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Mineralogic and compositional properties of Martian soil and dust: results from Mars Pathfinder

Mars Pathfinder obtained multispectral, elemental, magnetic, and physical measurements of soil and dust at the Sagan Memorial Station during the course of its 83 sol mission. We describe initial results from these measurements, concentrating on multispectral and elemental data, and use these data, along with previous Viking, SNC meteorite, and telescopic results, to help constrain the origin and evolution of Martian soil and dust. We find that soils and dust can be divided into at least eight distinct spectral units, based on parameterization of Imager for Mars Pathfinder (IMP) 400 to 1000 nm multispectral images. The most distinctive spectral parameters for soils and dust are the reflectivity in the red, the red/blue reflectivity ratio, the near-IR spectral slope, and the strength of the 800 to 1000 nm absorption feature. Most of the Pathfinder spectra are consistent with the presence of poorly crystalline or nanophase ferric oxide(s), sometimes mixed with small but varying degrees of well-crystalline ferric and ferrous phases. Darker soil units appear to be coarser-grained, compacted, and/or mixed with a larger amount of dark ferrous materials relative to bright soils. Nanophase goethite, akaganeite, schwertmannite, and maghemite are leading candidates for the origin of the absorption centered near 900 nm in IMP spectra. The ferrous component in the soil cannot be well-constrained based on IMP data. Alpha proton X-ray spectrometer (APXS) measurements of six soil units show little variability within the landing site and show remarkable overall similarity to the average Viking-derived soil elemental composition. Differences exist between Viking and Pathfinder soils, however, including significantly higher S and Cl abundances and lower Si abundances in Viking soils and the lack of a correlation between Ti and Fe in Pathfinder soils. No significant linear correlations were observed between IMP spectral properties and APXS elemental chemistry. Attempts at constraining the mineralogy of soils and dust using normative calculations involving mixtures of smectites and silicate and oxide minerals did not yield physically acceptable solutions. We attempted to use the Pathfinder results to constrain a number of putative soil and dust formation scenarios, including palagonitization and acid-fog weathering. While the Pathfinder soils cannot be chemically linked to the Pathfinder rocks by palagonitization, this study and McSween et al. [1999] suggest that palagonitic alteration of a Martian basaltic rock, plus mixture with a minor component of locally derived andesitic rock fragments, could be consistent with the observed soil APXS and IMP properties.

Journal of Geophysical Research E: Planets

Effects of coal storage in air on physical and chemical properties of coal and on gas adsorption

This paper investigates changes in the high-volatile bituminous Lower Block Coal Member from Indiana owing to moisture availability and oxidation in air at ambient pressure and temperature over storage time. Specifically, it investigates changes in chemistry, in surface area, and pore structure, as well as changes in methane and carbon dioxide adsorption capacities. Our results document that the methane adsorption capacity increased by 40%, whereas CO 2 adsorption capacity increased by 18% during a 13-month time period. These changes in adsorption are accompanied by changes in chemistry and surface area of the coal. The observed changes in adsorption capacity indicate that special care must be taken when collecting samples and preserving coals until adsorption characteristics are measured in the laboratory. High-pressure isotherms from partially dried coal samples would likely cause overestimation of gas adsorption capacities, lead to a miscalculation of coal-bed methane prospects, and provide deceptively optimistic prognoses for recovery of coal-bed methane or capture of anthropogenic CO 2 . ?? 2009 Elsevier B.V. All rights reserved.

International Journal of Coal Geology

An on-campus well field for hydrogeophysics education and undergraduate research

The emerging subdiscipline of hydrogeophysics is underdeveloped in undergraduate curricula relative to its importance in professional engineering/environmental practice. In 2001, the Bucknell Department of Geology initiated efforts to refocus an undergraduate geophysics course on near-surface geophysical methods for hydrologic, environmental, and engineering problems. In addition to offering students practical experience, treatment of hydrogeophysics provides important pedagogical opportunities. Field-based hydrogeophysics labs challenge students to integrate concepts from other geology courses, as well as from physics, math, and chemistry. We faced two challenges in revising our geophysics course: (1) access to wells for field exercises on borehole geophysics; and (2) the costs of acquiring and maintaining equipment. We pursued two strategies to solve these problems. First, we established an on-campus well field, which serves as a field laboratory for downhole and cross-hole experiments. Second, we incorporated field demonstrations and lectures by professional geoscientists, including alumni, into our courses. By adding field exercises to our syllabi and promoting undergraduate research, we are building a cutting-edge dataset that includes televiewer and standard wellbore logging, cross-hole tomography, and hydraulic-test data. Student-led analysis of these data has already provided valuable insights into the control of fractures on aquifer properties, and these observations are being combined with outcrop studies to place our results in a more regional context.

Pennsylvania

The high-pressure electronic structure of magnesiowustite (Mg, Fe)O: applications to the physics and chemistry of the lower mantle

The electronic structure of magnesiowustite is investigated using self-consistent field X α scattered wave (SCF- X α-SW) molecular orbital calculations on (FeO 6 ) 10− and (FeMg 12 O 14 ) 2− clusters. Calculated one-electron transition energies are used to interpret the optical spectrum of (Mg, Fe)O. The results are applied to the electrical and thermal conductivity of the lower mantle. The spin pairing of Fe 2+ and the effect of pressure on bonding in magnesiowustite, with some inferences regarding the incorporation of oxygen in the outer core, is also addressed. The approach used here appears to give a reliable description of the energy and pressure dependence of the spin-allowed 5 T 2 g → 5 E g ligand field transition and the spin-pairing transition of Fe 2+ in (Mg, Fe)O. However, the oxygen to metal charge transfer transitions in (Mg, Fe)O are not as reliably determined insofar as the p - d band gap varies with cluster size and the energies of the charge transfer states cannot be found without including configurational interaction. Nevertheless, it is argued that the charge transfer transitions that are intrinsic to (Fe, Mg)O are of a sufficiently high energy to be irrelevant to the electrical and thermal conductivity of the lower mantle. This is especially true if Fe 2+ adopts the low-spin configuration. The geophysically significant properties of (Fe, Mg)O probably result from defect Fe 3+ .

Journal of Geophysical Research

Timescales and processes of methane hydrate formation and breakdown, with application to geologic systems

Gas hydrate is an ice-like form of water and low molecular weight gas stable at temperatures of roughly -10ºC to 25ºC and pressures of ~3 to 30 MPa in geologic systems. Natural gas hydrates sequester an estimated one-sixth of Earth’s methane and are found primarily in deepwater marine sediments on continental margins, but also in permafrost areas and under continental ice sheets. When gas hydrate is removed from its stability field, its breakdown has implications for the global carbon cycle, ocean chemistry, marine geohazards, and interactions between the geosphere and the ocean-atmosphere system. Gas hydrate breakdown can also be artificially driven as a component of studies assessing the resource potential of these deposits. Furthermore, geologic processes and perturbations to the ocean-atmosphere system (e.g., warming temperatures) can cause not only dissociation, but also more widespread dissolution of hydrate or even formation of new hydrate in reservoirs. Linkages between gas hydrate and disparate aspects of Earth’s near-surface physical, chemical, and biological systems render an assessment of the rates and processes affecting the persistence of gas hydrate an appropriate Centennial Grand Challenge. This paper reviews the thermodynamic controls on methane hydrate stability and then describes the relative importance of kinetic, mass transfer, and heat transfer processes in the formation and breakdown (dissociation and dissolution) of gas hydrate. Results from numerical modeling, laboratory, and some fields studies are used to summarize the rates of hydrate formation and breakdown, followed by an extensive treatment of hydrate dynamics in marine and cryospheric gas hydrate systems.

Journal of Geophysical Research-Solid Earth

Mineralogy and chemistry of cobbles at Meridiani Planum, Mars, investigated by the Mars Exploration Rover Opportunity

Numerous loose rocks with dimensions of a few centimeters to tens of centimeters and with no obvious physical relationship to outcrop rocks have been observed along the traverse of the Mars Exploration Rover Opportunity. To date, about a dozen of these rocks have been analyzed with Opportunity's contact instruments, providing information about elemental chemistry (Alpha Particle X‐ray Spectrometer), iron mineralogy and oxidation states (Mössbauer Spectrometer) and texture (Microscopic Imager). These “cobbles” appear to be impact related, and three distinct groups can be identified on the basis of chemistry and mineralogy. The first group comprises bright fragments of the sulfate‐rich bedrock that are compositionally and texturally indistinguishable from outcrop rocks. All other cobbles are dark and are divided into two groups, referred to as the “Barberton group” and the “Arkansas group,” after the first specimen of each that was encountered by Opportunity. Barberton group cobbles are interpreted as meteorites with an overall chemistry and mineralogy consistent with a mesosiderite silicate clast composition. Arkansas group cobbles appear to be related to Meridiani outcrop and contain an additional basaltic component. They have brecciated textures, pointing to an impact‐related origin during which local bedrock and basaltic material were mixed.

Journal of Geophysical Research E: Planets

Network connectivity contributes to native small-bodied fish assemblages in the upper Mississippi River system

Effective management and conservation of fishes requires understanding habitat use across multiple life stages while ensuring necessary habitats are both available and accessible. Tributary habitats may play an important role in recruitment and dispersal of fishes in anthropogenically modified rivers such as the Mississippi and Illinois Rivers of the Midwest U.S.A. Identifying source locations that contribute to recruitment of fish populations can determine the importance of connectivity within river networks and pinpoint critical habitats that sustain fish populations. In the Upper Mississippi River System (UMRS), the environments that fish use in early life stages (i.e., natal origin) can be identified using otolith trace element analysis due to stability and distinctness in water chemistry (strontium: calcium [Sr:Ca]) among water bodies that is reflected in otoliths. Here, we used trace element analysis to determine natal origin of six small-bodied fishes including bullhead minnow ( Pimephales vigilax ), emerald shiner ( Notropis atherinoides ), gizzard shad ( Dorosoma cepedianum ), bluegill ( Lepomis macrochirus ), orangespotted sunfish ( Lepomis humilis ), and yellow perch ( Perca flavescens ) across six reaches of the UMRS (Pools 4, 8, 13, 26, the Open River of the Middle Mississippi River, and the La Grange Pool of the Illinois River). Otolith core Sr:Ca for fishes was quantified using laser ablation inductively coupled plasma mass spectrometry. Using the resulting Sr:Ca chemical signatures of otolith cores, natal origin (tributary, immigrant, or potential resident) was determined for individual fish based on family-specific relationships between otolith and water chemistries. We found that all species originated from tributaries and other reaches (i.e., were immigrants) to varying extents, which acted as evidence for network connectivity. Specifically, tributaries contributed up to 48% of individuals at a given reach. In certain reaches, Pool 26 and the Open River reach, up to 80% of individuals in a species immigrated from another mainstem river reach. Network connectivity was also important in both upstream and downstream directions. Contributions from network connectivity varied among species: bullhead minnow used less whereas orangespotted sunfish used more network connectivity than when all species were combined. Further, the use of network connectivity varied spatially where individuals captured in Pool 8 and the La Grange Pool less often and those from Pool 26 and the Open River more often originated from network connectivity compared to the whole assemblage across reaches. These results indicate that species' life history traits probably interacted with the physical environment, which differs spatially, to yield observed recruitment source patterns. Our results show that network connectivity contributes to established assemblages of native small-bodied fishes throughout the UMRS and underscore the role of interjurisdictional management in maintaining network connectivity to sustain fish populations.

Illinois, Iowa, Minnesota, Missouri, Wisconsin

Groundwater chemistry near an impoundment for produced water, Powder River Basin, Wyoming, USA

The Powder River Basin is one of the largest producers of coal-bed natural gas (CBNG) in the United States. An important environmental concern in the Basin is the fate of the large amounts of groundwater extracted during CBNG production. Most of this produced water is disposed of in unlined surface impoundments. A 6-year study of groundwater flow and water chemistry at one impoundment, Skewed Reservoir, has produced the most detailed data set for any impoundment in the Basin. Data were collected from a network of 21 observation wells and three suction lysimeters. A groundwater mound formed atop bedrock within initially unsaturated, unconsolidated deposits underlying the reservoir. Heterogeneity in physical and chemical properties of sediments resulted in complex groundwater flow paths and highly variable groundwater chemistry. Sulfate, bicarbonate, sodium, and magnesium were the dominant ions in all areas, but substantial variability existed in relative concentrations; pH varied from less than 3 to more than 9, and total dissolved solids concentrations ranged from less than 5000 to greater than 100,000 mg/L. Selenium was a useful tracer of reservoir water; selenium concentrations exceeded 300 μg/L in samples obtained from 18 of the 24 sampling points. Groundwater travel time from the reservoir to a nearby alluvial aquifer (a linear distance of 177 m) was calculated at 474 days on the basis of selenium concentrations. The produced water is not the primary source of solutes in the groundwater. Naturally occurring salts and minerals within the unsaturated zone, dissolved and mobilized by infiltrating impoundment water, account for most of the solute mass in groundwater. Gypsum dissolution, cation-exchange, and pyrite oxidation appear to be important reactions. The complex geochemistry and groundwater flow paths at the study site underscore the difficulty in assessing effects of surface impoundments on water resources within the Powder River Basin.

Wyoming

TiO 2 as a photocatalyst for control of the aquatic invasive alga, Cladophora, under natural and artificial light

Cladophora, a nuisance and invasive, filamentous algae (Chlorophyta), massively accumulates along the shores of the lower Great Lakes each summer causing great economic damage and compromising recreational opportunity and perhaps public health. In vitro experiments showed that Cladophora samples were physically and biologically degraded when subjected to TiO 2 -mediated photocatalysis. For the most successful photocatalytic process, TiO 2 was immobilized on a glass surface and used in combination with either sunlight or artificial UV light. The loss of vital algal pigments was monitored using UV–vis spectrophotometry, and cell structural changes were determined by microscopic observation. Cladophora, in the presence of TiO 2 -covered glass beads, experienced a loss of chloroplast pigments after 2 h of UV lamp light irradiation. In a separate experiment, sunlight exposure over 4 days (∼24 h) resulted in the complete oxidative degradation of the green chloroplast pigments, verified by the UV spectra of the algal extracts. These results suggest that TiO 2 , mobilized on sunlit silicates may be useful in controlling growth and survival of this alga in the Great Lakes, thus mitigating many of the economic, aesthetic ecological impacts of this invasive alga.

Journal of Photochemistry and Photobiology A: Chem

Importance of storm events in controlling ecosystem structure and function in a Florida Gulf Coast estuary

From 8/95 to 2/01, we investigated the ecological effects of intra- and inter-annual variability in freshwater flow through Taylor Creek in southeastern Everglades National Park. Continuous monitoring and intensive sampling studies overlapped with an array of pulsed weather events that impacted physical, chemical, and biological attributes of this region. We quantified the effects of three events representing a range of characteristics (duration, amount of precipitation, storm intensity, wind direction) on the hydraulic connectivity, nutrient and sediment dynamics, and vegetation structure of the SE Everglades estuarine ecotone. These events included a strong winter storm in November 1996, Tropical Storm Harvey in September 1999, and Hurricane Irene in October 1999. Continuous hydrologic and daily water sample data were used to examine the effects of these events on the physical forcing and quality of water in Taylor Creek. A high resolution, flow-through sampling and mapping approach was used to characterize water quality in the adjacent bay. To understand the effects of these events on vegetation communities, we measured mangrove litter production and estimated seagrass cover in the bay at monthly intervals. We also quantified sediment deposition associated with Hurricane Irene's flood surge along the Buttonwood Ridge. These three events resulted in dramatic changes in surface water movement and chemistry in Taylor Creek and adjacent regions of Florida Bay as well as increased mangrove litterfall and flood surge scouring of seagrass beds. Up to 5 cm of bay-derived mud was deposited along the ridge adjacent to the creek in this single pulsed event. These short-term events can account for a substantial proportion of the annual flux of freshwater and materials between the mangrove zone and Florida Bay. Our findings shed light on the capacity of these storm events, especially when in succession, to have far reaching and long lasting effects on coastal ecosystems such as the estuarine ecotone of the SE Everglades.

Journal of Coastal Research

Ultraviolet and visible remote sensing of volcanic gases

As magma rises in volcanic systems, volatile species exsolve from the silicate melt and are emitted as gases into the atmosphere. Measuring the magnitude and composition of gas emissions from volcanoes provides insights into processes occurring deep within the Earth and helps constrain the impact of volcanic degassing on atmospheric chemistry. Optical remote sensing techniques allow volcanic gas emissions to be characterized without the need to access hazardous areas near active volcanic vents. This paper reviews the state of the art in ultraviolet and visible volcanic gas remote sensing from the ground, air, and space. Special attention is given to discussing the physics of atmospheric radiative transfer on which these techniques are based. The functionality and limitations of different remote sensing instruments are examined, making clear that the ideal choice of instrumentation will depend on the volcanic system to which it is applied and the sought measurement parameters. Common algorithms for determining trace gas column densities, gas burdens, and volcanic emission rates from measurements of spectral radiance are outlined and compared, showing how some algorithms attempt to model the physics of the measurement while others maximize sensitivity. Several examples demonstrate how remote sensing measurements continue to advance our understanding of volcanic systems and their impact on the atmosphere. Finally, a few promising directions of inquiry are suggested that could lead to improvements in remote sensing instrumentation and analysis techniques. By combining spectroscopic and imaging techniques, improving our understanding of atmospheric radiative transfer, expanding the suite of target gases, and increasing the coverage and frequency of observations, we stand to significantly improve our ability to detect and quantify volcanic gas emissions and gain new insights into important Earth-system processes.

Journal of Volcanology and Geothermal Research

Species richness and distributions of boreal waterbirds in relation to nesting and brood-rearing habitats

Identification of ecological factors that drive animal distributions allows us to understand why distributions vary temporally and spatially, and to develop models to predict future changes to populations–vital tools for effective wildlife management and conservation. For waterbird broods in the boreal forest, distributions are likely driven by factors affecting quality of nesting and brood-rearing habitats, and the influence of these factors may extend beyond singles species, affecting the entire waterbird community. We used occupancy models to assess factors influencing species richness of waterbird broods on 72 boreal lakes, along with brood distributions of 3 species of conservation concern: lesser scaup ( Aythya affinis ), white-winged scoters ( Melanitta fusca ), and horned grebe ( Podiceps auritus ). Factors examined included abundance of invertebrate foods (Amphipoda, Diptera, Gastropoda, Hemiptera, Odonata), physical lake attributes (lake area, emergent vegetation), water chemistry (nitrogen, phosphorus, chlorophyll a concentrations), and nesting habitats (water edge, non-forest cover). Of the 5 invertebrates, only amphipod density was related to richness and occupancy, consistently having a large and positive relationship. Despite this importance to waterbirds, amphipods were the most patchily distributed invertebrate, with 17% of the study lakes containing 70% of collected amphipods. Lake area was the only other covariate that strongly and positively influenced species richness and occupancy of scaup, scoters, and grebes. All 3 water chemistry covariates, which provided alternative measures of lake productivity, were positively related to species richness but had little effect on scaup, scoter, and grebe occupancy. Conversely, emergent vegetation was negatively related to richness, reflecting avoidance of overgrown lakes by broods. Finally, nesting habitats had no influence on richness and occupancy, indicating that, at a broad spatial scale, brood distributions are largely driven by the presence of quality brood-rearing lakes, not nesting habitats. Our findings are relevant to generating conservation plans or management goals; specifically, boreal lakes with abundant amphipods and surface areas >25 ha are important habitat for waterbird broods and merit conservation, especially given the patchy distribution of amphipods. Moreover, these high quality brood-rearing lakes are much rarer, and thus more constraining, than are quality nesting habitats, which are likely abundant in the boreal.

Alaska

Understanding fish assemblage structure in lentic ecosystems: Relative effects of abiotic factors and management legacies

We investigated associations of fish assemblages and habitat characteristics (e.g., morphology and water chemistry) from 45 natural lakes and reservoirs in Iowa to determine whether species or trophic guild composition and environmental correlations were concordant between waterbodies of different origins. Overall, fish assemblage composition between natural lakes and reservoirs was consistently dissimilar based on a permutational multivariate ANOVA. Species composition from nonmetric multidimensional scaling ordinations for reservoirs was correlated with a variety of limnological and physical characteristics, whereas species composition and trophic composition of natural lakes were weakly associated with habitat characteristics. Species richness was positively related to waterbody and watershed size for reservoirs but not for natural lakes. Conversely, species richness was negatively correlated with increasing eutrophic conditions in natural lakes but not in reservoirs. Overall, distinct differences in assemblage composition were observed between natural and artificial lentic ecosystems and may have resulted from underlying differences in limnological, physical, and anthropogenic influences between systems. Dissimilar management legacies between waterbody types, such as limited or no stocking of nonrecreationally important species and the use of piscicides, may have additionally had overriding effects on the observed assemblage–environmental relationships. For instance, lower trophic richness and species richness in reservoirs appeared to have resulted from replacement of a diversity of small-bodied native species by relatively few commonly stocked sport fishes. Our results emphasize the need to consider waterbody origin and the potential influence of historical or current management strategies on fish assemblage characterization and subsequent inferences made from environmental correlations.

Iowa

Veneers, rinds, and fracture fills: Relatively late alteration of sedimentary rocks at Meridiani Planum, Mars

Veneers and thicker rinds that coat outcrop surfaces and partially cemented fracture fills formed perpendicular to bedding document relatively late stage alteration of ancient sedimentary rocks at Meridiani Planum, Mars. The chemistry of submillimeter thick, buff-colored veneers reflects multiple processes at work since the establishment of the current plains surface. Veneer composition is dominated by the mixing of silicate-rich dust and sulfate-rich outcrop surface, but it has also been influenced by mineral precipitation, including NaCl, and possibly by limited physical or chemical weathering of sulfate minerals. Competing processes of chemical alteration (perhaps mediated by thin films of water or water vapor beneath blanketing soils) and sandblasting of exposed outcrop surfaces determine the current distribution of veneers. Dark-toned rinds several millimeters thick reflect more extensive surface alteration but also indicate combined dust admixture, halite precipitation, and possible minor sulfate removal. Cemented fracture fills that are differentially resistant to erosion occur along the margins of linear fracture systems possibly related to impact. These appear to reflect limited groundwater activity along the margins of fractures, cementing mechanically introduced fill derived principally from outcrop rocks. The limited thickness and spatial distribution of these three features suggest that aqueous activity has been rare and transient or has operated at exceedingly low rates during the protracted interval since outcropping Meridiani strata were exposed on the plains surface.

Journal of Geophysical Research E: Planets

Determination of the components of stormflow using water chemistry and environmental isotopes, Mattole River basin, California

The chemical and isotopic composition of rainfall and stream water was monitored during a storm in the Mattole River basin of northwestern California. About 250 mm of rain fell during 6 days (∼80% within a 42 h period) in late January, 1972, following 24 days of little or no precipitation. River discharge near Petrolia increased from 22 m 3 s −1 to a maximum of 1300 m 3 s −1 while chloride and silica concentrations decreased only from 3.2 to 2.1 and 11.5 to 8.6 mgl −1 , respectively. Meanwhile, the isotopic composition of the river changed from δD = -42%, δ 18 O = -6.8% and 40 tritium units (T.U.) to extreme values at highest flow of δD = -35%, δ 18 O = -5.9% and 25 T.U. in response to volume-weighted rainfall averaging δD = -19.5%, δ 18 O = -3.1% and 18 T.U. Despite much rainfall of a composition quite different from that of the prestorm river water, “buffering” processes in the watershed greatly restricted changes in the chemical and isotopic content of the river during storm runoff. Because of the physical and hydrologic characteristics of the watershed, major contributions of groundwater to stormflow are very unlikely. The large increase in dissolved chemical load observed at maximum river discharge required that extensive interaction with, and presumably penetration of, soils occurred within a few hours time. Such a large increase in chemical load also required subsurface stormflow throughout a high proportion of the watershed. Chemical and isotopic stabilization of stormflow is believed to be due mainly to displacement of prestorm soil water, with some effects on river chemistry due to rapid rain-soil interactions. The isotopic and chemical composition of prestorm soil moisture cannot readily be predicted a priori because of possible variability in rainfall composition, evaporation, and exchange with atmospheric moisture, nor can it be assumed that baseflow has a predictable relation to the chemical or isotopic composition of water displaced from soils during storms. Therefore, it seems inappropriate to draw conclusions as to the relative proportions of groundwater and rainfall in runoff from a particular storm based only on the average compositions of rainfall, stormflow, and prestorm river water, as has been done in most previous isotope hydrograph studies. Given the great variation in hydrology, topography, soil characteristics, rainfall intensity and quantity, etc. from place to place, the relative amount of overland flow, subsurface flow from the unsaturated zone and of groundwater in stormflow can vary greatly in time and space.

California

Chemical variations in Yellowknife Bay formation sedimentary rocks analyzed by ChemCam on board the Curiosity rover on Mars

The Yellowknife Bay formation represents a ~5 m thick stratigraphic section of lithified fluvial and lacustrine sediments analyzed by the Curiosity rover in Gale crater, Mars. Previous works have mainly focused on the mudstones that were drilled by the rover at two locations. The present study focuses on the sedimentary rocks stratigraphically above the mudstones by studying their chemical variations in parallel with rock textures. Results show that differences in composition correlate with textures and both manifest subtle but significant variations through the stratigraphic column. Though the chemistry of the sediments does not vary much in the lower part of the stratigraphy, the variations in alkali elements indicate variations in the source material and/or physical sorting, as shown by the identification of alkali feldspars. The sandstones contain similar relative proportions of hydrogen to the mudstones below, suggesting the presence of hydrous minerals that may have contributed to their cementation. Slight variations in magnesium correlate with changes in textures suggesting that diagenesis through cementation and dissolution modified the initial rock composition and texture simultaneously. The upper part of the stratigraphy (~1 m thick) displays rocks with different compositions suggesting a strong change in the depositional system. The presence of float rocks with similar compositions found along the rover traverse suggests that some of these outcrops extend further away in the nearby hummocky plains.

Journal of Geophysical Research E: Planets

Investigating the role of gas bubble formation and entrapment in contaminated aquifers: Reactive transport modelling

In many natural and contaminated aquifers, geochemical processes result in the production or consumption of dissolved gases. In cases where methanogenesis or denitrification occurs, the production of gases may result in the formation and growth of gas bubbles below the water table. Near the water table, entrapment of atmospheric gases during water table rise may provide a significant source of O 2 to waters otherwise depleted in O 2 . Furthermore, the presence of bubbles will affect the hydraulic conductivity of an aquifer, resulting in changes to the groundwater flow regime. The interactions between physical transport, biogeochemical processes, and gas bubble formation, entrapment and release is complex and requires suitable analysis tools. The objective of the present work is the development of a numerical model capable of quantitatively assessing these processes. The multicomponent reactive transport code MIN3P has been enhanced to simulate bubble growth and contraction due to in-situ gas production or consumption, bubble entrapment due to water table rise and subsequent re-equilibration of the bubble with ambient groundwater, and permeability changes due to trapped gas phase saturation. The resulting formulation allows for the investigation of complex geochemical systems where microbially mediated redox reactions both produce and consume gases as well as affect solution chemistry, alkalinity, and pH. The enhanced model has been used to simulate processes in a petroleum hydrocarbon contaminated aquifer where methanogenesis is an important redox process. The simulations are constrained by data from a crude oil spill site near Bemidji, MN. Our results suggest that permeability reduction in the methanogenic zone due to in-situ formation of gas bubbles, and dissolution of entrapped atmospheric bubbles near the water table, both work to attenuate the dissolved gas plume emanating from the source zone. Furthermore, the simulations demonstrate that under the given conditions more than 50% of all produced CH 4 partitions to the gas phase or is aerobically oxidised near the water table, suggesting that these processes should be accounted for when assessing the rate and extent of methanogenic degradation of hydrocarbons.

Journal of Contaminant Hydrology

India National Gas Hydrate Program Expedition-02: Operational and technical summary

The India National Gas Hydrate Program is being steered by the government of India's Ministry of Petroleum and Natural Gas (MoPNG) with participation of Directorate General of Hydrocarbons (DGH), Oil and Natural Gas Corporation Limited (ONGC), and the National Oil Companies and Research Institutes of India. The India National Gas Hydrate Program Expedition 01 (NGHP-01) established the presence of gas hydrate in the Krishna Godavari (KG) and Mahanadi Basins and in the offshore area of the Andaman Sea Basin. However, the gas hydrates discovered during NGHP-01 were mainly distributed as fracture-filling material in fine-grained clay-rich sediments. The India National Gas Hydrate Program Expedition 02 (NGHP-02) was carried out with an objective to discover gas hydrate in sand-rich sediment along the eastern offshore margin of India. ONGC planned and executed NGHP-02 on the behalf of the MoPNG. NGHP-02 started on March 3, 2015 and was completed on July 28, 2015 (total 147 days) using the Japanese scientific Drilling Vessel Chikyu (D/V Chikyu). During NGHP-02, 42 holes at 25 sites were drilled, cored, and/or surveyed with downhole logging tools. These sites were located in four areas along the eastern margin of India and formally named Area A (Mahanadi Basin, three sites), Area B (northern part of the KG-Basin, twelve sites), Area C (central part of the KG-Basin, six sites), and Area E (southern part to the KG-Basin, four sites). All 25 sites established during NGHP-02 were first drilled and logged with logging-while-drilling (LWD) tools and an additional 17 holes were then drilled and/or cored with conventional coring tools (HPCS/ESCS) or pressure coring tools (PCTB). Wireline logging was conducted in 10 holes and formation tests using a dual packer Modular Formation Dynamics Tester (MDT) tool were carried out in two holes. The onboard science team used the laboratory facilities on the D/V Chikyu to examine and analyse the physical properties, geochemistry, and sedimentology of all the cores collected during the expedition. Core samples were also analysed in additional post-expedition shore-based studies conducted in numerous domestic and international gas hydrate research laboratories. The NGHP-02 sediment cores were archived at the National Gas Hydrate Core Repository in Mumbai (India), which is associated with the ONGC Gas Hydrate Research and Technology Centre (GHRTC). The necessary data for characterizing the occurrence of gas hydrate, such as interstitial water chlorinities, core-derived gas chemistry, physical and sedimentological properties, thermal images of the recovered cores, pressure core and downhole measured logging data (LWD and/or conventional wireline log data), were obtained from most of the drill sites established during NGHP-02. Almost all the drill sites yielded evidence for the occurrence of gas hydrate; however, the inferred in situ concentration of gas hydrate varied substantially from site to site. For the most part, the interpretation of downhole logging data, core thermal images, interstitial water analyses, and pressure core images from the sites established during NGHP-02 indicate that the occurrence of concentrated gas hydrate is mostly associated with coarser grained (sand-rich) sediments. This paper presents the operational and technical summary of NGHP-02. NGHP-02 started on March 3, 2015 and was completed on July 28, 2015 (total 147 days) using the Japanese scientific Drilling Vessel Chikyu (D/V Chikyu). During NGHP-02, 42 holes at 25 sites were drilled, cored, and/or surveyed with downhole logging tools. These sites were located in four areas along the eastern margin of India and formally named Area A (Mahanadi Basin, three sites), Area B (northern part of the KG-Basin, twelve sites), Area C (central part of the KG-Basin, six sites), and Area E (southern part to the KG-Basin, four sites). All 25 sites established during NGHP-02 were first drilled and logged with logging-while-drilling (LWD) to

Journal of Marine and Petroleum Geology