Influence of sulfide on diazotrophic growth of the methanogen Methanococcus maripaludis and its implications for the origin of nitrogenase.

Methanogens inhabit euxinic (sulfide-rich) or ferruginous (iron-rich) environments that promote the precipitation of transition metals as metal sulfides, such as pyrite, reducing metal or sulfur availability. Such environments have been common throughout Earth's history raising the question as to how anaerobes obtain(ed) these elements for the synthesis of enzyme cofactors. Here, we show a methanogen can synthesize molybdenum nitrogenase metallocofactors from pyrite as the source of iron and sulfur, enabling nitrogen fixation. Pyrite-grown, nitrogen-fixing cells grow faster and require 25-fold less molybdenum than cells grown under euxinic conditions. Growth yields are 3 to 8 times higher in cultures grown under ferruginous relative to euxinic conditions. Physiological, transcriptomic, and geochemical data indicate these observations are due to sulfide-promoted metal limitation, in particular molybdenum. These findings suggest that molybdenum nitrogenase may have originated in a ferruginous environment that titrated sulfide to form pyrite, facilitating the availability of sufficient iron, sulfur, and molybdenum for cofactor biosynthesis.

Tectonic settings influence the geochemical and microbial diversity of Peru hot springs.

Tectonic processes control hot spring temperature and geochemistry, yet how this in turn shapes microbial community composition is poorly understood. Here, we present geochemical and 16 S rRNA gene sequencing data from 14 hot springs from contrasting styles of subduction along a convergent margin in the Peruvian Andes. We find that tectonic influence on hot spring temperature and geochemistry shapes microbial community composition. Hot springs in the flat-slab and back-arc regions of the subduction system had similar pH but differed in geochemistry and microbiology, with significant relationships between microbial community composition, geochemistry, and geologic setting. Flat-slab hot springs were chemically heterogeneous, had modest surface temperatures (up to 45 °C), and were dominated by members of the metabolically diverse phylum Proteobacteria. Whereas, back-arc hot springs were geochemically more homogenous, exhibited high concentrations of dissolved metals and gases, had higher surface temperatures (up to 81 °C), and host thermophilic archaeal and bacterial lineages.

Effect of dissolved CO2 on a shallow groundwater system: a controlled release field experiment.

Capturing carbon dioxide (CO(2)) emissions from industrial sources and injecting the emissions deep underground in geologic formations is one method being considered to control CO(2) concentrations in the atmosphere. Sequestering CO(2) underground has its own set of environmental risks, including the potential migration of CO(2) out of the storage reservoir and resulting acidification and release of trace constituents in shallow groundwater. A field study involving the controlled release of groundwater containing dissolved CO(2) was initiated to investigate potential groundwater impacts. Dissolution of CO(2) in the groundwater resulted in a sustained and easily detected decrease of ~3 pH units. Several trace constituents, including As and Pb, remained below their respective detections limits and/or at background levels. Other constituents (Ba, Ca, Cr, Sr, Mg, Mn, and Fe) displayed a pulse response, consisting of an initial increase in concentration followed by either a return to background levels or slightly greater than background. This suggests a fast-release mechanism (desorption, exchange, and/or fast dissolution of small finite amounts of metals) concomitant in some cases with a slower release potentially involving different solid phases or mechanisms. Inorganic constituents regulated by the U.S. Environmental Protection Agency remained below their respective maximum contaminant levels throughout the experiment.

Experimental evaluation of wellbore integrity along the cement-rock boundary.

Leakage of CO(2) and brine from geologic storage reservoirs along wellbores is a major risk factor to the success of geologic carbon sequestration. We conducted multiphase [supercritical (sc)CO(2)-brine] coreflood experiments that simulate a leakage pathway along the cement/rock interface. A composite core constructed of oil-well cement and siltstone separated by a simulated damage zone (defect) containing ground cement and siltstone was flooded with brine + scCO(2) at 10 MPa and 60 °C parallel to the defect. During coinjection of scCO(2), the effective brine permeability decreased from ~200 to 90 mD due to transition to two-phase flow and then further declined to 35 mD. CO(2) injection resulted in a pH drop from 11 to 4 and carbonate-undersaturated conditions in the produced brine. Microscopy revealed leaching and erosion along the defect, a carbonation front extending 5 mm into the cement, parallel to the damage zone, and no change in the dimensions of the defect. Carbonation of cement does not appear to explain the permeability drop, which is attributed to the migration and reprecipitation of alteration products derived from cement within the defect. This study shows the potential for self-limiting flow along wellbore defects despite flow of aggressive scCO(2)-brine mixtures.

CO2/Brine transport into shallow aquifers along fault zones.

Unintended release of CO(2) from carbon sequestration reservoirs poses a well-recognized risk to groundwater quality. Research has largely focused on in situ CO(2)-induced pH depression and subsequent trace metal mobilization. In this paper we focus on a second mechanism: upward intrusion of displaced brine or brackish-water into a shallow aquifer as a result of CO(2) injection. Studies of two natural analog sites provide insights into physical and chemical mechanisms controlling both brackish water and CO(2) intrusion into shallow aquifers along fault zones. At the Chimayó, New Mexico site, shallow groundwater near the fault is enriched in CO(2) and, in some places, salinity is significantly elevated. In contrast, at the Springerville, Arizona site CO(2) is leaking upward through brine aquifers but does not appear to be increasing salinity in the shallow aquifer. Using multiphase transport simulations we show conditions under which significant CO(2) can be transported through deep brine aquifers into shallow layers. Only a subset of these conditions favor entrainment of salinity into the shallow aquifer: high aspect-ratio leakage pathways and viscous coupling between the fluid phases. Recognition of the conditions under which salinity is favored to be cotransported with CO(2) into shallow aquifers will be important in environmental risk assessments.