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USGS2003

The saturated zone at Yucca Mountain: An overview of the characterization and assessment of the saturated zone as a barrier to potential radionuclide migration

The US Department of Energy is pursuing Yucca Mountain, Nevada, for the development of a geologic repository for the disposal of spent nuclear fuel and high-level radioactive waste, if the repository is able to meet applicable radiation protection standards established by the US Nuclear Regulatory Commission and the US Environmental Protection Agency (EPA). Effective performance of such a repository would rely on a number of natural and engineered barriers to isolate radioactive waste from the accessible environment. Groundwater beneath Yucca Mountain is the primary medium through which most radionuclides might move away from the potential repository. The saturated zone (SZ) system is expected to act as a natural barrier to this possible movement of radionuclides both by delaying their transport and by reducing their concentration before they reach the accessible environment. Information obtained from Yucca Mountain Site Characterization Project activities is used to estimate groundwater flow rates through the site-scale SZ flow and transport model area and to constrain general conceptual models of groundwater flow in the site-scale area. The site-scale conceptual model is a synthesis of what is known about flow and transport processes at the scale required for total system performance assessment of the site. This knowledge builds on and is consistent with knowledge that has accumulated at the regional scale but is more detailed because more data are available at the site-scale level. The mathematical basis of the site-scale model and the associated numerical approaches are designed to assist in quantifying the uncertainty in the permeability of rocks in the geologic framework model and to represent accurately the flow and transport processes included in the site-scale conceptual model. Confidence in the results of the mathematical model was obtained by comparing calculated to observed hydraulic heads, estimated to measured permeabilities, and lateral flow rates calculated by the site-scale model to those calculated by the regional-scale flow model. In addition, it was confirmed that the flow paths leaving the region of the potential repository are consistent with those inferred from gradients of measured head and those independently inferred from water-chemistry data. The general approach of the site-scale SZ flow and transport model analysis is to calculate unit breakthrough curves for radionuclides at the interface between the SZ and the biosphere using the three-dimensional site-scale SZ flow and transport model. Uncertainties are explicitly incorporated into the site-scale SZ flow and transport abstractions through key parameters and conceptual models. ?? 2002 Elsevier Science B.V. All rights reserved.

Journal of Contaminant Hydrology↗
USGS2003

Modeling flow and transport in unsaturated fractured rock: An evaluation of the continuum approach

Because the continuum approach is relatively simple and straightforward to implement, it has been commonly used in modeling flow and transport in unsaturated fractured rock. However, the usefulness of this approach can be questioned in terms of its adequacy for representing fingering flow and transport in unsaturated fractured rock. The continuum approach thus needs to be evaluated carefully by comparing simulation results with field observations directly related to unsaturated flow and transport processes. This paper reports on such an evaluation, based on a combination of model calibration and prediction, using data from an infiltration test carried out in a densely fractured rock within the unsaturated zone of Yucca Mountain, Nevada. Comparisons between experimental and modeling results show that the continuum approach may be able to capture important features of flow and transport processes observed from the test. The modeling results also show that matrix diffusion may have a significant effect on the overall transport behavior in unsaturated fractured rocks, which can be used to estimate effective fracture-matrix interface areas based on tracer transport data. While more theoretical, numerical, and experimental studies are needed to provide a conclusive evaluation, this study suggests that the continuum approach is useful for modeling flow and transport in unsaturated, densely fractured rock. ?? 2002 Elsevier Science B.V. All rights reserved.

Journal of Contaminant Hydrology↗
USGS2000

Characterization of seismic hazard and structural response by energy flux

Seismic safety of structures depends on the structure's ability to absorb the seismic energy that is transmitted from ground to structure. One parameter that can be used to characterize seismic energy is the energy flux. Energy flux is defined as the amount of energy transmitted per unit time through a cross-section of a medium, and is equal to kinetic energy multiplied by the propagation velocity of seismic waves. The peak or the integral of energy flux can be used to characterize ground motions. By definition, energy flux automatically accounts for site amplification. Energy flux in a structure can be studied by formulating the problem as a wave propagation problem. For buildings founded on layered soil media and subjected to vertically incident plane shear waves, energy flux equations are derived by modeling the buildings as an extension of the layered soil medium, and considering each story as another layer. The propagation of energy flux in the layers is described in terms of the upgoing and downgoing energy flux in each layer, and the energy reflection and transmission coefficients at each interface. The formulation results in a pair of simple finite-difference equations for each layer, which can be solved recursively starting from the bedrock. The upgoing and downgoing energy flux in the layers allows calculation of the energy demand and energy dissipation in each layer. The methodology is applicable to linear, as well as nonlinear structures. ?? 2000 Published by Elsevier Science Ltd.

Soil Dynamics and Earthquake Engineering↗
USGS2002

3D near-surface soil response from H/V ambient-noise ratios

The applicability of the horizontal-to-vertical (H/V) ambient-noise spectral ratio for characterizing earthquake site effects caused by nearsurface topography and velocity structures was evaluated at sites underlain by thick (i.e. >100 m) sediment deposits near the southern-end of the New Madrid seismic zone in the central United States. Three-component ambient-noise and velocity models derived from seismic (shearwave) refraction/reflection surveys showed that a relatively horizontal, sharp shear-wave velocity interface in the soil column resulted in an H/V spectral ratio with a single well-defined peak. Observations at sites with more than one sharp shear-wave velocity contrast and horizontally arranged soil layers resulted in at least two well-defined H/V spectral ratio peaks. Furthermore, at sites where there were sharp shear-wave velocity contrasts in nonhorizontal, near-surface soil layers, the H/V spectra exhibited a broad-bandwidth, relatively low amplitude signal instead of a single well-defined peak.

Soil Dynamics and Earthquake Engineering↗
USGS2000

Quantification of the microphytobenthic primary production in european intertidal mudflats - A modelling approach

A deterministic model quantifying the dynamics of the microphytobenthic biomass in the first centimeter of the mud was formulated as part of the MAST-III/INTRMUD project. The main modelled processes are production by photosynthesis, active vertical migration of the microphytobenthos and global biomass losses, encompassing grazing, mortality and resuspension during immersion periods. The model emphasizes the role of the interface between mud and air, which is crucial for the production. The microalgal biofilm present at the mud surface during day-time emersion periods induces most of the differences between microphytobenthos and phytoplankton communities dynamics. The study of the mathematical properties of the system, under some simplifying assumptions, shows the convergence of the solutions to a stable cyclic equilibrium, in the whole observed range of the frequencies of the physical synchronizers of the production. Resilience time estimates suggest that microphytobenthic biomass attains an equilibrium rapidly, even after a strong perturbation. Around the equilibrium, the local model solutions agree fairly with the in situ observed dynamics of the total biomass. The sensitivity analysis suggests investigating the processes governing biomass losses, which are so far uncertain, and may further vary in space and time. (C) 2000 Elsevier Science Ltd.

Continental Shelf Research↗
USGS2002

Prediction of the fate of p,p'-DDE in sediment on the Palos Verdes shelf, California, USA

Long-term (60-yr) predictions of vertical profiles of p,p???-DDE concentrations in contaminated bottom sediments on the Palos Verdes shelf were calculated for three locations along the 60-m isobath using a numerical solution of the one-dimensional advection-diffusion equation. The calculations incorporated the following processes: sediment deposition (or erosion), depth-dependent solid-phase biodiffusive mixing, in situ diagenetic transformation, and loss of p,p???-DDE across the sediment-water interface by two mechanisms (resuspension of sediments by wave action and subsequent loss of p,p???-DDE to the water column by desorption, and desorption from sediments to porewater and subsequent molecular diffusion to the water column). A combination of field measurements, laboratory analyses, and calculations with supporting models was used to set parameters for the model. The model explains significant features observed in measurements made every 2 years from 1981 to 1997 by the County Sanitation Districts of Los Angeles (LACSD). Analyses of available data suggest that two sites northwest of the Whites Point sewage outfalls will remain depositional, even as particulate supply from the sewage-treatment plant and nearby Portuguese Bend Landslide decreases. At these sites, model predictions for 1991-2050 indicate that most of the existing inventory of p,p???-DDE will remain buried and that surface concentrations will gradually decrease. Analyses of data southeast of the outfalls suggest that erosion is likely to occur somewhere on the southeast edge of the existing effluent-affected deposit, and model predictions for such a site showed that erosion and biodiffusion will reintroduce the p,p???-DDE to the upper layer of sediments, with subsequent increases in surface concentrations and loss to the overlying water column.

California↗
USGS2003

Experimental and textural constraints on mafic enclave formation in volcanic rocks

We have used experiments and textural analysis to investigate the process of enclave formation during magma mixing at Southwest Trident volcano, Alaska. Andesite enclaves are present throughout the four dacite lava flows produced by the eruption, and resemble mafic enclaves commonly found in other volcanic rocks. Our experiments replicate the pressure–temperature–time path taken by enclave-forming andesite magma as it is engulfed in dacite during magma mixing. Pressure and temperature information for the andesite and dacite are from [Coombs et al., Contrib. Mineral. Petrol. 140 (2000) 99–118]. The andesite was annealed at 1000°C, and then cooled to 890°C at rates of 110°C h −1 , 10°C h −1 , and 2°C h −1 . Once cooled to 890°C, andesite was held at this lower temperature from times ranging from 1 to 40 h. The andesite that was cooled at the slower rates of 2°C h −1 and 10°C h −1 most resembles enclave groundmass texturally and compositionally. Based on simple thermal calculations, these rates are more consistent with cooling of the andesite groundmass below an andesite–dacite interface than with cooling of enclave-sized spheres. If enclaves do crystallize as spheres, post-crystallization disaggregation must occur. Calculations using the MELTS algorithm [Ghiorso and Sack, Contrib. Mineral. Petrol. 119 (1995) 197–212] show that for incoming andesite to become less dense than the dacite ∼34 volume % of its groundmass must crystallize to undergo ∼18 volume % vesiculation; these values are similar to those determined for Southwest Trident enclaves. Thus such crystallization may lead to ‘flotation’ of enclaves and be a viable mechanism for enclave formation and dispersal. The residual melt in the cooling experiments did not evolve to rhyolitic compositions such as seen in natural enclaves due to a lack of a decompression step in the experiments. Decompression experiments on Southwest Trident dacite suggest an average ascent rate for the eruption of ∼2–3 MPa h −1 . An andesite experiment that was cooled and then decompressed at this rate contains melt that matches that of the natural enclaves. It is apparent that decompression (ascent)-induced crystallization occurs in enclaves, but not in the form of microlites as happens in the dacite host, due either to insufficient residence time at chamber temperatures or to the pre-existing microphenocrysts which act as sites for new growth.

Alaska↗
USGS1996

Mobility of 2,2',5,5'-tetrachlorobiphenyl in model systems containing bottom sediments and water from the lower Fox River, Wisconsin

Sediment-water partitioning and diffusive transport of 2,2’,5,5’-tetrachlorobiphenyl, PCB congener IUPAC #52 (TCB52) were examined in laboratory experiments with sediments from two sites in the lower Fox River, Wisconsin. Native water was pumped at controlled flow rates through cells containing sediments amended with a known activity of carbon-14-labeled TCB52. Concentrations of TCB52 in water and sediments were determined by liquid scintillation measurements of carbon-14 activity. Sediment-water partitioning was independent of flow rate for rates up to 8 m/d. Distribution coefficients (K d ) and soil-sorption coefficients (K oc ) were found to be at maximum levels 5–10 cm below the surface, despite an absence of significant variation in the fraction of organic carbon (f oc ) through the same profile. Other factors, such as the effects of colloids and microbial activity in the sediments, are likely to be important in controlling the PCB distribution. Log K d and log K oc ranges were 4.1–4.9 and 5.3–6.1, respectively, and calculated effective diffusivities at the sediment-water interface ranged from 3 to 8 × 10 −10 cm 2 /s. Gradual increases with time in TCB52 concentrations in the water phase, possibly due to effects of microbial activity, were observed. Diffusion experiments and models showed that the TCB52 migration rate within the sediment column is 8-9 mm/yr.

Journal of Great Lakes Research↗
USGS2002

A census of marine life: Unknowable or just unknown?

As an introduction to the entire volume, this article outlines the relationships among the five elements of the Census of Marine Life (CoML) that create new knowledge: (1) The Ocean Biogeographic Information System (OBIS), a marine component of the Global Biodiversity Information Facility, links marine databases around the world to provide an Internet accessible, dynamic interface for comparing species-level, geo-referenced biodiversity data in relation to ocean habitats. The entire CoML field project data will be managed in and accessible through OBIS. (2) The History of Marine Animal Populations (HMAP) is a unique new synthesis of historical and biological research that will document marine biodiversity, globally, up to 500 years ago, before significant human impact, and store it in formats compatible with modern data in OBIS. (3) The Scientific Committee on Oceanic Research Working Group 118 monitors and recommends advanced marine technologies, ready to be routinely used in CoML field projects. (4) CoML Initial Field Projects develop and calibrate these technologies in selected regions to facilitate and accelerate global biodiversity research. As calibrated technologies and protocols are adopted in many regions, qualitative and quantitative biodiversity discoveries accumulate. (5) The Future of Marine Animal Populations (FMAP) program will insure that the data in OBIS are suitable for modeling and predicting changes in global biodiversity in response to fishing, pollution, and climate change challenges. It will make datasets available for hindcasting and forecasting analyses linked to physical ocean observations and assist in documenting the impacts of conservation efforts on sustainability.

Oceanologica Acta↗
USGS2002

A pitfall in shallow shear-wave refraction surveying

The shallow shear-wave refraction method works successfully in an area with a series of horizontal layers. However, complex near-surface geology may not fit into the assumption of a series of horizontal layers. That a plane SH-wave undergoes wave-type conversion along an interface in an area of nonhorizontal layers is theoretically inevitable. One real example shows that the shallow shear-wave refraction method provides velocities of a converted wave rather than an SH- wave. Moreover, it is impossible to identify the converted wave by refraction data itself. As most geophysical engineering firms have limited resources, an additional P-wave refraction survey is necessary to verify if velocities calculated from a shear-wave refraction survey are velocities of converted waves. The alternative at this time may be the surface wave method, which can provide reliable S-wave velocities, even in an area of velocity inversion (a higher velocity layer underlain by a lower velocity layer). ?? 2002 Elsevier Science B.V. All rights reserved.

Journal of Applied Geophysics↗
USGS2008

GSTARS computer models and their applications, part I: theoretical development

GSTARS is a series of computer models developed by the U.S. Bureau of Reclamation for alluvial river and reservoir sedimentation studies while the authors were employed by that agency. The first version of GSTARS was released in 1986 using Fortran IV for mainframe computers. GSTARS 2.0 was released in 1998 for personal computer application with most of the code in the original GSTARS revised, improved, and expanded using Fortran IV/77. GSTARS 2.1 is an improved and revised GSTARS 2.0 with graphical user interface. The unique features of all GSTARS models are the conjunctive use of the stream tube concept and of the minimum stream power theory. The application of minimum stream power theory allows the determination of optimum channel geometry with variable channel width and cross-sectional shape. The use of the stream tube concept enables the simulation of river hydraulics using one-dimensional numerical solutions to obtain a semi-two- dimensional presentation of the hydraulic conditions along and across an alluvial channel. According to the stream tube concept, no water or sediment particles can cross the walls of stream tubes, which is valid for many natural rivers. At and near sharp bends, however, sediment particles may cross the boundaries of stream tubes. GSTARS3, based on FORTRAN 90/95, addresses this phenomenon and further expands the capabilities of GSTARS 2.1 for cohesive and non-cohesive sediment transport in rivers and reservoirs. This paper presents the concepts, methods, and techniques used to develop the GSTARS series of computer models, especially GSTARS3. ?? 2008 International Research and Training Centre on Erosion and Sedimentation and the World Association for Sedimentation and Erosion Research.

International Journal of Sediment Research↗
USGS2001

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↗
USGS2002

Accelerated solvent extraction followed by on-line solid-phase extraction coupled to ion trap LC/MS/MS for analysis of benzalkonium chlorides in sediment samples

Benzalkonium chlorides (BACs) were successfully extracted from sediment samples using a new methodology based on accelerated solvent extraction (ASE) followed by an on-line cleanup step. The BACs were detected by liquid chromatography/ion trap mass spectrometry (LC/MS) or tandem mass spectrometry (MS/MS) using an electrospray interface operated in the positive ion mode. This methodology combines the high efficiency of extraction provided by a pressurized fluid and the high sensitivity offered by the ion trap MS/MS. The effects of solvent type and ASE operational variables, such as temperature and pressure, were evaluated. After optimization, a mixture of acetonitrile/water (6:4 or 7:3) was found to be most efficient for extracting BACs from the sediment samples. Extraction recoveries ranged from 95 to 105% for C12 and C14 homologues, respectively. Total method recoveries from fortified sediment samples, using a cleanup step followed by ASE, were 85% for C12BAC and 79% for C14-BAC. The methodology developed in this work provides detection limits in the subnanogram per gram range. Concentrations of BAC homologues ranged from 22 to 206 ??g/kg in sediment samples from different river sites downstream from wastewater treatment plants. The high affinity of BACs for soil suggests that BACs preferentially concentrate in sediment rather than in water.

Analytical Chemistry↗
USGS2021

The role of behavioral ecotoxicology in environmental protection

For decades, we have known that chemicals affect human and wildlife behavior. Moreover, due to recent technological and computational advances, scientists are now increasingly aware that a wide variety of contaminants and other environmental stressors adversely affect organismal behavior and subsequent ecological outcomes in terrestrial and aquatic ecosystems. There is also a groundswell of concern that regulatory ecotoxicology does not adequately consider behavior, primarily due to a lack of standardized toxicity methods. This has, in turn, led to the exclusion of many behavioral ecotoxicology studies from chemical risk assessments. To improve understanding of the challenges and opportunities for behavioral ecotoxicology within regulatory toxicology/risk assessment, a unique workshop with international representatives from the fields of behavioral ecology, ecotoxicology, regulatory (eco)toxicology, neurotoxicology, test standardization, and risk assessment resulted in the formation of consensus perspectives and recommendations, which promise to serve as a roadmap to advance interfaces among the basic and translational sciences, and regulatory practices.

Environmental Science & Technology↗
USGS2021

Discrete sample introduction module for quantitative and isotopic analysis of methane and other gases by cavity ring-down spectroscopy

Carbon dioxide (CO 2 ) and methane (CH 4 ) are natural and anthropogenic products that play a central role in the global carbon cycle and regulating Earth’s climate. Applications utilizing laser absorption spectroscopy, which continuously measure concentrations and stable isotope ratios of these greenhouse gases, are routinely employed to measure the source and magnitude of atmospheric inputs. We developed a discrete sample introduction module (DSIM) to enable measurements of methane and CO 2 concentrations and δ 13 C values from limited volume (5–100 mL) gas samples when interfaced with a commercially available cavity ring-down spectroscopy (CRDS) analyzer. The analysis has a dynamic range that spans six orders of magnitude from 100% analyte to the lower limit of instrument detection (2 ppm). We demonstrate system performance for methane by comparing concentrations and δ 13 C results from the DSIM-CRDS system and traditional methods for a variety of sample types, including low concentration (nanomolar CH 4 ) seawater and high concentration (>90% CH 4 ) natural gas. The expansive concentration range of the field-portable DSIM-CRDS system can measure enhances analytical performance for investigating methane and CO 2 dynamics and, potentially, other gases measured by laser absorption spectroscopy.

Environmental Science & Technology↗
USGS2023

Seasonal differences and grazing pressure alter the fate of gold nanoparticles in a microcosm experiment

Gold nanoparticles (AuNPs) are used as models to track and predict NP fates and effects in ecosystems. Previous work found that aquatic macrophytes and their associated biofilm primarily drove the fate of AuNPs within aquatic ecosystems and that seasonality was an important abiotic factor in the fate of AuNPs. Therefore, the present work aims to study if grazers, by feeding on these interfaces, modify the AuNP fate and if this is altered by seasonal fluctuations. Microcosms were dosed with 44.8 μg/L of AuNP weekly for 4 weeks and maintained in environmental chambers simulating Spring and Fall light and temperature conditions. We discovered that seasonal changes and the presence of grazers significantly altered the fate of Au. Higher temperatures in the warmer season increased dissolved organic carbon (DOC) content in the water column, leading to stabilization of Au in the water column. Additionally, snail grazing on biofilm growing on the Egeria densa surface led to a transfer of Au from macrophytes to the organic matter above the sediments. These results demonstrate that climate and grazers significantly impacted the fate of Au from AuNPs, highlighting the role that grazers might have in a large and biologically more complex ecosystem.

Environmental Science & Technology↗
USGS2026

An ecosystem-scale model of PFAS dynamics in stream-to-riparian food webs

Per- and polyfluoroalkyl substances (PFAS) are widespread contaminants in aquatic ecosystems, where they bioaccumulate and trophically transfer through food webs. We derived an ecosystem-scale model assessing Σ 12 PFAS partitioning, bioaccumulation by larval aquatic insects, bioamplification by adult aquatic insects, and trophic transfer from aquatic insects to riparian spiders using data collected across five streams in a mildly impacted watershed. Partitioning involved the greatest PFAS enrichments (range in posterior median log 10 k d values = 1.5–2.1), with lesser concentration increases from particulates to larval aquatic insects and from larval to adult aquatic insects, and Σ 12 PFAS concentration decreases from adult aquatic insects to spiders. Among the 12 compounds, PFOS had the largest proportional contribution to Σ 12 PFAS concentrations for all sample types, with consistently increasing concentrations from surface water to adult aquatic insects. Σ 12 PFAS concentrations (5.4–51 ppb wet weight), body burdens (0.44–5.2 ng per individual), and bioamplification factors (0.15–4.9) differed considerably among five common aquatic insect taxa. This study presents a robust modeling framework for PFAS trophodynamics and offers insights into the biological controls that contribute to the context dependency of PFAS at the interfaces of aquatic and terrestrial food webs.

Connecticut, Massachusetts↗
USGS1998

Polycrystalline methane hydrate: Synthesis from superheated ice, and low-temperature mechanical properties

We describe a new and efficient technique to grow aggregates of pure methane hydrate in quantities suitable for physical and material properties testing. Test specimens were grown under static conditions by combining cold, pressurized CH 4 gas with granulated H 2 O ice, and then warming the reactants to promote the reaction CH 4 (g) + 6H 2 O(s→l) → CH 4 ·6H 2 O (methane hydrate). Hydrate formation evidently occurs at the nascent ice/liquid water interface on ice grain surfaces, and complete reaction was achieved by warming the system above the ice melting point and up to 290 K, at 25−30 MPa, for approximately 8 h. The resulting material is pure, cohesive, polycrystalline methane hydrate with controlled grain size and random orientation. Synthesis conditions placed the H 2 O ice well above its melting temperature while reaction progressed, yet samples and run records showed no evidence for bulk melting of the unreacted portions of ice grains. Control experiments using Ne, a non-hydrate-forming gas, showed that under otherwise identical conditions, the pressure reduction and latent heat associated with ice melting are easily detectable in our fabrication apparatus. These results suggest that under hydrate-forming conditions, H 2 O ice can persist metastably to temperatures well above its ordinary melting point while reacting to form hydrate. Direct observations of the hydrate growth process in a small, high-pressure optical cell verified these conclusions and revealed additional details of the hydrate growth process. Methane hydrate samples were then tested in constant-strain-rate deformation experiments at T = 140−200 K, P c = 50−100 MPa, and ε = 10 - 4 −10 - 6 s - 1 . Measurements in both the brittle and ductile fields showed that methane hydrate has measurably different strength than H 2 O ice, and work hardens to an unusually high degree compared to other ices as well as to most metals and ceramics at high homologous temperatures. This work hardening may be related to a changing stoichiometry under pressure during plastic deformation; X-ray analyses showed that methane hydrate undergoes a process of solid-state disproportionation or exsolution during deformation at conditions well within its conventional stability field.

Energy and Fuels↗