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At least 37 records · Page 2

Geochemical Changes in Response to CO 2 Injection in a CO 2 -EOR Complex in Northern Michigan

The overall purpose of the geochemical monitoring program under Midwestern Regional Carbon Sequestration Partnership (MRCSP) is 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..

54 ENVIRONMENTAL SCIENCES↗

Geochemical data package for performance assessment calculations related to the Savannah River Site

The Savannah River Site (SRS) disposes of low-level radioactive waste (LLW) and stabilizes high-level radioactive waste (HLW) tanks in the subsurface environment. Calculations used to establish the radiological limits of these facilities are referred to as Performance Assessments (PAs), Special Analyses (SAs), and Composite Analyses (CAs). The purpose of this document is to revise the existing geochemical data package used for these calculations (Kaplan, 2016). This work builds on earlier compilations of geochemical data, referred to a geochemical data packages (Kaplan, 2007; Kaplan, 2010; Kaplan, 2016; McDowell-Boyer et al., 2000). This work is being conducted as part of the on-going maintenance program of the SRS PA programs that periodically updates calculations and data packages when new information becomes available.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Geochemical and Microbial Dynamics of Hydrogen in a Methane Storage Reservoir

Hydrogen has been identified as a flexible energy carrier with zero or negative emission across multiple energy systems, and existing natural gas infrastructure could be leveraged if hydrogen gas (H2) was blended with methane (CH4). For example, subsurface methane storage reservoirs could be slightly modified to also store hydrogen if a methane/hydrogen blend were injected. However, the compatibility of methane storage reservoirs to include H2 injection has not been fully demonstrated, and this could lead to geochemical and microbiological reactions that alter the reservoir and stored gas content. It is essential that we understand the impact of H2 gas on the biogeochemistry of subsurface storage reservoirs before deploying large-scale H2-CH4 storage, We collected produced fluid from two separate methane storage reservoirs in the Southwestern US. First, we completed a baseline analysis of the biogeochemistry through qPCR, 16S rRNA sequencing, metagenomic sequencing, and geochemical analysis. Each reservoir was found to have unique geochemical conditions and a unique microbial community structure, with Site 1 having a higher TDS and an abundance of Shewanella and Site 2 having a lower TDS and high abundance of Eubacterium and Acetobacterium. Next, we ran a series of high pressure, high temperature reactors under hydrogen storage conditions with the biological sample from one of the storage reservoirs and a 20% H2-80% CH4 gas blend for up to 7 days. Our results show a decrease of hydrogen by 5% in reactors as early as 1-3 days. Previous hydrogen storage work has linked subsurface microorganisms with methanogenesis hydrogen sulfide production, acid production, and microbial corrosion. Our results show minimal change in the fluid chemistry, with the exception of a decrease in dissolved sulfate concentrations. Taxonomic sequencing demonstrated the presence of microorganisms capable of iron redox, acid generation, and hydrogen sulfide production throughout the reactors, suggesting microbial hydrogen consumption may occur through various metabolic pathways. This work demonstrates that site-specific geochemistry and microbiology may impact the efficiency of hydrogen storage in methane storage reservoirs.

environmental microbiology↗

Porewater Geochemical Assessment of Seismic Indications for Gas Hydrate Presence and Absence: Mahia Slope, East of New Zealand’s North Island

We compare sediment vertical methane flux off the Mahia Peninsula, on the Hikurangi Margin, east of New Zealand’s North Island, with a combination of geochemical, multichannel seismic and sub-bottom profiler data. Stable carbon isotope data provided an overview of methane contributions to shallow sediment carbon pools. Methane varied considerably in concentration and vertical flux across stations in close proximities. At two Mahia transects, methane profiles correlated well with integrated seismic and TOPAS data for predicting vertical methane migration rates from deep to shallow sediment. However, at our “control site”, where no seismic blanking or indications of vertical gas migration were observed, geochemical data were similar to the two Mahia transect lines. This apparent mismatch between seismic and geochemistry data suggests a potential to underestimate gas hydrate volumes based on standard seismic data interpretations. To accurately assess global gas hydrate deposits, multiple approaches for initial assessment, e.g., seismic data interpretation, heatflow profiling and controlled-source electromagnetics, should be compared to geochemical sediment and porewater profiles. A more thorough data matrix will provide better accuracy in gas hydrate volume for modeling climate change and potential available energy content.

03 NATURAL GAS↗

Prediction of Long-Term Geochemical Change in Bentonite Based on the Interpretative THMC Model of the FEBEX In Situ Test

Since nuclear energy is crucial in the decarbonization of the energy supply, one hurdle to remove is the handling of high-level radioactive waste (HLW). Disposal of HLW in a deep geological repository has long been deemed a viable permanent option. In the design of a deep geological repository, compacted bentonite is the most commonly proposed buffer material. Predicting the long-term chemical evolution in bentonite, which is important for the safety assessment of a repository, has been challenging because of the complex coupled processes. Models for large-scale tests and predictions based on such models have been some of the best practices for such purposes. An 18-year-long in situ test with two dismantling events provided a unique set of chemical data that allowed for studying chemical changes in bentonite. In this paper, we first developed coupled thermal, hydrological, mechanical, and chemical (THMC) models to interpret the geochemical data collected in the in situ test and then extended the THMC model to 200 years to make long-term prediction of the geochemical evolution of bentonite. The interpretive coupled THMC model shows that the geochemical profiles were strongly affected by THM processes such as evaporation/condensation, porosity change caused by swelling, permeability change, and the shape of concentration profiles for major cations were largely controlled by transport processes, but concentration levels were regulated by chemical reactions, and the profiles of some species such as pH, bicarbonate, and sulfate were dominated by these reactions. The long-term THMC model showed that heating prolongs the time that bentonite becomes fully saturated in the area close to the heater/canister; however, once the bentonite becomes fully saturated, high concentrations of ions in bentonite near the heater, which was observed in the field test, will disappear; illitization continues for 50 years but will not proceed further.

Zheng, Liange↗

Enhanced orbital geochemical images by the Laplacian subtraction method

Orbital geochemical studies of the moon based on X-ray fluorescence and gamma-ray spectroscopy have been successful. There are, however, difficulties if geologic units or other features to be investigated are too small. Investigations have been conducted with the objective to improve with the aid of image enhancement methods both spatial resolution and contrast for the geochemical experiments. A description is provided of the Laplacian subtraction method of enhancement. It was found that the application of a least-squares version of this method to the Mg/Al ratios obtained by orbital X-ray fluorescence improved geochemical images considerably. The spatial resolution increased by about a factor of 2 and the contrast also increased. The Laplacian of an image can also be used to detect very small 'hot' or 'cold' spots in an image.

Schonfeld, E.↗

Chemical mixing model studies of lunar orbital geochemical data - Apollo 16 and 17 highlands compositions

Chemical mixing model studies of lunar geochemical data for the central and Taurus-Littrow lunar highlands were performed utilizing pristine highland rock types as end member compositions. The central highlands show considerable diversity in composition; anorthosite is the principal rock type in the Apollo 16/Descartes region, while norite predominates in the highlands west of the landing site. This change in crustal composition is coincident with a major color boundary seen in earth-based multispectral data and probably represents the presence of distinct geochemical provinces within the central highlands. The Taurus-Littrow highlands are dominated by norite; anorthosite is far less abundant than in the central highlands. This suggests that the impact target for the Serenitatis basin was different than that of the Nectaris basin and further strengthens the hypothesis that the lunar highlands are petrologically heterogeneous on a regional basis. It is suggested that the lunar highlands should be viewed in terms of geochemical provinces that have undergone distinct and complex igneous and impact histories.

Spudis, P. D.↗

The origin of selected lunar geochemical anomalies Implications for early volcanism and the formation of light plains

The geochemical anomalies on the eastern limb and far side of the moon are presently identified and characterized, and their formation processes are investigated, in light of Apollo spacecraft geochemical and photogeologic remote sensing data sets. The results of recent spectral reflectance studies of dark-haloed impact craters, together with considerations of anomaly surface chemistry, indicate that the geochemical anomalies associated with light plains deposits displaying dark-haloed impact craters are due to basaltic units that are either covered by varying thicknesses of highland debris or have a surface contaminated by significant amounts of highland materials.

Hawke, B. R.↗

Mineralogical and geochemical anomalous data of the K-T boundary samples

Cretaceous-Tertiary boundary problem has been discussed previously from the geological research, mainly by fossil changes. Although geochemical bulk data of Ir anomaly suggest the extraterrestrial origin of the K-T boundary, the exact formation process discussed mainly by mineralogical and geochemical study has been started recently, together with noble gas contents. The K-T boundary sample at Kawaruppu River, Hokkaido was collected, in order to compare with the typical K-T boundary samples of Bubbio, Italy, Stevns Klint, Denmark, and El Kef, Tunisia. The experimental data of the silicas and calcites in these K-T boundary samples were obtained from the X-ray unit-cell dimension (i.e., density), ESR signal and total linear absorption coefficient, as well as He and Ne contents. The K-T boundary samples are usually complex mixture of the terrestrial activities after the K-T boundary event. The mineralogical and geochemical anomalous data indicate special terrestrial atmosphere at the K-T boundary formation probably induced by asteroid impact, followed the many various terrestrial activities (especially the strong role of sea-water mixture, compared with terrestrial highland impact and impact craters in the other earth-type planetary bodies).

Miura, Y.↗

A carbonate-silicate aqueous geochemical cycle model for Mars

A model for the carbonate-silicate geochemical cycle of an early, wet Mars is under development. The results of this study will be used to constrain models of the geochemical history of Mars and the likely mineralogy of its present surface. Although Mars today is a cold, dry planet, it may once have been much warmer and wetter. Values of total outgassed CO2 from several to about 10 bars are consistent with present knowledge (Pollack et al. 1987), and this amount of CO2 implies an amount of water outgassed at least equal to an equivalent depth of 500-1000 meters (Carr 1986). Pollack et al. (1987), in addition, estimate that a thick CO2 atmosphere may have existed for an extended period of time, perhaps as long as a billion years. The greenhouse effect of such an atmosphere would permit the presence of liquid water on the surface, most likely in the form of a shallow sea in the lowest regions of the planet, such as the northern plains (Schaefer 1990). The treatment of geochemical cycles as complex kinetic chemical reactions has been undertaken for terrestrial systems in recent years with much success (Lasaga 1980, 1981; Berner et al. 1983; Lasaga et al. 1985). Although the Martian system is vastly less well understood, and hence less well-constrained, it is also a much simpler system, due to the lack of biogenic reactions that make the terrestrial system so complex. It should be possible, therefore, to use the same techniques to model the Martian system as have been used for terrestrial systems, and to produce useful results. A diagram of the carbonate-silicate cycle for Mars (simplified from the terrestrial system) is given.

Schaefer, M. W.↗

Geochemical comparison of impact glasses from lunar meteorites ALHA81005 and MAC88105 and Apollo 16 regolith 64001

Parameterizations have been developed for impact glass compositions which makes its possible to acquire geochemical information about pre-impact target materials. The impact glass populations among unrelated highland regoliths including Apollo 16 regolith 64001 and the lunar meteorites ALHA81005 and MAC88105 have been compared. It is concluded that the Apollo 16 impact glasses are compositionally more diverse than those in the lunar meteorites. This diversity reflects the complex geology of the Apollo 16 region, in which extensive exposures of mare basalts occur within 300 km. Apollo 16 regolith 64001 contains a distinctive subset of impact glasses with major element compositions similar to lunar highland meteorite. These impact glasses (less than 100 micrograms) indicate that the lunar highlands are geochemically more diverse than the compositional range currently represented by large (more than 1 gram) samples. Lunar impact glasses provide geochemical constraints on the full range of regolith compositions that occur on the moon.

Delano, John W.↗

Geochemical Evidence for a Terrestrial Magma Ocean

The aftermath of phase separation and crystal-liquid fractionation in a magma ocean should leave a planet geochemically differentiated. Subsequent convective and other mixing processes may operate over time to obscure geochemical evidence of magma ocean differentiation. On the other hand, core formation is probably the most permanent, irreversible part of planetary differentiation. Hence the geochemical traces of core separation should be the most distinct remnants left behind in the mantle and crust, In the case of the Earth, core formation apparently coincided with a magma ocean that extended to a depth of approximately 1000 km. Evidence for this is found in high pressure element partitioning behavior of Ni and Co between liquid silicate and liquid iron alloy, and with the Ni-Co ratio and the abundance of Ni and Co in the Earth's upper mantle. A terrestrial magma ocean with a depth of 1000 km will solidify from the bottom up and first crystallize in the perovskite stability field. The largest effect of perovskite fractionation on major element distribution is to decrease the Si-Mg ratio in the silicate liquid and increase the Si-Mg ratio in the crystalline cumulate. Therefore, if a magma ocean with perovskite fractionation existed, then one could expect to observe an upper mantle with a lower than chondritic Si-Mg ratio. This is indeed observed in modern upper mantle peridotites. Although more experimental work is needed to fully understand the high-pressure behavior of trace element partitioning, it is likely that Hf is more compatible than Lu in perovskite-silicate liquid pairs. Thus, perovskite fractionation produces a molten mantle with a higher than chondritic Lu-Hf ratio. Arndt and Blichert-Toft measured Hf isotope compositions of Barberton komatiites that seem to require a source region with a long-lived, high Lu-Hf ratio. It is plausible that that these Barberton komatiites were generated within the majorite stability field by remelting a perovskite-depleted part of the upper mantle transition zone.

Agee, Carl B.↗

Mineralogical and Geochemical Trends in a Fluviolacustrine Sequence in Gale Crater, Mars

The Mars Science Laboratory rover, Curiosity, landed at Gale crater in August 2012 and has been investigating a sequence of dominantly fluviolacustrine sediments deposited 3.6-3.2 billion years ago. Curiosity collects quantitative mineralogical data with the CheMin XRD/XRF instrument and quantitative chemical data with the APXS and ChemCam instruments. These datasets show stratigraphic mineralogical and geochemical variability that suggest a complex aqueous history. The Murray Formation, primarily composed of fine-laminated mudstone, has been studied in detail since the arrival at the Pahrump Hills in September 2014. CheMin data from four samples show variable amounts of iron oxides, phyllosilicates, sulfates, amorphous and crystalline silica, and mafic silicate minerals. Geochemical data throughout the section show that there is significant variability in Zn, Ni, and Mn concentrations. Mineralogical and geochemical trends with stratigraphy suggest one of possibly several aqueous episodes involved alteration in an open system under acidic pH, though other working hypotheses may explain these and other trends. Data from the Murray Formation contrast with those collected from the Sheepbed mudstone located approximately 60 meters below the base of the Murray Formation, which showed evidence for diagenesis in a closed system at circumneutral pH. Ca-sulfates filled late-stage veins in both mudstones.

Rampe, E.↗

Geochemical Advances in Mercury Science Facilitated by a Landed Mission

The data from the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft have revealed several surprising characteristics about the surface of Mercury, leading to its classification as a geochemical endmember among the terrestrial planets. Some of these features include elevated abundances of up to 3 wt% S, C enrichment as high as 4 wt% over the local mean in low reflectance materials (LRM), Na up to 5 wt% at high northern latitudes, and Fe abundances typically lower than 2 wt% [e.g., 1–4]. The S and Fe concentrations have been used to infer that Mercury’s igneous history evolved under highly reduced oxygen fugacity conditions between 2.6 and 7.3 log10 units below the iron-wüstite buffer [e.g., 5], which is more reducing than any other terrestrial planet in the solar system [e.g., 6]. This highly reduced nature has important consequences for the differentiation and thermal/magmatic evolution of Mercury. While the immense amount of data collected by MESSENGER revealed Mercury as a geochemical endmember, this new knowledge gained raised additional questions that necessitate continued exploration of the planet. Fortunately, BepiColombo launched in October of 2018, and this joint ESA/JAXA dual-orbiter spacecraft is the most ambitious effort yet attempted to explore Mercury [e.g., 7]. Looking beyond BepiColombo, there are major aspects of Mercury’s geochemical character and evolution for which significant knowledge gaps can be dramatically improved with data acquired from the planet’s surface via in situ landed science.

Vander Kaaden, K. E.↗

Timing and Geochemical Evolution of Triassic and Jurassic Magmatism during the Break-up of Pangea along the Eastern North American Margin

While our understanding of continental break-up has seen dramatic advances over the past decades, the impact of syn-rift melt generation on the transition from mechanical stretching to seafloor spreading remains enigmatic. Early Mesozoic continental break-up along the U.S. Eastern North American Margin (ENAM) is characterized by protracted Triassic lithospheric stretching and syn-rift deposition interrupted by voluminous Central Atlantic Magmatic Province (CAMP) magmatism. This magmatic phase is followed by ~50 Myr of protracted rifting prior to steady-state seafloor spreading. Mesozoic magmatism recognized in outcrop and aeromagnetic datasets along the ENAM has been summarily attributed to CAMP, although extensive regional dikes preserved in the ENAM proximal rift domain remain largely undated. This study provides new constraints on the timing, duration, and geochemical evolution of syn-rift ENAM magmatism using in-situ apatite U-Pb geochronology and whole-rock geochemistry and integrates these data into a tectonic model. We present in-situ apatite U-Pb ages and whole-rock geochemical data for 16 diabase dikes and sills from NJ, PA, VA, NC, and SC. A Palisades Sill sample yielded an age of 201 ± 8 Ma and agrees with previous 40 Ar/39 Ar and U-Pb ages. Our new in-situ apatite U-Pb ages fall into three clusters and suggest three main pulses of magmatism along the ENAM, with an initial pulse of magmatism at ~205-195 Ma attributed to CAMP. Whole-rock geochemistry of this pulse shows silica (46-53 wt.%), total alkalis (2-4 wt.%), and enrichment of LREEs relative to HREEs, comparable to previously reported geochemical data for CAMP-related rocks along the ENAM. A second magmatic pulse occurred between ~181-175 Ma and shows slightly higher silica and total alkalis, compared to the older CAMP-age phase. The third pulse between ~166-145 Ma generally shows slightly higher silica and total alkalis. LOI and Sr/Yb values of the two younger pulses are similar to CAMP-age samples suggesting no post-crystallization alteration. These new data demonstrate long-lived syn-rift off-axis magmatism persisted ~50 Myr after the onset of CAMP. This post-CAMP off-axis magmatism is likely related to slow magma-limited spreading during the protracted transition to symmetric seafloor spreading along the ENAM.

Z. Foster-Baril↗

Geochemical Assessment for Carbon Sequestration in the Conasauga Group, Northwest Georgia, USA

Sedimentary geological formations are known to be great candidates for geological carbon sequestration. Published studies suggest the southeast of the United States contains many formations suitable for carbon storage. The Cassville 1 Stratigraphic Borehole well could act as a potential carbon reservoir for nearby energy resource facilities in Georgia, United States. Although studies have shown that porous formations are adequate for geological carbon sequestration, it is important to understand possible geochemical reactions between CO 2 and the targeted geological formation before injecting any fluids. In this study, a sandstone sample from the Cassville 1 well is being considered for geological carbon sequestration in the Conasauga Group in Northwest Georgia. Here, the collected sandstone sample, consisting of quartz, K-feldspar, micas, kaolinite, and carbonate minerals such as calcite and dolomite, has a 6% porosity. Leveraging the formation composition and porosity, a one-dimensional continuum reactive transport model was built using CrunchFlow to assess possible geochemical reactions between injected CO 2 and the geological formation. Simulation results show that the carbonate minerals, calcite and dolomite, dissolve during the injection period of 10,000 days, increasing formation porosity from 6% to as much as 30%. The rate and extent of carbonate mineral dissolution and resulting porosity increase are highly sensitive to mineral reactive surface area values. No evidence of mineral precipitation was observed, suggesting that dissolution reactions will control porosity evolution during the CO 2 injection period.

42 ENGINEERING↗

Predicting the potential for mineral scale precipitation in unconventional reservoirs due to fluid-rock and fluid mixing geochemical reactions

Mineral precipitation within hydraulically fractured shale may affect fluid flow pathways and impact longterm hydrocarbon production. The ability to predict geochemical reactions that lead to problematic mineral precipitation will lead to active reservoir management strategies to improve overall production. Using the Marcellus Shale as a case study, a combination of laboratory experiments and reaction path modeling was applied to determine which reactions are likely to occur upon introduction of hydraulic fracturing fluid into the shale reservoir. Experimental results indicate that contact between fracturing fluid and shale will result in dissolution of primary minerals (quartz, feldspars, kaolinite, chlorite, pyrite) and secondary mineral precipitation over time periods of less than one week. Precipitation of barite, Fe-oxides, feldspars, amorphous silica and clay is likely to occur within the reservoir during shut in and early flowback due to mixing between fracturing fluid and reservoir brine as based on modeling saturation indices using experimental fluid data. Reaction path modeling of the experimental scenarios corroborates the specific dissolution and precipitation reactions observed experimentally. Comparison of the results to injected and produced waters from a Marcellus Shale well pad in Greene County, PA, USA, shows that the mineral reactions occur during the hydraulic fracturing, shut in, and early flowback periods. The results presented in this paper demonstrate the value in applying experimental approaches to identify mineral precipitation/dissolution reactions that may significantly impact reservoir performance. The good agreement between geochemical models and experimental results provides confidence that numerical models can be applied to screen the potential fluid-mineral and fluid-mixing reactions in unconventional reservoirs that result in undesired mineral scale precipitation.

58 GEOSCIENCES↗

Influence of geochemical reactions on the creep behavior of Mt. Simon sandstone

The capture and subsurface storage of carbon dioxide is a sustainable option that is currently pursued worldwide to mitigate greenhouse gas effect. However, predicting the long-term mechanical integrity of CO 2 underground storage systems remains a challenge. To address that question, it is essential to understand the influence of fluid-rock chemo-mechanical interactions on the long-term and on the time-dependent mechanical properties. In turn, the long-term mechanical response and the time-dependent mechanical behavior can be represented by the creep response. We investigate the impact of CO 2 -induced geochemical reaction on the creep response of Mt. Simon sandstone with a 50–400 micron grain size. We perform static and dynamic flow experiments on Mt. Simon sandstone specimens under geological conditions, at a temperature of T = 50 - 53 °C and for CO 2 pressures of P = 8:62; 17:2 MPa under both static flow and dynamic flow-through conditions. After aging, we employ creep indentation testing, high-resolution SEM-EDS, computer vision, machine learning, and micromechanics modeling to probe changes on the microstructure and mechanical properties. Following both static and dynamic flow-through experiments, we observe a 10–22% decrease in quartz volume fraction and an increase in both the microporosity (7–28%) and nanoporosity (60–65%). Additional CO 2 -induced microstructural changes include an enlargement of pore throats and the formation of channels. These observations point to the presence of CO 2 -induced K-feldspar dissolution and clay dissolution reactions. Here, the macroscopic creep behavior is logarithmic and the macroscopic creep modulus varies depending on the microporosity and the relative quartz and feldspar content. As a result of these geochemical reactions and of the related microstructural changes, a 55-60% decrease in the macroscopic logarithmic creep modulus is predicted.

58 GEOSCIENCES↗