the type of surface complexes may change from binary uranyl-ferrihydrite to ternary carbonato-uranyl-ferrihydrite complexes. These different binding mechanisms are likely to influence the binding stability and retention of U(VI) at the macroscopic level.     

Advanced characterization of marine dissolved organic matter by combining reversed-phase liquid chromatography and FT-ICR-MS

Marine dissolved organic matter (DOM) was separated by reversed-phase (RP) liquid chromatography method and analyzed with fluorescence/absorption detection and Fourier transform ion cyclotron mass spectrometry (FT-ICR-MS). The three key characteristics of the RP method are: (a) The C18-RP column chosen provides enhanced separation when the aqueous phase is 100% buffer-free water, and it does not degrade over time; (b) the water eluent adjusted to pH 7 significantly improves the resolution of water soluble compounds; (c) the initial flow maintained at low levels improves the separation of polar compounds. In samples, containing “fresh” DOM, specific peaks were detected, which were absent in “old” DOM samples. The combination with size exclusion chromatography (SEC) also demonstrated the relation between polarity and molecular size of DOM. FT-ICR-MS was applied to evaluate the quality of separation on a molecular scale demonstrating that physico-chemical characteristics of DOM can be related to molecular formulas. Sample extracts were separated into 4 preparative fractions, and a large suite of the identified molecular formulas only occurred in specific fractions. This is an important basis for the application of further analytical techniques in order to perform a more target-oriented analysis aiming at the determination of source and process biomarkers for DOM.