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At least 91 records · Page 5

Mars Hematite Site: Potential for Preservation of Microfossils

Defining locations where conditions may have been favorable for life is a key objective for the exploration of Mars. Of prime importance are sites where conditions may have been favorable for the preservation of evidence of pre-biotic or biotic processes. Areas displaying significant concentrations of the mineral hematite (alpha-Fe2O3) have been identified from orbit by thermal emission spectrometry. The largest such deposit, in Sinus Meridiani, is a strong candidate landing site for one of the twin Mars Exploration Rovers, scheduled to launch in 2003. The Martian hematite site may have significance in the search for evidence of extraterrestrial life. Since iron oxides can form as aqueous mineral precipitates, the potential exists for preserving microscopic evidence of life in ecosystems that deposit iron oxides. Terrestrial hematite deposits proposed as possible analogs for the hematite sites on Mars include massive (banded) iron formations, iron oxide hydrothermal deposits, iron-rich laterites and ferricrete soils, and rock varnish. We are engaged in a systematic effort to document the evidence of life preserved in iron oxide deposits from each of these environments.

Allen, Carlton C.↗

Mound Spring Complexes in Central Australia: An Analog for Martian Groundwater Fed Outflow Channels?

The arid inland of Australia contains a diversity of landscapes and landscape processes, often of great antiquity, extending back to the Mesozoic and Paleozoic. The potential of this landscape as a source of Mars analogs has, however, been little explored. The few examples studied so far include radiation-tolerant microbes in thermal springs and hematite-silica hydrothermal alteration near Arkaroola in the Finders Ranges, and aeolian landforms at Gurra Gurra water hole the north east of Arkaroola. Further Australian Mars analog studies were provided by the studies of Bourke and Zimbelman of the paleoflood record of the Todd and Hale Rivers in central Australia. To facilitate study of such analogues, Mars Society Australia has embarked on a project to construct a Mars Analog Research Station near Arkaroola. The international scientific community will soon have the opportunity to participate in Mars analog studies in central Australia utilizing this facility. An area of considerable Mars analog potential is the mound spring complexes that occur at the margins of the Great Artesian Basin (GAB) which underlies 22% of the Australian continent and covers 1.7 million km2. The mound springs are formed when ground water flows to a topographic low, and subsurface strata dips up causing a hydrological head at the surface. Minerals precipitated at the spring discharge zone form low mesas or "mounds", the height of which are controlled by the hydrological head. This paper describes the Dalhousie Mound Spring Complex (DMC) in the northern part of South Australia (Figure 1), and its potential as a Mars analog. Hydrogeology: The DMC consists of a cluster of more than 60 active springs formed by natural discharge from the GAB). Total measured discharge from the GAB is 1.74 GL per day, estimated unfocussed natural leakage through the aquaclude is thought be approximately equal to this figure. Some 54 ML per day are currently discharged by the DMC, 3% of the measured total. The discharged artesian waters are of low to moderate salinity (700 - 9400 ppm), near neutral pH (6.8-7.3) and warm (20-46 C). The elevated temperatures are due to passage of the groundwater through deeply buried (up to 3 km) aquifers in an region of high heat flow, rather than magmatic heating. The waters also contain high levels of dissolved iron and H2S and less than 1 ppm dissolved oxygen. The water is carried in the Late Jurassic Algebuckina Sandstone beneath the aquaclude of the Bulldog Shale. It is brought near the surface by the mid-Cenozoic Dalhousie anticline and the ground water flow focused along a series of faults that breach the anticline's crest.

Clarke, J. D. A.↗

Mars Sulfate Formation Sourced in Sulfide-Enriched Subsurface Fluids: The Rio Tinto Model

The extensive evidence for sulfate deposits on Mars provided by analyses of MER and Mars Express data shows that the sulfur played an essential role in the geochemical cycles of the planet, including reservoirs in the atmosphere, hydro-sphere and geosphere. Overall the data are consistent with a fluvial/lacustrine-evaporative origin of at least some of the sulfate deposits, with mineral precipitation through oversaturation of salty acidic fluids enriched in sulfates. This scenario requires reservoirs of sulfur and associated cations, as well as an acidic and oxidizing hydrochemistry which could be provided by surface and subsurface catching of meteoric waters resulting in the presence of sulfur-bearing gases and steam photochemistry. In this work we suggest a new scenario for the extensive generation of sulfates in Mars based on the observation of seasonal changes in the redox and pH of subsurface waters enriched in sulfur that supply the acidic Mars process analog of Rio Tinto. This model considers the long-term subsurface storage of sulfur during most of Noachian and its release from the late Noachian to Hesperian time through weathering by meteoric fluids that would acidify and oxidize the sulfur bearing compounds stored in the subsurface.

Fernandez-Remolar, D. C.↗

Isotope Variations in Terrestrial Carbonates and Thermal Springs as Biomarkers: Analogs for Martian Processes

Stable isotope measurements of carbonate minerals contained within ALH84001 [1] suggest that fluids were present at 3.9 Gy on Mars [2, 3, 4, 5]. Both oxygen and carbon isotopes provide independent means of deciphering paleoenvironmental conditions at the time of carbonate mineral precipitation. In terrestrial carbonate rocks oxygen isotopes not only indicate the paleotemperature of the precipitating fluid, but also provide clues to environmental conditions that affected the fluid chemistry. Carbon isotopes, on the other hand, can indicate the presence or absence of organic compounds during precipitation (i.e. biogenically vs. thermogenically-generated methane), thus serving as a potential biomarker. We have undertaken a study of micro scale stable isotope variations measured in some terrestrial carbonates and the influence of organic compounds associated with the formation of these carbonates. Preliminary results indicate that isotope variations occur within narrow and discrete intervals, providing clues to paleoenvironmental conditions that include both biological and non-biological activity. These results carry implications for deciphering Martian isotope data and therefore potential biological prospecting on the planet Mars. Recently, Fourier Transform Spectrometer observations have detected methane occurring in the Martian atmosphere [6] that could be attributed to a possible biogenic source. Indeed, Mars Express has detected the presence of methane in the Martian atmosphere [7], with evidence indicating that methane abundances are greatest above those basins with high water concentrations.

Socki, Richard A.↗

Deep-Sea Hydrothermal-Vent Sampler

An apparatus is being developed for sampling water for signs of microbial life in an ocean hydrothermal vent at a depth of as much as 6.5 km. Heretofore, evidence of microbial life in deep-sea hydrothermal vents has been elusive and difficult to validate. Because of the extreme conditions in these environments (high pressures and temperatures often in excess of 300 C), deep-sea hydrothermal- vent samplers must be robust. Because of the presumed low density of biomass of these environments, samplers must be capable of collecting water samples of significant volume. It is also essential to prevent contamination of samples by microbes entrained from surrounding waters. Prior to the development of the present apparatus, no sampling device was capable of satisfying these requirements. The apparatus (see figure) includes an intake equipped with a temperature probe, plus several other temperature probes located away from the intake. The readings from the temperature probes are utilized in conjunction with readings from flowmeters to determine the position of the intake relative to the hydrothermal plume and, thereby, to position the intake to sample directly from the plume. Because it is necessary to collect large samples of water in order to obtain sufficient microbial biomass but it is not practical to retain all the water from the samples, four filter arrays are used to concentrate the microbial biomass (which is assumed to consist of particles larger than 0.2 m) into smaller volumes. The apparatus can collect multiple samples per dive and is designed to process a total volume of 10 L of vent fluid, of which most passes through the filters, leaving a total possibly-microbe-containing sample volume of 200 mL remaining in filters. A rigid titanium nose at the intake is used for cooling the sample water before it enters a flexible inlet hose connected to a pump. As the water passes through the titanium nose, it must be cooled to a temperature that is above a mineral-precipitation temperature of 100 C but below the upper working temperature (230 C) of switching valves and tubes in the apparatus. The sample water then passes into a manifold tube, from whence the switching valves can direct the water through either a bypass tube or any one of the filter arrays, without contamination from a previous sample. Each filter array consists of series of filters having pore sizes decreasing in the direction of flow: 90-, 60-, 15-, and 7-micron prefilters and a large-surface-area 0.2-micron collection filter. All the filter taps are located between the intake and the bypass tube so that each time the bypass tube is used, the entire manifold tube is flushed as well.

Behar, Alberto E.↗

Seeking Signs of Life on Mars: A Strategy for Selecting and Analyzing Returned Samples from Hydrothermal Deposits

Highly promising locales for biosignature prospecting on Mars are ancient hydrothermal deposits, formed by the interaction of surface water with heat from volcanism or impacts. On Earth, they occur throughout the geological record (to at least approx. 3.5 Ga), preserving robust mineralogical, textural and compositional evidence of thermophilic microbial activity. Hydrothermal systems were likely present early in Mars' history, including at two of the three finalist candidate landing sites for M2020, Columbia Hills and NE Syrtis Major. Hydrothermal environments on Earth's surface are varied, constituting subaerial hot spring aprons, mounds and fumaroles; shallow to deep-sea hydrothermal vents (black and white smokers); and vent mounds and hot-spring discharges in lacustrine and fluvial settings. Biological information can be preserved by rapid, spring-sourced mineral precipitation, but also could be altered or destroyed by postdepositional events. Thus, field observations need to be followed by detailed laboratory analysis to verify potential biosignatures. See Attachment

Campbell, K. A.↗

Untangling Source-To-Sink Geochemical Signals in a ~3.5 Ga Martian Lake: Sedimentology and Geochemistry of the Murray Formation

Sedimentary rocks are historical archives of planetary surface processes; their grains, textures, and chemistry integrate the effects of source terrains, paleoclimatic conditions, weathering and transport processes, authigenic mineral precipitation, and diagenesis, which records groundwater chemistry through time. “Source to Sink” basin analysis seeks to constrain the influence of each of these different signals through sedimentary and geochemical analyses. Here, we use Mars Science Laboratory (MSL) Curiosity rover images and geochemical and mineralogical data from a traverse across a portion of the Murray formation—the lowermost unit exposed in the Gale crater central mound—to begin to constrain the aspects of the source to sink system that formed this Martian mudstone between 3.7 and 3.2 Ga.

Siebach, K. L.↗

Porosity-Permeability Evolution During Simultaneous Mineral Dissolution and Precipitation

Permeability in reactive porous media evolves in complex ways that are hard to predict. Macroscopic empirical equations are often used to estimate permeability evolution but fail to reflect the impact of pore scale reactions on permeability. This work aims to understand the evolution of permeability in systems where mineral dissolution and precipitation occur simultaneously. Pore network models are used for permeability simulation of a Paluxy sandstone using pore and pore-throat size distributions from the analysis of X-ray CT images. Pore and pore-throat radii are increased and decreased to reflect the effects of dissolution and precipitation reactions. Varying spatial distributions of reactions are simulated and the resulting porosity and permeability values compared with commonly used macroscopic equations. It is observed that when dissolution occurs at the inlet and precipitation at the outlet, porosity increases while permeability decreases. Similar results are also observed in the respective opposite scenario where precipitation occurs at the inlet and dissolution at the outlet. When dissolution and precipitation reactions are randomly distributed throughout the network, porosity increases with little change in permeability that is not captured by the empirical equations. When reactions are controlled by pore and pore-throat sizes, such as dissolution occurring in pores and pore-throats of small size and precipitation in pores and pore-throats of larger size, porosity and permeability decrease. When precipitation occurs in pores and pore-throats of smaller size and dissolution in pores and pore-throats of larger size, porosity and permeability increase and is described relatively well by the Verma-Pruess porosity-permeability equation.

54 ENVIRONMENTAL SCIENCES↗

Comprehensive parametric study of CO 2 sequestration in deep saline aquifers

Carbon dioxide injection in deep saline aquifers is a key method for permanently sequestering anthropogenic CO 2 . Here this study employs a reactive transport model to explore mineral precipitation/dissolution and its impact on reservoir properties in deep saline aquifers. We also assess capillary pressure and relative permeability hysteresis on various CO 2 trapping mechanisms. Results from this study reveal the significant influence of initial brine composition on mineral precipitation/dissolution. The dissolution and precipitation of minerals have different effects around the wellbores compared to the overall reservoir. Additionally, salt concentration (Ca ++ and Mg ++ ) and quartz surface area affect CO 2 mineralization, while Na + impacts halite precipitation, altering flow properties. The effect of capillary pressure is significant, as including the capillary pressure in the simulation case resulted in significantly improved CO 2 trapping, achieving almost total dissolution of the injected CO 2 in around 300 years. This study offers novel insights into the interactions of reservoir minerals, brine properties, and the injected CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mathematical Model for the Mineralization of Bone

A mathematical model is presented for the transport and precipitation of mineral in refilling osteons. One goal of this model was to explain calcification 'halos,' in which the bone near the haversian canal is more highly mineralized than the more peripheral lamellae, which have been mineralizing longer. It was assumed that the precipitation rate of mineral is proportional to the difference between the local concentration of calcium ions and an equilibrium concentration and that the transport of ions is by either diffusion or some other concentration gradient-dependent process. Transport of ions was assumed to be slowed by the accumulation of mineral in the matrix along the transport path. The model also mimics bone apposition, slowing of apposition during refilling, and mineralization lag time. It was found that simple diffusion cannot account for the transport of calcium ions into mineralizing bone, because the diffusion coefficient is two orders of magnitude too low. If a more rapid concentration gradient-driven means of transport exists, the model demonstrates that osteonal geometry and variable rate of refilling work together to produce calcification halos, as well as the primary and secondary calcification effect reported in the literature.

Martin, Bruce↗

Mathematical Model for the Mineralization of Bone

A mathematical model is presented for the transport and precipitation of mineral in refilling osteons. One goal of this model was to explain calcification 'halos,' in which the bone near the haversian canal is more highly mineralized than the more peripheral lamellae, which have been mineralizing longer. It was assumed that the precipitation rate of mineral is proportional to the difference between the local concentration of calcium ions and an equilibrium concentration and that the transport of ions is by either diffusion or some other concentration gradient-dependent process. Transport of ions was assumed to be slowed by the accumulation of mineral in the matrix along the transport path. ne model also mimics bone apposition, slowing of apposition during refilling, and mineralization lag time. It was found that simple diffusion cannot account for the transport of calcium ions into mineralizing bone, because the diffusion coefficient is two orders of magnitude too low. If a more rapid concentration gradient-driven means of transport exists, the model demonstrates that osteonal geometry and variable rate of refilling work together to produce calcification halos, as well as the primary and secondary calcification effect reported in the literature.

Martin, Bruce↗

A combined experimental and modelling study of granite hydrothermal alteration

Geochemical reactions can induce significant changes of rock reservoir porosity and permeability via mineral dissolution and precipitation processes, affecting the long-term fluid behaviour within various geological systems. Here, the understanding and quantification of these reactions rely on field and experimental studies and on the predictions of reactive transport models. The present study was aimed at assessing the extent to which current geochemical models integrating available mineral dissolution/precipitation rate equations can reproduce the experimental data obtained from 4 to 17-day long hydrothermal alteration experiments of a muscovite-biotite granite and, thus, help provide an accurate description of the evolution of geothermal systems within granitic reservoirs. The experiments were conducted at a constant temperature of 180 °C and over an aqueous fluid pH range of 2 to 8.5, using both mixed-flow and static batch reactors. Modelled major element (K, Al, Si, Ca, and Mg) concentrations were generally in satisfactory agreement with the corresponding measured elemental fluxes – the differences between modelled and experimental values were generally within a factor of 5 – and the predicted identity and mass of formed secondary phases were consistent with the microscopic observations of the reacted solids. However, larger differences between measured and modelled element concentrations were observed when significant amounts of secondary phases formed, notably at pH 2 to 3, and for longer-term batch experiments. Much of this concentration difference stems from the underestimation of the amounts of Al-phases formed at acid to near-neutral pH. Although an idealized rock composition was considered, the observed mismatch between model calculations and experimental data can be attributed to inadequate mineral precipitation reaction rates and a poor description of reactive surface areas in existing geochemical modelling codes. More accurate quantification of precipitation kinetics, including nucleation and growth, and improved descriptions of the temporal change of mineral surface area would enhance the predictive capabilities of reactive transport models and benefit, particularly, the efforts aimed at increasing the sustainability of EGS reservoirs.

58 GEOSCIENCES↗

Fluid Induced Elemental and Mineralogy Alterations of Caney Shale

ABSTRACT: Studies were conducted on cores and rock cuttings recovered from two wells drilled in Caney shale in the Southern Oklahoma. Mineralogical compositions of these samples were obtained by X-Ray Diffraction (XRD) measurements using two methods of sample preparation: conventional powder (by crushing and grinding of rock fragments) and spray-drying of micronized rock powder method. Microstructure and microanalysis were acquired by Scanning Electron Microscopy/Energy Dispersive Spectroscopy (SEM/EDS). Batch experiments were then conducted using selected rock samples and fracturing fluid whilst deionized water was used as control sample for fluid/rock interaction. These were conducted at 95°C and ambient pressure for various time periods to assess the geochemical reactivity of the Caney shale. The rock samples were subsequently recovered from fluid, dried and analysis repeated using identical XRD and SEM/EDS measurements, following the same conditions. Preliminary experimental results show rock mineralogical compositions are predominantly quartz with relatively high clay content. The clay minerals are mainly illite. Carbonate content is less than 10% by weight for most samples, with other non-clay minerals pyrite, albite, dolomite, and some apatite. In general, sprayed samples showed more intense peaks and less full width at half maxima (FWHM) relative to conventional rock-powder samples. Post-experimental mineralogical changes were observed in samples with clay portions breaking down to amorphous entities. As expected, dissolution of carbonates (calcite and dolomite) was observed and newly detected dissolution of biogenic micro quartz resulted in formation of amorphous silica. 1.0 INTRODUCTION Formation of sedimentary rocks involves processes where rock sediments are emplaced with fluids starting interactions that persist over long periods. During the lithification process, sediments and fluids react and attain equilibrium state. This equilibrium is disturbed during drilling, completion, hydraulic fracturing and other operations that involve the introduction of engineered fluids into the subsurface. To return to equilibrium, dissolution and precipitation of minerals may occur. These reactions have implications on the petrophysical properties of the reservoir. Whiles dissolution and precipitation of minerals can enhance porosity and permeability, the reverse can also be true. For example, when acidic fluids are introduced into formations with high carbonate contents, carbonate minerals dissolve into solution thus increasing the porosity and permeability of the formation. In contrast, when alkaline fluids with pH above 11 are introduced into an illite-rich shale formation, the rock-fluid interaction leads to de-flocculation of illite platelets causing substantial increase in clay fines migration, consequently significant reduction in permeability (Salles et al., 2008).

Awejori, G.↗

Sulfur isotope fractionation between aqueous and carbonate-associated sulfate in abiotic calcite and aragonite

Sulfate (SO 4 2– ) incorporated into calcium carbonate minerals enables measurements of sulfur (S) isotope ratios in carbonate rocks. This Carbonate Associated Sulfate (CAS) in marine carbonate minerals is thought to faithfully represent the S isotope composition of the seawater sulfate incorporated into the mineral, with little or no S isotope fractionation in the process. However, comparison between different calcifying species reveals both positive and negative S isotope fractionation between CAS and seawater sulfate, and a large range of S isotope ratios can be found within a single rock sample, depending on the component measured. To better understand the isotopic effects associated with sulfate incorporation into carbonate minerals, we precipitated inorganic calcite and aragonite over a range covering more than two orders of magnitude of sulfate concentration and precipitation rate. Coupled measurements of CAS concentration, S isotope composition and X-ray absorption near-edge spectra (XANES) permit characterization and explanation of the observed dependence of S isotope fractionation between CAS and aqueous sulfate (CAS-SO 4 2– isotope fractionation) on sulfate concentration and precipitation rate. In aragonite, the CAS-SO 4 2– isotope fractionation is 1.0 ± 0.3‰ and independent of the sulfate (and CAS) concentration. In contrast, we note the CAS-SO 4 2– isotope fractionation in calcite covaries strongly with the sulfate concentration and weakly with the precipitation rate, between values of 1.3 ± 0.1 and 3.1 ± 0.6‰. We suggest that the correlation between aqueous sulfate concentration and CAS-SO 4 2– isotope fractionation in calcite reflects a dependence of the equilibrium S isotope fractionation on the concentration of CAS, through the effect of the sulfate impurity on the carbonate mineral’s energetic state.

58 GEOSCIENCES↗

Evaluation of the Maximum Soluble Water Recovery from Pretreated Urine Brines in Low Earth Orbit

The Urine Processor Assembly (UPA) on the International Space Station recovers water from pretreated urine by thin-film, vacuum compression distillation (VCD). A number of iterative improvements to the distiller assembly (DA) have enabled increases in on-orbit water recovery and improved distillate water quality at on-orbit recoveries up to 87% by volume relative to the volume of pretreated urine. The phosphoric acid-based pretreatment formulation has enabled these higher recoveries on-orbit since May of 2016. Application of simple empirical chemistry models have allowed water recovery of sulfuric-acid pretreated urine from the Russian Orbiting segment to be distilled with phosphoric acid pretreated urine from the U.S. Orbiting Segment. Returned liquid brine from brine filters in the UPA brine loop have enabled empirical measurement of gypsum solubility as a function of recovery, conductivity, or mass density in the real brines of ISS. Calculations of maximum soluble recovery, MSR, are based on preventing the precipitation of gypsum, which is the first mineral to precipitate for both types of pretreated urine. A statistical urine model of urine composition provides an estimate of worst-case urine from a crew of three during one year of operations on ISS. The MSR is defined based on the worst-case concentrations of urinary calcium and urinary sulfate that are pretreated, pooled, and distilled. The potential to increase water recoveries above 87% without gypsum precipitation are evaluated. The potential benefits and costs of the addition of a conductivity sensor or a Coriolis mass flow meter to the brine loop are evaluated.

Dean L Muirhead↗

Geochemical Changes in Response to CO 2 Injection in a CO 2 -EOR Complex in Northern Michigan (Volume II.1)

The Midwest Regional Carbon Sequestration Partnership (MRCSP) was founded in 2003 as part of the U.S. Department of Energy’s (DOE’s) Regional Carbon Sequestration Partnership initiative. Since its founding, MRCSP has made significant strides toward making CCUS a viable option for states in the region. The public/private consortium, funded through the DOE Regional Carbon Sequestration Initiative, brings together nearly 40 industry partners and 10 states. Battelle, as the project lead, oversees research, development and operations and coordinates activities among the partners. The incremental, phased approach has built a valuable knowledge base for the industry and paved the way for commercial-scale adoption of CCUS technologies. From 2008 to 2020, MRCSP Phase III focused on the development of large-scale injection projects. This report is part of a series of reports prepared under the Midwestern Regional Carbon Sequestration Partnership (MRCSP) Phase III (Development Phase). These reports summarize and detail the findings of the work conducted under the Phase III project. The report describes the geochemical monitoring program under MRCSP to use stable and radiogenic isotope geochemistry in concert with analysis of general geochemical parameters of fluids and gases and analysis of core samples to determine geochemical processes occurring in the reef structure because of CO 2 injection. Specifically, brine and gas samples were collected and analyzed to determine changes occurring between reefs prior to and following CO 2 injection. The analytical results for general geochemical parameters were modeled with chemical equilibrium models to determine if the injection of CO 2 resulted in the mineral dissolution or precipitation. Finally, core samples were collected and analyzed to determine if there was evidence of dissolution features or mineral precipitation.

01 COAL, LIGNITE, AND PEAT↗