Flow-through compression cell for small-angle and ultra-small-angle neutron scattering measurements.

In situ measurements of geological materials under compression and with hydrostatic fluid pressure are important in understanding their behavior under field conditions, which in turn provides critical information for application-driven research. In particular, understanding the role of nano- to micro-scale porosity in the subsurface liquid and gas flow is critical for the high-fidelity characterization of the transport and more efficient extraction of the associated energy resources. In other applications, where parts are produced by the consolidation of powders by compression, the resulting porosity and crystallite orientation (texture) may affect its in-use characteristics. Small-angle neutron scattering (SANS) and ultra SANS are ideal probes for characterization of these porous structures over the nano to micro length scales. Here we show the design, realization, and performance of a novel neutron scattering sample environment, a specially designed compression cell, which provides compressive stress and hydrostatic pressures with effective stress up to 60 MPa, using the neutron beam to probe the effects of stress vectors parallel to the neutron beam. We demonstrate that the neutron optics is suitable for the experimental objectives and that the system is highly stable to the stress and pressure conditions of the measurements.

Oedometric Small-Angle Neutron Scattering: In Situ Observation of Nanopore Structure During Bentonite Consolidation and Swelling in Dry and Hydrous CO2 Environments.

Results of oedometric consolidation experiments linked with small-angle neutron scattering (SANS) measurements are presented, using SWy-2 Wyoming bentonite clay in dry and water-bearing N2 and CO2 atmospheres. Oedometric SANS involves deforming a porous sample under uniaxial strain conditions with applied axial force and internal pore pressure control, and combines with SANS for in situ observation of pore structure evolution and interaction. Scattering from both interlayer (clay intra-aggregate) and free (interaggregate) pores is observed, showing decreasing pore size with dry consolidation and interactions between interlayer and free pore types with swelling and consolidation. Introduction of dry liquid CO2 at zero effective stress (axial stress minus pore pressure) produces large shifts in interlayer scatterers, but is reversible back to pre-CO2 levels upon decreasing pore pressure and increasing effective stress. Introduction of wet liquid CO2, conversely, produces large but irreversible changes in interlayer scatterers, which are interpreted to be the combined result of CO2 and H2O intercalation under hydrostatic conditions, but which diminish with application of effective pressure and consolidation to higher bentonite dry densities. Consideration of CO2 intercalation in smectite-bearing CO2 caprocks needs to include effects of both water and nonhydrostatic stress.

Multiwell CO2 injectivity: impact of boundary conditions and brine extraction on geologic CO2 storage efficiency and pressure buildup.

CO2 storage efficiency is a metric that expresses the portion of the pore space of a subsurface geologic formation that is available to store CO2. Estimates of storage efficiency for large-scale geologic CO2 storage depend on a variety of factors including geologic properties and operational design. These factors govern estimates on CO2 storage resources, the longevity of storage sites, and potential pressure buildup in storage reservoirs. This study employs numerical modeling to quantify CO2 injection well numbers, well spacing, and storage efficiency as a function of geologic formation properties, open-versus-closed boundary conditions, and injection with or without brine extraction. The set of modeling runs is important as it allows the comparison of controlling factors on CO2 storage efficiency. Brine extraction in closed domains can result in storage efficiencies that are similar to those of injection in open-boundary domains. Geomechanical constraints on downhole pressure at both injection and extraction wells lower CO2 storage efficiency as compared to the idealized scenario in which the same volumes of CO2 and brine are injected and extracted, respectively. Geomechanical constraints should be taken into account to avoid potential damage to the storage site.

Hydrogeologic controls on induced seismicity in crystalline basement rocks due to fluid injection into basal reservoirs.

A series of Mb 3.8-5.5 induced seismic events in the midcontinent region, United States, resulted from injection of fluid either into a basal sedimentary reservoir with no underlying confining unit or directly into the underlying crystalline basement complex. The earthquakes probably occurred along faults that were likely critically stressed within the crystalline basement. These faults were located at a considerable distance (up to 10 km) from the injection wells and head increases at the hypocenters were likely relatively small (∼70-150 m). We present a suite of simulations that use a simple hydrogeologic-geomechanical model to assess what hydrogeologic conditions promote or deter induced seismic events within the crystalline basement across the midcontinent. The presence of a confining unit beneath the injection reservoir horizon had the single largest effect in preventing induced seismicity within the underlying crystalline basement. For a crystalline basement having a permeability of 2 × 10(-17) m(2) and specific storage coefficient of 10(-7) /m, injection at a rate of 5455 m(3) /d into the basal aquifer with no underlying basal seal over 10 years resulted in probable brittle failure to depths of about 0.6 km below the injection reservoir. Including a permeable (kz = 10(-13) m(2) ) Precambrian normal fault, located 20 m from the injection well, increased the depth of the failure region below the reservoir to 3 km. For a large permeability contrast between a Precambrian thrust fault (10(-12) m(2) ) and the surrounding crystalline basement (10(-18) m(2) ), the failure region can extend laterally 10 km away from the injection well.

Ganglion dynamics and its implications to geologic carbon dioxide storage.

Capillary trapping of a nonwetting fluid phase in the subsurface has been considered as an important mechanism for geologic storage of carbon dioxide (CO(2)). This mechanism can potentially relax stringent requirements for the integrity of cap rocks for CO(2) storage and therefore can significantly enhance storage capacity and security. We here apply ganglion dynamics to understand the capillary trapping of supercritical CO(2) (scCO(2)) under relevant reservoir conditions. We show that, by breaking the injected scCO(2) into small disconnected ganglia, the efficiency of capillary trapping can be greatly enhanced, because the mobility of a ganglion is inversely dependent on its size. Supercritical CO(2) ganglia can be engineered by promoting CO(2)-water interface instability during immiscible displacement, and their size distribution can be controlled by injection mode (e.g., water-alternating-gas) and rate. We also show that a large mobile ganglion can potentially break into smaller ganglia due to CO(2)-brine interface instability during buoyant rise, thus becoming less mobile. The mobility of scCO(2) in the subsurface is therefore self-limited. Vertical structural heterogeneity within a reservoir can inhibit the buoyant rise of scCO(2) ganglia. The dynamics of scCO(2) ganglia described here provides a new perspective for the security and monitoring of subsurface CO(2) storage.

Effect of oxidation rate and Fe(II) state on microbial nitrate-dependent Fe(III) mineral formation.

A nitrate-dependent Fe(II)-oxidizing bacterium was isolated and used to evaluate whether Fe(II) chemical form or oxidation rate had an effect on the mineralogy of biogenic Fe(III) (hydr)oxides resulting from nitrate-dependent Fe(II) oxidation. The isolate (designated FW33AN) had 99% 16S rRNA sequence similarity to Klebsiella oxytoca. FW33AN produced Fe(III) (hydr)oxides by oxidation of soluble Fe(II) [Fe(II)sol] or FeS under nitrate-reducing conditions. Based on X-ray diffraction (XRD) analysis, Fe(III) (hydr)oxide produced by oxidation of FeS was shown to be amorphous, while oxidation of Fe(II)sol yielded goethite. The rate of Fe(II) oxidation was then manipulated by incubating various cell concentrations of FW33AN with Fe(II)sol and nitrate. Characterization of products revealed that as Fe(II) oxidation rates slowed, a stronger goethite signal was observed by XRD and a larger proportion of Fe(III) was in the crystalline fraction. Since the mineralogy of Fe(III) (hydr)oxides may control the extent of subsequent Fe(III) reduction, the variables we identify here may have an effect on the biogeochemical cycling of Fe in anoxic ecosystems.

Role for Fe(III) minerals in nitrate-dependent microbial U(IV) oxidation.

Microbiological reduction of soluble U(VI) to insoluble U(IV) is a means of preventing the migration of that element in groundwater, but the presence of nitrate in U(IV)-containing sediments leads to U(IV) oxidation and remobilizaton. Nitrite or iron(III) oxyhydroxides may oxidize U(IV) under nitrate-reducing conditions, and we determined the rate and extent of U(IV) oxidation by these compounds. Fe(III) oxidized U(IV) at a greater rate than nitrite (130 and 10 microM U(IV)/day, respectively). In aquifer sediments, Fe(III) may be produced during microbial nitrate reduction by oxidation of Fe(II) with nitrite, or by enzymatic Fe(II) oxidation coupled to nitrate reduction. To determine which of these mechanisms was dominant, we isolated a nitrate-dependent acetate- and Fe(ll)-oxidizing bacterium from a U(VI)- and nitrate-contaminated aquifer. This organism oxidized U(IV) at a greater rate and to a greater extent under acetate-oxidizing (where nitrite accumulated to 50 mM)than under Fe(II)-oxidizing conditions. We showthatthe observed differences in rate and extent of U(IV) oxidation are due to mineralogical differences between Fe(III) produced by reaction of Fe(II) with nitrite (amorphous) and Fe(III) produced enzymatically (goethite or lepidocrocite). Our results suggest the mineralogy and surface area of Fe(III) minerals produced under nitrate-reducing conditions affect the rate and extent of U(IV) oxidation. These results may be useful for predicting the stability of U(IV) in aquifers.

Particle size and energetics of gouge from earthquake rupture zones.

Grain size reduction and gouge formation are found to be ubiquitous in brittle faults at all scales, and most slip along mature faults is observed to have been localized within gouge zones. This fine-grain gouge is thought to control earthquake instability, and thus understanding its properties is central to an understanding of the earthquake process. Here we show that gouge from the San Andreas fault, California, with approximately 160 km slip, and the rupture zone of a recent earthquake in a South African mine with only approximately 0.4 m slip, display similar characteristics, in that ultrafine grains approach the nanometre scale, gouge surface areas approach 80 m2 g(-1), and grain size distribution is non-fractal. These observations challenge the common perception that gouge texture is fractal and that gouge surface energy is a negligible contributor to the earthquake energy budget. We propose that the observed fine-grain gouge is not related to quasi-static cumulative slip, but is instead formed by dynamic rock pulverization during the propagation of a single earthquake.

Survey of archaeal diversity reveals an abundance of halophilic Archaea in a low-salt, sulfide- and sulfur-rich spring.

The archaeal community in a sulfide- and sulfur-rich spring with a stream water salinity of 0.7 to 1.0% in southwestern Oklahoma was studied by cloning and sequencing of 16S rRNA genes. Two clone libraries were constructed from sediments obtained at the hydrocarbon-exposed source of the spring and the microbial mats underlying the water flowing from the spring source. Analysis of 113 clones from the source library and 65 clones from the mat library revealed that the majority of clones belonged to the kingdom Euryarchaeota, while Crenarchaeota represented less than 10% of clones. Euryarchaeotal clones belonged to the orders Methanomicrobiales, Methanosarcinales, and Halobacteriales, as well as several previously described lineages with no pure-culture representatives. Those within the Halobacteriales represented 36% of the mat library and 4% of the source library. All cultivated members of this order are obligately aerobic halophiles. The majority of halobacterial clones encountered were not affiliated with any of the currently described genera of the family Halobacteriaceae. Measurement of the salinity at various locations at the spring, as well as along vertical gradients, revealed that soils adjacent to spring mats have a much higher salinity (NaCl concentrations as high as 32%) and a lower moisture content than the spring water, presumably due to evaporation. By use of a high-salt-plus-antibiotic medium, several halobacterial isolates were obtained from the microbial mats. Analysis of 16S rRNA genes indicated that all the isolates were members of the genus Haloferax. All isolates obtained grew at a wide range of salt concentrations, ranging from 6% to saturation, and all were able to reduce elemental sulfur to sulfide. We reason that the unexpected abundance of halophilic Archaea in such a low-salt, highly reduced environment could be explained by their relatively low salt requirement, which could be satisfied in specific locations of the shallow spring via evaporation, and their ability to grow under the prevalent anaerobic conditions in the spring, utilizing zero-valent sulfur compounds as electron acceptors. This study demonstrates that members of the Halobacteriales are not restricted to their typical high-salt habitats, and we propose a role for the Halobacteriales in sulfur reduction in natural ecosystems.

Bacterial diversity and sulfur cycling in a mesophilic sulfide-rich spring.

An artesian sulfide- and sulfur-rich spring in southwestern Oklahoma is shown to sustain an extremely rich and diverse microbial community. Laboratory incubations and autoradiography studies indicated that active sulfur cycling is occurring in the abundant microbial mats at Zodletone spring. Anoxygenic phototrophic bacteria oxidize sulfide to sulfate, which is reduced by sulfate-reducing bacterial populations. The microbial community at Zodletone spring was analyzed by cloning and sequencing 16S rRNA genes. A large fraction (83%) of the microbial mat clones belong to sulfur- and sulfate-reducing lineages within delta-Proteobacteria, purple sulfur gamma-Proteobacteria, epsilon -Proteobacteria, Chloroflexi, and filamentous Cyanobacteria of the order Oscillatoria as well as a novel group within gamma-Proteobacteria. The 16S clone library constructed from hydrocarbon-exposed sediments at the source of the spring had a higher diversity than the mat clone library (Shannon-Weiner index of 3.84 compared to 2.95 for the mat), with a higher percentage of clones belonging to nonphototrophic lineages (e.g., Cytophaga, Spirochaetes, Planctomycetes, Firmicutes, and Verrucomicrobiae). Many of these clones were closely related to clones retrieved from hydrocarbon-contaminated environments and anaerobic hydrocarbon-degrading enrichments. In addition, 18 of the source clones did not cluster with any of the previously described microbial divisions. These 18 clones, together with previously published or database-deposited related sequences retrieved from a wide variety of environments, could be clustered into at least four novel candidate divisions. The sulfate-reducing community at Zodletone spring was characterized by cloning and sequencing a 1.9-kb fragment of the dissimilatory sulfite reductase (DSR) gene. DSR clones belonged to the Desulfococcus-Desulfosarcina-Desulfonema group, Desulfobacter group, and Desulfovibrio group as well as to a deeply branched group in the DSR tree with no representatives from cultures. Overall, this work expands the division-level diversity of the bacterial domain and highlights the complexity of microbial communities involved in sulfur cycling in mesophilic microbial mats.