Experimental formation of massive hydrate deposits from accumulation of CH4 gas bubbles within synthetic and natural sediments

In order for methane to be economically produced from the seafloor, prediction and detection of massive hydrate deposits will be necessary. In many cases, hydrate samples recovered from seafloor sediments appear as veins or nodules, suggesting that there are strong geologic controls on where hydrate is likely to accumulate. Experiments have been conducted examining massive hydrate accumulation from methane gas bubbles within natural and synthetic sediments in a large volume pressure vessel through temperature and pressure data, as well as visual observations. Observations of hydrate growth suggest that accumulation of gas bubbles within void spaces and at sediment interfaces likely results in the formation of massive hydrate deposits. Methane hydrate was first observed as a thin film forming at the gas/water interface of methane bubbles trapped within sediment void spaces. As bubbles accumulated, massive hydrate growth occurred. These experiments suggest that in systems containing free methane gas, bubble pathways and accumulation points likely control the location and habit of massive hydrate deposits.     

Geochemistry of the Uintjiesberg kimberlite, South Africa: petrogenesis of an off-craton, group I, kimberlite

The Uintjiesberg kimberlite diatreme occurs within the Proterozoic Namaqua–Natal Belt, South Africa, approximately 60 km to the southwest of the Kaapvaal craton boundary. It is a group I, calcite kimberlite that has an emplacement age of 100 Ma. Major and trace element data, in combination with petrography, are used to evaluate its petrogenesis and the nature of its source region. Macrocryst phases are predominantly olivine with lesser phlogopite, with very rare garnet and Cr-rich clinopyroxene. Geochemical variation amongst the macrocrystic samples (Mg# 0.85–0.87, SiO₂=27.0–29.3%, MgO=26.1–30.5%, CaO=10.9–13.5%) is shown to result from 10% to 40% entrainment and partial assimilation of peridotite xenoliths, whereas that shown by the aphanitic samples (Mg# 0.80–0.83, SiO₂=19.1–23.0%, MgO=17.9–23.9%, CaO=16.5–23.7%) is consistent with 7–25% crystal fractionation of olivine and minor phlogopite. Changing trajectories on chemical variation diagrams allow postulation of a primary magma composition with 25% SiO₂, 26% MgO, 2.3% Al₂O₃, 5%H₂O, 8.6% CO₂ and Mg#=0.85.

Forward melting models, assuming 0.5% melting, indicate derivation of the primary Uintjiesberg kimberlite magma from a source enriched in light rare earth elements (LREE) by 10× chondrite and heavy REE (HREE) by 0.8–2× chondrite, the latter being dependent on the proportion of residual garnet. Significant negative Rb, K, Sr, Hf and Ti anomalies present in the inferred primary magma composition are superimposed on otherwise generally smooth primitive mantle-normalized trace element patterns, and are inferred to be a characteristic of the primary magma composition. The further requirement for a source with chondritic or lower HREE abundances, residual olivine with high Fo content (Fo₉₄) suggests derivation from a mantle previously depleted in mafic melt but subsequently enriched in highly incompatible elements prior to kimberlite genesis. These requirements are interpreted in the context of melting of continental lithospheric mantle previously enriched by metasomatic fluids derived from a sublithospheric (plume?) source.     

Effects of variation in loading protocol on the strength and deformation capacity of ductile reinforced concrete beams

Understanding the impact of prior earthquake damage on residual capacity is important for postearthquake damage assessment of buildings; however, interpretation of such impact is challenging when based on tests using traditional reversed‐cyclic loading protocols. A new loading protocol, consisting of a dynamic earthquake displacement history followed by quasi‐static reversed‐cyclic loading to failure, is presented as an alternative to traditional simulated seismic loading protocols. Data are analyzed from a set of 12 nominally identical ductile reinforced concrete beams that were tested by using variations of this protocol and traditional reversed‐cyclic and monotonic protocols. Differences in the cycle content of the earthquake displacement histories applied to the test specimens allowed for the effects of load history variation below 2.2% drift to be isolated. It is found that such variation had no effect on the beam deformation capacities. The effects of dynamic loading rates are also analyzed and compared against control quasi‐static specimens. Relative strength increases due to dynamic loading are found to be more significant at yield than at ultimate. Dynamic loading rates led to modest reductions in the beam deformation capacities, but the presence of causality between these variables remains uncertain.     

Seismic performance of steel friction connections considering direct-repair costs

This study compares seismic losses considering initial construction costs and direct-repair costs for New Zealand steel moment-resisting frame buildings with friction connections and those with extended bolted-end-plate connections. A total of 12 buildings have been designed and analysed considering both connection types, two building heights (4-storey and 12-storey), and three locations around New Zealand (Auckland, Christchurch, and Wellington). It was found that buildings with friction connections required design to a higher design ductility, yet are generally stiffer due to larger beams being required to satisfy higher connection overstrength requirements. This resulted in the frames with friction connections experiencing lower interstorey drifts on most floors but similar peak total floor accelerations, and subsequently incurring lower drift-related seismic repair losses. Frames with friction connections tended to have lower expected net-present-costs within 50 years of the building being in service for shorter buildings and/or if located in regions of high seismicity. None of the frames with friction connections in Auckland showed any benefits due to the low seismicity of the region.     

Building and Testing an <Emphasis Type="Italic">a priori</Emphasis> Geophysical Model for Western Eurasia and North Africa

We construct and evaluate a new three-dimensional model of crust and upper mantle structure in Western Eurasia and North Africa (WENA) extending to 700 km depth and having 1° parameterization. The model is compiled in an a priori fashion entirely from existing geophysical literature, specifically, combining two regionalized crustal models with a high-resolution global sediment model and a global upper mantle model. The resulting WENA1.0 model consists of 24 layers: water, three sediment layers, upper, middle, and lower crust, uppermost mantle, and 16 additional upper mantle layers. Each of the layers is specified by its depth, compressional and shear velocity, density, and attenuation (quality factors, Q _P and Q _S ). The model is tested by comparing the model predictions with geophysical observations including: crustal thickness, surface wave group and phase velocities, upper mantle _n velocities, receiver functions, P-wave travel times, waveform characteristics, regional 1-D velocities, and Bouguer gravity. We find generally good agreement between WENA1.0 model predictions and empirical observations for a wide variety of independent data sets. We believe this model is representative of our current knowledge of crust and upper mantle structure in the WENA region and can successfully be used to model the propagation characteristics of regional seismic waveform data. The WENA1.0 model will continue to evolve as new data are incorporated into future validations and any new deficiencies in the model are identified. Eventually this a priori model will serve as the initial starting model for a multiple data set tomographic inversion for structure of the Eurasian continent.     

A Simple Relation to Constrain Groundwater Models Using Surface Deformation

A simple relation between pore pressure change and one-dimensional surface deformation is presented. The relation is for pore pressure change in a confined aquifer that causes surface deformation. It can be applied to groundwater models of any discretization and is computationally efficient. The estimated surface deformation from model results can be compared to observed surface deformation through geodetic techniques such as Differential Interferometric Synthetic Aperture Radar. Model parameters then are constrained using the observed surface deformation. The validity of this relation is shown through constraint of model parameters for surface uplift due to pore pressure increase caused by wastewater disposal injection.     

Quantifying hydrogen‐deuterium exchange of meteoritic dicarboxylic acids during aqueous extraction

Abstract— Hydrogen isotope ratios of organic compounds in carbonaceous chondrites provide critical information about their origins and evolutionary history. However, because many of these compounds are obtained by aqueous extraction, the degree of hydrogen‐deuterium (H/D) exchange that occurs during the process needs to be quantitatively evaluated. This study uses compound‐specific hydrogen isotopic analysis to quantify the H/D exchange during aqueous extraction. Three common meteoritic dicarboxylic acids (succinic, glutaric, and 2‐methyl glutaric acids) were refluxed under conditions simulating the extraction process. Changes in δD values of the dicarboxylic acids were measured following the reflux experiments. A pseudo‐first order rate law was used to model the H/D exchange rates which were then used to calculate the isotope exchange resulting from aqueous extraction. The degree of H/D exchange varies as a result of differences in molecular structure, the alkalinity of the extraction solution and presence/absence of meteorite powder. However, our model indicates that succinic, glutaric, and 2‐methyl glutaric acids with a δD of 1800%***_o would experience isotope changes of 38_o, 10_o, and 6_o, respectively during the extraction process. Therefore, the overall change in δD values of the dicarboxylic acids during the aqueous extraction process is negligible. We also demonstrate that H/D exchange occurs on the chiral α‐carbon in 2‐methyl glutaric acid. The results suggest that the racemic mixture of 2‐methyl glutaric acid in the Tagish Lake meteorite could result from post‐synthesis aqueous alteration. The approach employed in this study can also be used to quantify H/D exchange for other important meteoritic compounds such as amino acids.     

Kinetics of methane clathrate formation and dissociation under Mars relevant conditions

Spectral observations have detected methane within the martian atmosphere (Formisano, V., Atreya, S., Encrenaz, T., Ignatiev, N., Giuranna, M. [2004]. Science 306, 1758–1761; Mumma, M.J. et al. [2009]. Science 323, 1041–1045), however, the origin of the methane has not been determined. Methane clathrate (also referred to as methane hydrate) has been suggested as a potential subsurface reservoir, storing and releasing biologic and/or abiogenic methane. In this study, rates of methane hydrate formation and dissociation were measured experimentally at 234–264 K and 1.4–4.7 MPa to test the clathrate reservoir hypothesis. Initial formation rates range from 4.3 × 10^?6 to 8.1 × 10^?5 mol m^?2 s^?1. Results show decreasing rates of formation over time in individual experiments, indicating initial rapid clathration, followed by diffusion-limited transport of methane into the ice through the previously formed hydrate. These experiments indicate increased pressure results in increased formation rates, likely the result of higher concentration gradients, enhancing the methane diffusion flux into the solid phase. Experiments conducted at elevated temperatures produced faster initial rates of formation, resulting from increased kinetic energy of methane molecules and/or thickening of the Quasi-Liquid Layer. Based on this temperature dependence, the activation energy for methane hydrate formation from ice was determined to be 35.9 kJ/mol. Hydrate dissociation experiments initiated by depressurization or warming at conditions between 222 K and 265 K and 0.1–2.0 MPa were conducted following each formation experiment, yielding methane hydrate dissociation rates from 3.01 × 10^?6 to 9.92 × 10^?5 mol m^?2 s^?1. While both hydrate dissociation and formation showed decreasing instantaneous rates over the course of each experiment, the transition between the initial rate of dissociation and the interpreted diffusion-limited period of continued dissociation was more abrupt than that observed in formation experiments, supporting an ice shielding effect. The initial concentration of methane in the solid phase had a significant effect on hydrate dissociation rates. Higher methane concentrations in the solid phase produce faster initial rates, likely due to increased concentration gradients, thus increasing the diffusion component of dissociation. Increased temperatures also produced faster dissociation rates, yielding an activation energy for dissociation of 32.7 kJ/mol. The rates determined within this study suggest that small near-surface methane hydrate reservoirs are a feasible source for recent methane plumes detected on Mars. Rates of methane release from gas hydrates also indicate that gas hydrate dissociation may have played a role in forming ancient chaos terrain and associated outflow channels.     

Quantifying sedimentation patterns of small landslide-dammed lakes in the central Oregon Coast Range

Understanding sedimentation patterns in small coastal watersheds due to landscape perturbations is critical for connecting hillslope and fluvial processes, in addition to managing aquatic habitats for anadromous fish and other aquatic species in the Oregon Coast Range (OCR). Changes in sedimentation patterns spanning the last 250 years are preserved in two landslide-dammed lakes in small watersheds (< 10 km²) underlain by the Tyee Formation in the central OCR. Dendrochronology of drowned Douglas-fir stumps in both lakes provided precise timing of the damming and formation of the lakes, with Klickitat Lake forming in winter ad 1751/52 and Wasson Lake in winter ad 1819/20. Perturbations from wildfires, logging and road development, and previously underappreciated snow events affect sedimentation rates in the lakes to different degrees, and are identified in the sediment record using cesium-137 (¹³⁷Cs), high-resolution charcoal stratigraphy, local fire records, and aerial photography. Each lake has variable sedimentation accumulation rates (0.05–4.4 cm yr⁻¹) and mass accumulation rates (0.02–1.42 g cm⁻² yr⁻¹). Sedimentation rates remained low from the landslide-damming events until the mid-19th century, when they increased following stand-replacing wildfires. Aside from a sediment remobilization triggered by human modification of the landslide dam at Klickitat Lake around 1960, the largest peaks in mass accumulation rates in the mid-20th century at both lakes in the early 1950s precede major road construction and logging activity in the watersheds. Subsequent sedimentation rates are lower, but variable, and possible effects of logging and road development might be exacerbated by abnormal precipitation and heavy snow events. A comparison of previous studies of landslide-dammed lakes in larger watershed of the OCR are consistent with our findings of increased sedimentation in the mid-20th century, as well as higher sedimentation rates in the debris-flow dominated southern Tyee Formation than in the lower-relief northern Tyee Formation.     

An evaluation of hemolymph cholinesterase activities in the tropical scallop,Euvola (Pecten) ziczac,for the rapid assessment of pesticide exposure

The use of sequential measurements of hemolymph cholinesterase activities as a non-invasive biomarker of seasonal organophosphate/carbamate exposure was investigated for the tropical scallop, Euvola (Pecten) ziczac. Overall activities of both acetylcholinesterase and butyrylcholinesterase were relatively high compared to studies with bivalve tissues. Acute in vivo experiments showed inhibition of hemolymph acetylcholinesterase activity at concentrations of the organophosphate insecticide chlorpyrifos of 0.1, 1 and 10 ng l(-1). Monthly sampling of hemolymph from scallops at two sites in Bermuda over a 15 month period showed seasonal acetylcholinesterase and butyrylcholinesterase inhibition. Direct and indirect evidence suggests that this inhibition did not relate to biochemical or physiological changes associated with gonad maturation and spawning, but rather reflected diffuse contamination of the marine environment by cholinesterase inhibitors or increased bioavailability of such inhibitors at these times. Repetitive sampling of scallop hemolymph for cholinesterase activities represents a rapid, sensitive and non-invasive method for assessing seasonal, sublethal pesticide exposure in these commercially important bivalves and suggests a wider use in marine pollution monitoring.