Thomas A. Dewers

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 ∼160 km slip, and the rupture zone of a recent earthquake in a South African mine with only ∼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.

Bacterial Diversity and Sulfur Cycling in a Mesophilic Sulfide-Rich Spring

ABSTRACT 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 δ-Proteobacteria, purple sulfur γ-Proteobacteria, ε-Proteobacteria, Chloroflexi, and filamentous Cyanobacteria of the order Oscillatoria as well as a novel group within γ-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.

Rate laws for water-assisted compaction and stress-induced water-rock interaction in sandstones

Mineral-water interactions under conditions of nonhydrostatic stress play a role in subjects as diverse as ductile creep in fault zones, phase relations in metamorphic rocks, mass redistribution and replacement reactions during diagenesis, and loss of porosity in deep sedimentary basins. As a step toward understanding the fundamental geochemical processes involved, using naturally rounded St. Peter sand, we have investigated the kinetics of pore volume loss and quartz-water reactions under nonhydrostatic, hydrothermal conditions in flow-through reactors. Rate laws for creep and mineral-water reaction are derived from the time rate of change of pore volume, sand-water dissolution kinetics, and (flow rate independent) steady state silica concentrations, and reveal functional dependencies of rates on grain size, volume strain, temperature, effective pressure (confining minus pore pressure), and specific surface areas. Together the mechanical and chemical rate laws form a self-consistent model for coupled deformation and water-rock interaction of porous sands under nonhydrostatic conditions. Microstructural evidence shows a progressive widening of nominally circular and nominally flat grain-grain contacts with increasing strain or, equivalently, porosity loss, and small quartz overgrowths occurring at grain contact peripheries. The mechanical and chemical data suggest that the dominant creep mechanism is due to removal of mass from grain contacts (termed pressure solution or solution transfer), with a lesser component of time-dependent crack growth and healing. The magnitude of a stress-dependent concentration increase is too large to be accounted for by elastic or dislocation strain energy-induced supersaturations, favoring instead the normal stress dependence of molar Gibbs free energy associated with grain-grain interfaces.

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.

SURVEY OF ARCHAEAL DIVERSITY REVEALS AN ABUNDANCE OF HALOPHILIC ARCHAEA IN A LOW-SALT, SULFIDE- AND SULFUR-RICH SPRING

ABSTRACT 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.

Pore networks in continental and marine mudstones: characteristics and controls on sealing behavior.

Mudstone pore networks are strong modifiers of sedimentary basin fluid dynamics and have a critical role in the distribution of hydrocarbons and containment of injected fluids. Using core samples from continental and marine mudstones, we investigate properties of pore types and networks from a variety of geologic environments, together with estimates of capillary breakthrough pressures by mercury intrusion porosimetry. Analysis and interpretation of quantitative and qualitative three-dimensional (3D) observations, obtained by dual focused ion beam–scanning electron microscopy, suggest seven dominant mudstone pore types distinguished by geometry and connectivity. A dominant planar pore type occurs in all investigated mudstones and generally has high coordination numbers (i.e., number of neighboring connected pores). Connected networks of pores of this type contribute to high mercury capillary pressures due to small pore throats at the junctions of connected pores and likely control most matrix transport in these mudstones. Other pore types are related to authigenic (e.g., replacement or pore-lining precipitation) clay minerals and pyrite nodules; pores in clay packets adjacent to larger, more competent clastic grains; pores in organic phases; and stylolitic and microfracture-related pores. Pores within regions of authigenic clay minerals often form small isolated networks (

The role of carboxylic acids in albite and quartz dissolution: An experimental study under diagenetic conditions

Abstract Simple water soluble organic acids may promote secondary porosity development in sandstones during diagenesis by increasing feldspar solubility and dissolution rate. To test this hypothesis, Amelia albite and Brazilian hydrothermal quartz were reacted with 0.07 m acetate and 0.07 m acetate-0.005 m oxalate solutions at selected pH values, and distilled water. Pore fluid chemistry was monitored through time at various flow rates to obtain both solubility and dissolution rate data. The experiments were conducted in large volume, semi-static, flow-through systems at 100°C and 347 bars. These systems simulate subsurface flow rates, low mass water/rock, and high surface area/fluid mass. Acetate and acetate + oxalate solutions significantly increase albite solubility at temperatures, pressures, and pH values typical of diagenetic environments. Albite solubilities increased in acetate and acetate + oxalate solutions by factors of 2 and 3.4, respectively, compared to distilled water. In these same solutions, Al concentrations were ≈ 140 and ≈480 times higher than that calculated for kaolinite solubility at the same conditions without organic species. These enhanced solubilities occur at pH values (4.6–4.8) that may overlap with formation waters. In contrast to albite, quartz solubility was essentially identical in all solutions investigated. Dissolution rates in the acid region decreased with increasing pH in the acetate and acetate + oxalate solutions. Slopes of log rate vs. pH curves were ≈0.6 for acetate and ≈0.3 for acetate + oxalate. Although the effects of acetate on the dissolution rate are small, the effects of oxalate are significant. A rate law valid for albite dissolution at 100°C, oxalate concentrations to 0.01 m, and pH values ranging from 3.4 to 5.5 is given below (assuming activity coefficients = 1 and acetate rate ≈ the proton-promoted rate): R total = 5.88 × 10 −11 + 5.01 × 10 −8 m 0.56 H+ + 6.7 ×10 −10 2.3 × 10 −4 m O x /(1.0+2.3 × 10 −4 m O x ), where m O x and m H + are oxalate and H + molal concentrations, respectively. Reacted albite grains examined by SEM show extensive dissolution concentrated along cleavage planes and structural imperfections such as twin boundaries and fluid inclusions, consistent with surface-controlled reaction kinetics. No authigenic aluminosilicate minerals were observed. The lack of authigenic clays indicates the efficiency of oxalate and acetate in mobilizing and transporting Al. The combination of enhanced solubility and increased dissolution rates indicates that carboxylic acids may play major roles in feldspar dissolution and secondary-porosity development during diagenesis of feldspathic sandstones.

Effect of Oxidation Rate and Fe(II) State on Microbial Nitrate-Dependent Fe(III) Mineral Formation

ABSTRACT 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.

Three-dimensional pore networks and transport properties of a shale gas formation determined from focused ion beam serial imaging

Three-dimensional pore network reconstructions of mudstone properties are made using dual focused ion beam-scanning electron microscopy (FIB-SEM). Samples of Jurassic Haynesville Formation mudstone are examined with FIB-SEM and image analysis to determine pore properties, topology, and tortuosity. Resolvable pore morphologies (>~10 nm) include large slit-like pores between clay aggregates and smaller pores in strain shadows surrounding larger clastic grains. Mercury injection capillary pressure (MICP) data suggest a dominant 1–10 nm or less size of pores barely resolvable by FIB-SEM imaging. Computational fluid dynamics modelling is used to calculate single phase permeability of the larger pore networks on the order of a few nanodarcys (which compare favourably with core-scale permeability tests). This suggests a pore hierarchy wherein permeability may be limited by connected networks of inter-aggregate pores larger than about 20 nm, while MICP results reflect smaller connected networks of pores residing ...

Implications of replacement for reaction-transport modeling

Abstract Mineral replacement in rocks consists of growth of guest mineral and dissolution of host. The two reactions are coupled by the grain–grain stress generated by growth of the guest grain in a rigid or very viscous rock in which it has initially no available room. This stress self-adjusts to make the volumetric rates of guest growth and host dissolution equal to each other, which accounts for the volume conservation typical of replacement. Volume preservation during replacement is required by conservation of mass and momentum as well. The two reactions are also simultaneous and proceed by a sequence of many tiny alternating increments; where these increments are small enough, internal textural details of the host grain or grain aggregate are morphologically preserved (as ghost textures) by the replacement. The strong variation of mineral reaction rates with stress required by replacement is evidenced also experimentally. Reported widespread replacement in many rocks (laterites, diagenesis of siliciclastics and carbonates, metasomatic ores, metamorphic rocks, and hydrothermal alteration) warrants creating water–rock reactive transport models that predict when and where in a system replacement should take place. Current geochemical models implicitly view replacement as sequential, uncoupled dissolution of host and growth of guest; this sequence of reactions may also occur in rocks, but crucially differs from replacement. Implications of replacement for water–rock reaction modeling include: 1. balancing of replacement reactions on volume; 2. use of Helmholtz (rather than Gibbs) free energies of minerals involved in replacement; 3. taking account of the strong stress-dependence of mineral growth and dissolution rates in rocks; and 4. taking account of possible accommodation of growth by local deformation (as well as pressure solution) of the host rock, and of the effect of strain rate (=growth rate) on local rock viscosity.