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.     

Great South Bay After Sandy: Changes in Circulation and Flushing due to New Inlet

The coastal ocean model FVCOM is applied to quantify the changes in circulation, flushing, and exposure time in Great South Bay, New York, after Superstorm Sandy breached the barrier island in 2012. Since then, the lagoon system is connected to the Atlantic via five instead of four inlets. The model simulations are run on two high-resolution unstructured grids, one for the pre-breach configuration, one including the new inlet, with tidal-only forcing, and summer and winter forcing conditions. Despite its small cross-sectional size, the breach has a relatively large net inflow that leads to a strengthening of the along-bay through-flow in Great South Bay (GSB); the tidally driven volume transport in central GSB quadrupled. The seasonal forcing scenarios show that the southwesterly sea breeze in summer slows down the tidally driven flow, while the forcing conditions in winter are highly variable, and the circulation is dependent on wind direction and offshore sea level. Changes in flushing and exposure time associated with the modified transport patterns are evaluated using a Eulerian passive tracer technique. Results show that the new inlet produced a significant decrease in flushing time (approximately 35% reduction under summer wind conditions and 20% reduction under winter wind conditions). Maps of exposure time reflect the local changes in circulation and flushing.     

Detection of Temperature-Dependent Spectral Variation on the Asteroid Eros and New Evidence for the Presence of an Olivine-Rich Silicate Assemblage

Data obtained by the near-infrared spectrometer carried by the NEAR-Shoemaker spacecraft show that the spectral properties of the asteroid Eros vary with temperature. The manner in which they vary demonstrates that the mineral olivine is a major constituent of the surface. The near-IR temperature-dependent spectral properties of Eros in the northern hemisphere, and for two individual regions on the surface, show clear evidence of the presence of the mineral olivine and are a close match to the temperature-spectral behavior of LL-type ordinary chondrite meteorites. While the presence of other olivine-rich meteorites cannot be excluded, H-type ordinary chondrites are clearly too pyroxene-rich to be permitted as a major surface component of Eros. The results of the thermal-spectral analysis are consistent with results from analysis of conventional reflectance spectra of the asteroid and contribute unambiguous detection of olivine to the understanding of the surface composition of Eros.     

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.     

Vesta,Vestoids, and the howardite,eucrite, diogenite group: Relationships and the origin of spectral differences

Abstract— Spectra of asteroid 4 Vesta and 21 small (estimated diameters less than 10 km) asteroids with Vesta‐like spectral properties (Vestoids) were measured at visible and near‐infrared wavelengths (～0.44 to ～1.65 μm). All of the measured small asteroids (except for 2579 Spartacus) have reflectance spectra consistent with surface compositions similar to eucrites and howardites and consistent with all being derived from Vesta. None of the observed asteroids have spectra similar to diogenites. We find no spectral distinction between the 15 objects tabulated as members of the Vesta dynamical family and 6 of the 7 sampled “non‐family” members that reside just outside the semi‐major axis (a), eccentricity (e), and inclination (i) region of the family. The spectral consistency and close orbital (a‐e‐i) match of these “non‐family” objects to Vesta and the Vesta family imply that the true bounds of the family extend beyond the subjective cut‐off for membership. Asteroid 2579 Spartacus has a spectrum consistent with a mixture of eucritic material and olivine. Spartacus could contain olivine‐rich material from Vesta's mantle or may be unrelated to Vesta altogether. Laboratory measurements of the spectra of eucrites show that samples having nearly identical compositions can display a wide range of spectral slopes. Finer particle sizes lead to an increase in the slope, which is usually referred to as reddening. This range of spectral variation for the best‐known meteoritic analogs to the Vestoids, regardless of whether they are actually related to each other, suggests that the extremely red spectral slopes for some Vestoids can be explained by very fine‐grained eucritic material on their surfaces.     

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.     

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.     

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.     

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.