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A path-independent integral for the characterization of solute concentration and flux at biofilm detachments

A path-independent (conservation) integral is developed for the characterization of solute concentration and flux in a biofilm in the vicinity of a detachment or other flux limiting boundary condition. Steady state conditions of solute diffusion are considered and biofilm kinetics are described by an uptake term which can be expressed in terms of a potential (Michaelis-Menten kinetics). An asymptotic solution for solute concentration at the tip of the detachment is obtained and shown to be analogous to that of antiplane crack problems in linear elasticity. It is shown that the amplitude of the asymptotic solution can be calculated by evaluating a path-independent integral. The special case of a semi-infinite detachment in an infinite strip is considered and the amplitude of the asymptotic field is related to the boundary conditions and problem parameters in closed form for zeroth and first order kinetics and numerically for Michaelis-Menten kinetics. ?? Springer Science+Business Media, Inc. 2007.

International Journal of Fracture

Dual-porosity analysis of conservative tracer testing in saturated volcanic rocks at Yucca Mountain in Nye County, Nevada

A radially convergent conservative tracer injection test was conducted between boreholes UE-25 #2 and UE-25 c #3 of the C-hole complex at Yucca Mountain to determine effective porosity and longitudinal dispersivity. Approximately 47% of the tracer mass was recovered and a dual-porosity analytical model replicates the breakthrough curve. Fractured-rock analyses focus on the fracture-porosity and geometry as the controlling factors in transport.

International Journal of Rock Mechanics and Mining

Borehole sampling of fracture populations - compensating for borehole sampling bias in crystalline bedrock aquifers, Mirror Lake, Grafton County, New Hampshire

The clustering of orientations of hydraulically conductive fractures in bedrock at the Mirror Lake, New Hampshire fractured rock study site was investigated by comparing the orientations of fracture populations in two subvertical borehole arrays with those mapped on four adjacent subvertical roadcuts. In the boreholes and the roadcuts, the orientation of fracture populations appears very similar after borehole data are compensated for undersampling of steeply dipping fractures. Compensated borehole and pavement fracture data indicate a northeast-striking population of fractures with varying dips concentrated near that of the local foliation in the adjacent rock. The data show no correlation between fracture density (fractures/linear meter) and distance from lithologic contacts in both the boreholes and the roadcuts. The population of water-producing borehole fractures is too small (28 out of 610 fractures) to yield meaningful orientation comparisons. However, the orientation of large aperture fractures (which contains all the producing fractures) contains two or three subsidiary clusters in orientation frequency that are not evident in stereographic projections of the entire population containing all aperture sizes. Further, these subsidiary orientation clusters do not coincide with the dominant (subhorizontal and subvertical) regional fracture orientations.

International Journal of Rock Mechanics and Mining

Porosity of the Marcellus Shale: A contrast matching small-angle neutron scattering study

Neutron scattering techniques were used to determine the effect of mineral matter on the accessibility of water and toluene to pores in the Devonian Marcellus Shale. Three Marcellus Shale samples, representing quartz-rich, clay-rich, and carbonate-rich facies, were examined using contrast matching small-angle neutron scattering (CM-SANS) at ambient pressure and temperature. Contrast matching compositions of H 2 O, D 2 O and toluene, deuterated toluene were used to probe open and closed pores of these three shale samples. Results show that although the mean pore radius was approximately the same for all three samples, the fractal dimension of the quartz-rich sample was higher than for the clay-rich and carbonate-rich samples, indicating different pore size distributions among the samples. The number density of pores was highest in the clay-rich sample and lowest in the quartz-rich sample. Contrast matching with water and toluene mixtures shows that the accessibility of pores to water and toluene also varied among the samples. In general, water accessed approximately 70–80% of the larger pores (>80 nm radius) in all three samples. At smaller pore sizes (~5–80 nm radius), the fraction of accessible pores decreases. The lowest accessibility to both fluids is at pore throat size of ~25 nm radii with the quartz-rich sample exhibiting lower accessibility than the clay- and carbonate-rich samples. The mechanism for this behaviour is unclear, but because the mineralogy of the three samples varies, it is likely that the inaccessible pores in this size range are associated with organics and not a specific mineral within the samples. At even smaller pore sizes (~<2.5 nm radius), in all samples, the fraction of accessible pores to water increases again to approximately 70–80%. Accessibility to toluene generally follows that of water; however, in the smallest pores (~<2.5 nm radius), accessibility to toluene decreases, especially in the clay-rich sample which contains about 30% more closed pores than the quartz- and carbonate-rich samples. Results from this study show that mineralogy of producing intervals within a shale reservoir can affect accessibility of pores to water and toluene and these mineralogic differences may affect hydrocarbon storage and production and hydraulic fracturing characteristics

International Journal of Coal Geology

Stratigraphy and structure of coalbed methane reservoirs in the United States: an overview

Stratigraphy and geologic structure determine the shape, continuity and permeability of coal and are therefore critical considerations for designing exploration and production strategies for coalbed methane. Coal in the United states is dominantly of Pennsylvanian, Cretaceous and Tertiary age, and to date, more than 90% of the coalbed methane produced is from Pennsylvanian and cretaceous strata of the Black Warrior and San Juan Basins. Investigations of these basins establish that sequence stratigraphy is a promising approach for regional characterization of coalbed methane reservoirs. Local stratigraphic variation within these strata is the product of sedimentologic and tectonic processes and is a consideration for selecting completion zones. Coalbed methane production in the United States is mainly from foreland and intermontane basins containing diverse compression and extensional structures. Balanced structural models can be used to construct and validate cross sections as well as to quantify layer-parallel strain and predict the distribution of fractures. Folds and faults influence gas and water production in diverse ways. However, interwell heterogeneity related to fractures and shear structures makes the performance of individual wells difficult to predict.Stratigraphy and geologic structure determine the shape, continuity and permeability of coal and are therefore critical considerations for designing exploration and production strategies for coalbed methane. Coal in the United States is dominantly of Pennsylvanian, Cretaceous and Tertiary age, and to date, more than 90% of the coalbed methane produced is from Pennsylvanian and Cretaceous strata of the Black Warrior and San Juan Basins. Investigations of these basins establish that sequence stratigraphy is a promising approach for regional characterization of coalbed methane reservoirs. Local stratigraphic variation within these strata is the product of sedimentologic and tectonic processes and is a consideration for selecting completion zones. Coalbed methane production in the United States is mainly from foreland and intermontane basins containing diverse compressional and extensional structures. Balanced structural models can be used to construct and validate cross sections as well as to quantify layer-parallel strain and predict the distribution of fractures. Folds and faults influence gas and water production in diverse ways. However, interwell heterogeneity related to fractures and shear structures makes the performance of individual wells difficult to predict.

International Journal of Coal Geology

An analytical solution for transient flow of Bingham viscoplastic materials in rock fractures

We present below an analytical solution to model the one-dimensional transient flow of a Bingham viscoplastic material in a fracture with parallel walls (smooth or rough) that is subjected to an applied pressure gradient. The solution models the acceleration and the deceleration of the material as the pressure gradient changes with time. Two cases are considered: A pressure gradient applied over a finite time interval and an applied pressure gradient that is constant over time. The solution is expressed in dimensionless form and can therefore be used for a wide range of Bingham viscoplastic materials. The solution is also capable of capturing the transition that takes place in a fracture between viscoplastic flow and rigid plug flow. Also, it shows the development of a rigid central layer in fractures, the extent of which depends on the fluid properties (viscosity and yield stress), the magnitude of the pressure gradient, and the fracture aperture and surface roughness. Finally, it is shown that when a pressure gradient is applied and kept constant, the solution for the fracture flow rate converges over time to a steady-state solution that can be defined as a modified cubic law. In this case, the fracture transmissivity is found to be a non-linear function of the head gradient. This solution provides a tool for a better understanding of the flow of Bingham materials in rock fractures, interfaces, and cracks. ?? 2001 Elsevier Science Ltd. All rights reserved.

International Journal of Rock Mechanics and Mining

Spatial analysis of extension fracture systems: A process modeling approach

Little consensus exists on how best to analyze natural fracture spacings and their sequences. Field measurements and analyses published in geotechnical literature imply fracture processes radically different from those assumed by theoretical structural geologists. The approach adopted in this paper recognizes that disruption of rock layers by layer-parallel extension results in two spacing distributions, one representing layer-fragment lengths and another separation distances between fragments. These two distributions and their sequences reflect mechanics and history of fracture and separation. Such distributions and sequences, represented by a 2 ?? n matrix of lengthsL, can be analyzed using a method that is history sensitive and which yields also a scalar estimate of bulk extension, e (L). The method is illustrated by a series of Monte Carlo experiments representing a variety of fracture-and-separation processes, each with distinct implications for extension history. Resulting distributions of e (L)are process-specific, suggesting that the inverse problem of deducing fracture-and-separation history from final structure may be tractable. ?? 1985 Plenum Publishing Corporation.

Journal of the International Association for Mathe

Fracture network of the Ferron Sandstone Member of the Mancos Shale, east-central Utah, USA

The fracture network at the outcrop of the Ferron Sandstone Member of the Mancos Shale was studied to gain an understanding of the tectonic history of the region and to contribute data to studies of gas and water transmissivity related to the occurrence and production of coal-bed methane. About 1900 fracture readings were made at 40 coal outcrops and 62 sandstone outcrops in the area from Willow Springs Wash in the south to Farnham dome in the north of the study area in east-central Utah.Two sets of regional, vertical to nearly vertical, systematic face cleats were identified in Ferron coals. A northwest-striking set trends at a mean azimuth of 321??, and a northeast-striking set has a mean azimuth of 55??. Cleats were observed in all coal outcrops examined and are closely spaced and commonly coated with thin films of iron oxide.Two sets of regional, systematic joint sets in sandstone were also identified and have mean azimuths of 321?? and 34??. The joints of each set are planar, long, and extend vertically to nearly vertically through multiple beds; the northeast-striking set is more prevalent than the northwest-striking set. In some places, joints of the northeast-striking set occur in closely spaced clusters, or joint zones, flanked by unjointed rock. Both sets are mineralized with iron oxide and calcite, and the northwest-striking set is commonly tightly cemented, which allowed the northeast-striking set to propagate across it. All cleats and joints of these sets are interpreted as opening-mode (mode I) fractures. Abutting relations indicate that the northwest-striking cleats and joints formed first and were later overprinted by the northeast-striking cleats and joints. Burial curves constructed for the Ferron indicate rapid initial burial after deposition. The Ferron reached a depth of 3000 ft (1000 m) within 5.2 million years (m.y.), and this is considered a minimum depth and time for development of cleats and joints. The Sevier orogeny produced southeast-directed compressional stress at this time and is thought to be the likely mechanism for the northwest-striking systematic cleats and joints. The onset of the Laramide orogeny occurred at about 75 Ma, within 13.7 m.y. of burial, and is thought to be the probable mechanism for development of the northeast-striking systematic cleats and joints. Uplift of the Ferron in the late Tertiary contributed to development of butt cleats and secondary cross-joints and probably enhanced previously formed fracture sets. Using a study of the younger Blackhawk Formation as an analogy, the fracture pattern of the Ferron in the subsurface is probably similar to that at the surface, at least as far west as the Paradise fault and Joe's Valley graben. Farther to the west, on the Wasatch Plateau, the orientations of Ferron fractures may diverge from those measured at the outcrop. ?? 2003 Elsevier B.V. All rights reserved.

International Journal of Coal Geology

Deep syntectonic burial of the Anthracite belt, Eastern Pennsylvania

Fluid inclusion microthermometry and Raman spectroscopy of fluid inclusions in quartz veins from the Pennsylvanian rocks of the Anthracite belt, eastern Pennsylvania support a deep burial model of coalification in favor of focused orogenic hot fluid flow. High-temperature (250 to 255 °C) trapping of CH 4 ± CO 2 saturated aqueous fluids and CH 4 ± CO 2 inclusions indicate fluid trapping at depths of 11.5 to 13.4 km under a cover of Pennsylvanian to Permian(?) syntectonic load. In the folded rocks to the south of the Anthracite belt, CH 4 ± CO 2 fluid inclusions indicate a sediment load that was up to 16.3 km thick. Re -equilibrated aqueous fluid inclusions from veins in Silurian through Devonian rocks give the same range of trapping conditions but a wide range of fluid salinities suggesting that folding, fracturing, and meteoric recharge resulted in the intermixing of fluids from throughout the stratigraphic succession.

Pennsylvania

Compartmentalization of the Coso East Flank geothermal field imaged by 3-D full-tensor MT inversion

Previous magnetotelluric (MT) studies of the high-temperature Coso geothermal system in California identified a subvertical feature of low resistivity (2–5 Ohm m) and appreciable lateral extent (>1 km) in the producing zone of the East Flank field. However, these models could not reproduce gross 3-D effects in the recorded data. We perform 3-D full-tensor inversion and retrieve a resistivity model that out-performs previous 2-D and 3-D off-diagonal models in terms of its fit to the complete 3-D MT data set as well as the degree of modelling bias. Inclusion of secondary Z xx and Z yy data components leads to a robust east-dip (60†) to the previously identified conductive East Flank reservoir feature, which correlates strongly with recently mapped surface faults, downhole well temperatures, 3-D seismic reflection data, and local microseismicity. We perform synthetic forward modelling to test the best-fit dip of this conductor using the response at a nearby MT station. We interpret the dipping conductor as a fractured and fluidized compartment, which is structurally controlled by an unmapped blind East Flank fault zone.

Coso Range

Shear failure of a granite pin traversing a sawcut fault

Fault heterogeneities such as bumps, bends, and stepovers are commonly observed on natural faults, but are challenging to recreate under controlled laboratory conditions. We study deformation and microseismicity of a 76 mm-diameter Westerly granite cylinder with a sawcut fault with known frictional properties. An idealized asperity is added by emplacing a precision-ground 21 mm-diameter solid granite dowel that crosses the center of the fault at right angles. This intact granite ‘pin’ provides a strength contrast that resists fault slip. Upon loading to 80 MPa in a triaxial machine, we first observed a M -4 slip event that ruptured the sawcut fault, slipped 40 µm, but was halted by the granite pin. With continued loading, the pin failed in a swarm of thousands of M -6 to M -8 events known as acoustic emissions (AEs). Once the pin was fractured to a critical point, it permitted complete rupture events (M -3) on the sawcut fault (stick-slip instabilities). Subsequent slip events were preceded by clusters of foreshock-like AEs, all located on the fault plane, and the spatial extent of the foreshock clusters is consistent with our estimate of a critical nucleation dimension h*. We also identified an aseismic zone on the fault plane surrounding the fractured rock pin. A post-mortem analysis of the sample showed a thick gouge layer where the pin intersected the fault, suggesting that dilatancy of this gouge propped open the fault and prevented microseismic events in its vicinity. Recorded microseismicity separates into three categories: slip on the sawcut fault, fracture of the intact rock pin, and off-fault seismicity associated with pin-related rock joints. We found that pin fracture events were exclusively implosive (anticrack) even though the shear process zone was overall dilatant. This shows how aseismic effects can lead to unexpected seismic manifestations of certain faulting processes.

International Journal of Rock Mechanics and Mining

Manganese nodules

The existence of manganese (Mn) nodules (Figure 1) has been known since the late 1800s when they were collected during the Challenger expedition of 1873–1876. However, it was not until after WWII that nodules were further studied in detail for their ability to adsorb metals from seawater. Many of the early studies did not distinguish Mn nodules from Mn crusts. Economic interest in Mn nodules began in the late 1950s and early 1960s when John Mero finished his Ph.D. thesis on this subject, which was published in the journal Economic Geology (Mero, 1962) and later as a book (Mero, 1965). By the mid-1970s, large consortia had formed to search for and mine Mn nodules that occur between the Clarion and Clipperton fracture zones (CCZ) in the NE Pacific (Figure 2). This is still the area considered of greatest economic potential in the global ocean because of high nickel (Ni), copper (Cu), and Mn contents and the dense distribution of nodules in the area. While the mining of nodules was fully expected to begin in the late 1970s or early 1980s, this never occurred due to a downturn in the price of metals on the global market. Since then, many research cruises have been undertaken to study the CCZ nodules, and now 15 contracts for exploration sites have been given or are pending by the International Seabed Authority (ISA). Many books and science journal articles have been published summarizing the early work (e.g., Baturin, 1988; Halbach et al., 1988), and research has continued to the present day (e.g., ISA, 1999; ISA, 2010). Although the initial attraction for nodules was their high Ni, Cu, and Mn contents, subsequent work has shown that nodules host large quantities of other critical metals needed for high-tech, green-tech, and energy applications (Hein et al., 2013; Hein and Koschinsky, 2014).

Book chapter

A review of environmental impacts of salts from produced waters on aquatic resources

Salts are frequently a major constituent of waste waters produced during oil and gas production. These produced waters or brines must be treated and/or disposed and provide a daily challenge for operators and resource managers. Some elements of salts are regulated with water quality criteria established for the protection of aquatic wildlife, e.g. chloride (Cl − ), which has an acute standard of 860 mg/L and a chronic standard of 230 mg/L. However, data for establishing such standards has only recently been studied for other components of produced water, such as bicarbonate (HCO 3 − ), which has acute median lethal concentrations (LC50s) ranging from 699 to > 8000 mg/L and effects on chronic toxicity from 430 to 657 mg/L. While Cl− is an ion of considerable importance in multiple geographical regions, knowledge about the effects of hardness (calcium and magnesium) on its toxicity and about mechanisms of toxicity is not well understood. A multiple-approach design that combines studies of both individuals and populations, conducted both in the laboratory and the field, was used to study toxic effects of bicarbonate (as NaHCO 3 ). This approach allowed interpretations about mechanisms related to growth effects at the individual level that could affect populations in the wild. However, additional mechanistic data for HCO 3 − , related to the interactions of calcium (Ca 2 + ) precipitation at the microenvironment of the gill would dramatically increase the scientific knowledge base about how NaHCO 3 might affect aquatic life. Studies of the effects of mixtures of multiple salts present in produced waters and more chronic effect studies would give a better picture of the overall potential toxicity of these ions. Organic constituents in hydraulic fracturing fluids, flowback waters, etc. are a concern because of their carcinogenic properties and this paper is not meant to minimize the importance of maintaining vigilance with respect to potential organic contamination.

International Journal of Coal Geology

Resin rodlets in shale and coal (Lower Cretaceous), Baltimore Canyon Trough

Rodlets, occurring in shale and coal (uppermost Berriasian to middle Aptian, Lower Cretaceous), were identified from drill cuttings taken from depths between 9330 ft (2844 m) and 11, 460 ft (3493 m) in the Texaco et al., Federal Block 598, No. 2 well, in the Baltimore Canyon Trough. Under the binocular microscope, most of the rodlets appear black, but a few are reddish brown, or brownish and translucent on thin edges. They range in diameter from about 0.4 to 1.7 mm and are commonly flattened. The rodlets break with a conchoidal fracture, and some show an apparent cellular cast on their longitudinal surfaces. When polished and viewed in reflected light, the rodlets appear dark gray and have an average random reflectance of less than 0.1% whereas mean maximum reflectances are 0.48–0.55% for vitrinite in the associated shale and coal. These vitrinite reflectances indicate either subbituminous A or high-volatile C bituminous coal. The rodlets fluoresce dull gray yellow to dull yellow. The scanning electron microscope (SEM) and light microscope reveal the presence of swirl-like features in the rodlet interiors. Minerals associated with the rodlets occur as sand-size grains attached to the outer surface, as finely disseminated interior grains, and as fracture fillings. Electron microprobe and SEM-energy-dispersive X-ray (EDX) anlayses indicate that the minerals are dominantly clays (probably illite and chlorite) and iron disulfide; calcium carbonate, silicon dioxide, potassium aluminum silicate (feldspar), titanium dioxide, zinc sulfide, and iron sulfate minerals have been also identified. The rodlets were analyzed directly for C, H, N, O, and total S and are interpreted as true resins on the basis of C and H contents that range from 75.6 to 80.3 and from 7.4 to 8.7 wt. % (dry, ash-free basis), respectively. Elemental and infrared data support a composition similar to that of resinite from bituminous coal. Elements determined to be organically associated in the rodlets include S (0.2–0.5 wt.%), Cl (0.03–0.1 wt.%), and Si (0.05–0.08 wt.%). The ash content of the resin rodlets ranges from 4 to 24 wt.% and averages 12 wt.%. Total sulfur contents range from 1.7 to 3.6 wt.%. Resins of fossil plants are known to have little or no sulfur and ash; therefore, these data and the presence of minerals in fractures indicate that most of the sulfur and mineral matter were introduced into the resin partly or wholly after the time of brittle fracture of the resin. The probable source of the resin rodlets is fossil pinaceous conifer cones, which are known to have resin canals as much as 2400 μm in diameter.

International Journal of Coal Geology

Structural control of coalbed methane production in Alabama

Thin-skinned structures are distributed throughout the Alabama coalbed methane fields, and these structures affect the production of gas and water from coal-bearing strata. Extensional structures in Deerlick Creek and Cedar Cove fields include normal faults and hanging-wall rollovers, and area balancing indicates that these structures are detached in the Pottsville Formation. Compressional folds in Gurnee and Oak Grove fields, by comparison, are interpreted to be detachment folds formed above decollements at different stratigraphic levels. Patterns of gas and water production reflect the structural style of each field and further indicate that folding and faulting have affected the distribution of permeability and the overall success of coalbed methane operations. Area balancing can be an effective way to characterize coalbed methane reservoirs in structurally complex regions because it constrains structural geometry and can be used to determine the distribution of layer-parallel strain. Comparison of calculated requisite strain and borehole expansion data from calliper logs suggests that strain in coalbed methane reservoirs is predictable and can be expressed as fracturing and small-scale faulting. However, refined methodology is needed to analyze heterogeneous strain distributions in discrete bed segments. Understanding temporal variation of production patterns in areas where gas and water production are influenced by map-scale structure will further facilitate effective management of coalbed methane fields.Thin-skinned structures are distributed throughout the Alabama coalbed methane fields, and these structures affect the production of gas and water from coal-bearing strata. Extensional structures in Deerlick Creek and Cedar Cove fields include normal faults and hanging-wall rollovers, and area balancing indicates that these structures are detached in the Pottsville Formation. Compressional folds in Gurnee and Oak Grove fields, by comparison, are interpreted to be detachment folds formed above decollements at different stratigraphic levels. Patterns of gas and water production reflect the structural style of each field and further indicate that folding and faulting have affected the distribution of permeability and the overall success of coalbed methane operations. Area balancing can be an effective way to characterize coalbed methane reservoirs in structurally complex regions because it constrains structural geometry and can be used to determine the distribution of layer-parallel strain. Comparison of calculated requisite strain and borehole expansion data from calliper logs suggests that strain in coalbed methane reservoirs is predictable and can be expressed as fracturing and small-scale faulting. However, refined methodology is needed to analyze heterogeneous strain distributions in discrete bed segments. Understanding temporal variation of production patterns in areas where gas and water production are influenced by map-scale structure will further facilitate effective management of coalbed methane fields.

International Journal of Coal Geology

Estimating the pressure-limited CO2 injection and storage capacity of the United States saline formations: Effect of the presence of hydrocarbon reservoirs

The U.S. Geological Survey (USGS) national assessment of carbon dioxide (CO 2 ) storage capacity evaluated 192 saline Storage Assessment Units (SAUs) in 33 U.S. onshore sedimentary basins that may be utilized for CO 2 storage (see USGS Circular 1386). Similar to many other available models, volumetric analysis was utilized to estimate the initial CO 2 injection and storage capacity of these SAUs based on aquifer characteristics and buoyant and residual trapping. The factor being almost always overlooked in most CO 2 storage capacity models is that many of the evaluated SAUs contain large numbers of both conventional and unconventional discovered and undiscovered oil and gas reservoirs. The hydrocarbon production and pressure distribution of the resident oil and gas reservoirs may be negatively influenced by the propagated CO 2 plume and pressure front resulting from a CO 2 injection and storage operation in the surrounding SAU. To have a more realistic and accurate estimation of CO 2 injection and storage capacity in saline formations, a model was previously developed that considers the CO 2 injectivity of a given formation, underground pressure build-up limitations imposed by the rock fracturing pressure and the presence of hydrocarbon reservoirs within these aquifers. The developed method estimates the pre–brine extraction, pressure-limited CO 2 injection and storage capacity of a saline formation by applying 3D numerical simulation only on the effective injection area (A eff ) surrounding each CO 2 injection well utilizing TOUGH2-ECO2N simulation software.

Sligo and Hosston Formations

A viscoelastic damage model with applications to stable and unstable fracturing

A viscoelastic damage rheology model is presented that provides a generalization of Maxwell viscoelasticity to a non-linear continuum mechanics framework incorporating material degradation and recovery, transition from stable to unstable fracturing and gradual accumulation of non-reversible deformation. The model is a further development of the damage rheology framework of Lyakhovsky et al. for evolving effective elasticity. The framework provides a quantitative treatment for macroscopic effects of evolving distributed cracking with local density represented by an intensive state variable. The formulation, based on thermodynamic principles, leads to a system of kinetic equations for the evolution of damage. An effective viscosity inversely proportional to the rate of damage increase is introduced to account for gradual accumulation of irreversible deformation due to dissipative processes. A power-law relation between the damage variable and elastic moduli leads to a non-linear coupling between the rate of damage evolution and the damage variable itself. This allows the model to reproduce a transition from stable to unstable fracturing of brittle rocks and the Kaiser effect. 3-D numerical simulations based on the model formulation for homogeneous and heterogeneous materials account for the main features of rock behaviour under large strain. The model coefficients are constrained, using triaxial laboratory experiments with low-porosity Westerly granite and high-porosity Berea sandstone samples.

Geophysical Journal International

Organic substances in produced and formation water from unconventional natural gas extraction in coal and shale

Organic substances in produced and formation water from coalbed methane (CBM) and gas shale plays from across the USA were examined in this study. Disposal of produced waters from gas extraction in coal and shale is an important environmental issue because of the large volumes of water involved and the variable quality of this water. Organic substances in produced water may be environmentally relevant as pollutants, but have been little studied. Results from five CBM plays and two gas shale plays (including the Marcellus Shale) show a myriad of organic chemicals present in the produced and formation water. Organic compound classes present in produced and formation water in CBM plays include: polycyclic aromatic hydrocarbons (PAHs), heterocyclic compounds, alkyl phenols, aromatic amines, alkyl aromatics (alkyl benzenes, alkyl biphenyls), long-chain fatty acids, and aliphatic hydrocarbons. Concentrations of individual compounds range from < 1 to 100 μg/L, but total PAHs (the dominant compound class for most CBM samples) range from 50 to 100 μg/L. Total dissolved organic carbon (TOC) in CBM produced water is generally in the 1–4 mg/L range. Excursions from this general pattern in produced waters from individual wells arise from contaminants introduced by production activities (oils, grease, adhesives, etc.). Organic substances in produced and formation water from gas shale unimpacted by production chemicals have a similar range of compound classes as CBM produced water, and TOC levels of about 8 mg/L. However, produced water from the Marcellus Shale using hydraulic fracturing has TOC levels as high as 5500 mg/L and a range of added organic chemicals including, solvents, biocides, scale inhibitors, and other organic chemicals at levels of 1000 s of μg/L for individual compounds. Levels of these hydraulic fracturing chemicals and TOC decrease rapidly over the first 20 days of water recovery and some level of residual organic contaminants remain up to 250 days after hydraulic fracturing. Although the environmental impacts of the organics in produced water are not well defined, results suggest that care should be exercised in the disposal and release of produced waters containing these organic substances into the environment because of the potential toxicity of many of these substances.

International Journal of Coal Geology