Interplay between microorganisms and geochemistry in geological carbon storage

DOE PAGES

Altman, Susan J.; Kirk, Matthew Fletcher; Santillan, Eugenio-Felipe U.; ...

2016-02-28

Researchers at the Center for Frontiers of Subsurface Energy Security (CFSES) have conducted laboratory and modeling studies to better understand the interplay between microorganisms and geochemistry for geological carbon storage (GCS). We provide evidence of microorganisms adapting to high pressure CO 2 conditions and identify factors that may influence survival of cells to CO 2 stress. Factors that influenced the ability of cells to survive exposure to high-pressure CO 2 in our experiments include mineralogy, the permeability of cell walls and/or membranes, intracellular buffering capacity, and whether cells live planktonically or within biofilm. Column experiments show that, following exposure tomore » acidic water, biomass can remain intact in porous media and continue to alter hydraulic conductivity. Our research also shows that geochemical changes triggered by CO 2 injection can alter energy available to populations of subsurface anaerobes and that microbial feedbacks on this effect can influence carbon storage. Our research documents the impact of CO 2 on microorganisms and in turn, how subsurface microorganisms can influence GCS. Furthermore, we conclude that microbial presence and activities can have important implications for carbon storage and that microorganisms should not be overlooked in further GCS research.« less

Evaluating Impacts of CO2 Gas Intrusion Into a Confined Sandstone aquifer: Experimental Results

DOE PAGES

Qafoku, Nikolla; Lawter, Amanda R.; Shao, Hongbo; ...

2014-12-31

Deep subsurface storage and sequestration of CO2 has been identified as a potential mitigation technique for rising atmospheric CO2 concentrations. Sequestered CO2 represents a potential risk to overlying aquifers if the CO2 leaks from the deep storage reservoir. Experimental and modeling work is required to evaluate potential risks to groundwater quality and develop a systematic understanding of how CO2 leakage may cause important changes in aquifer chemistry and mineralogy by promoting dissolution/precipitation, adsorption/desorption, and redox reactions. Sediments from the High Plains aquifer in Kansas, United States, were used in this investigation, which is part of the National Risk Assessment Partnershipmore » Program sponsored by the US Department of Energy. This aquifer was selected to be representative of consolidated sand and gravel/sandstone aquifers overlying potential CO2 sequestration repositories within the continental US. In this paper, we present results from batch experiments conducted at room temperature and atmospheric pressure with four High Plains aquifer sediments. Batch experiments simulate sudden, fast, and short-lived releases of the CO2 gas as would occur in the case of well failure during injection. Time-dependent release of major, minor, and trace elements were determined by analyzing the contacting solutions. Characterization studies demonstrated that the High Plains aquifer sediments were abundant in quartz and feldspars, and contained about 15 to 20 wt% montmorillonite and up to 5 wt% micas. Some of the High Plains aquifer sediments contained no calcite, while others had up to about 7 wt% calcite. The strong acid extraction tests confirmed that in addition to the usual elements present in most soils, rocks, and sediments, the High Plains aquifer sediments had appreciable amounts of As, Cd, Pb, Cu, and occasionally Zn, which potentially may be mobilized from the solid to the aqueous phase during or after exposure to CO2. However, the results from the batch experiments showed that the High Plains sediments mobilized only low concentrations of trace elements (potential contaminants), which were detected occasionally in the aqueous phase during these experiments. Importantly, these occurrences were more frequent in the calcite-free sediment. Results from these investigations provide useful information to support site selection, risk assessment, and public education efforts associated with geological CO2 storage and sequestration.« less

Migration of carbon dioxide included micro-nano bubble water in porous media and its monitoring

NASA Astrophysics Data System (ADS)

Takemura, T.; Hamamoto, S.; Suzuki, K.; Koichi, O.

2017-12-01

The distributed CO2 storage is the small scale storage and its located near the emission areas. In the distributed CO2 storage, the CO2 is neutralized by sediment and underground water in the subsurface region (300-500m depth). Carbon dioxide (CO2) included micro-nano bubbles is one approach in neutralizing CO2 and sediments by increasing CO2 volume per unit volume of water and accelerating the chemical reaction. In order to design underground treatment for CO2 gas in the subsurface, it is required to elucidate the behavior of CO2 included micro-nano bubbles in the water. In this study, we carried out laboratory experiment using the soil tank, and measure the amount of leakage of CO2 gas at the surface. In addition, the process of migration of carbon dioxide included micro-nano bubble was monitored by the nondestructive method, wave velocity and resistivity.

Development of anomaly detection models for deep subsurface monitoring

NASA Astrophysics Data System (ADS)

Sun, A. Y.

2017-12-01

Deep subsurface repositories are used for waste disposal and carbon sequestration. Monitoring deep subsurface repositories for potential anomalies is challenging, not only because the number of sensor networks and the quality of data are often limited, but also because of the lack of labeled data needed to train and validate machine learning (ML) algorithms. Although physical simulation models may be applied to predict anomalies (or the system's nominal state for that sake), the accuracy of such predictions may be limited by inherent conceptual and parameter uncertainties. The main objective of this study was to demonstrate the potential of data-driven models for leakage detection in carbon sequestration repositories. Monitoring data collected during an artificial CO2 release test at a carbon sequestration repository were used, which include both scalar time series (pressure) and vector time series (distributed temperature sensing). For each type of data, separate online anomaly detection algorithms were developed using the baseline experiment data (no leak) and then tested on the leak experiment data. Performance of a number of different online algorithms was compared. Results show the importance of including contextual information in the dataset to mitigate the impact of reservoir noise and reduce false positive rate. The developed algorithms were integrated into a generic Web-based platform for real-time anomaly detection.

The potential of near-surface geophysical methods in a hierarchical monitoring approach for the detection of shallow CO2 seeps at geological storage sites

NASA Astrophysics Data System (ADS)

Sauer, U.; Schuetze, C.; Dietrich, P.

2013-12-01

The MONACO project (Monitoring approach for geological CO2 storage sites using a hierarchic observation concept) aims to find reliable monitoring tools that work on different spatial and temporal scales at geological CO2 storage sites. This integrative hierarchical monitoring approach based on different levels of coverage and resolutions is proposed as a means of reliably detecting CO2 degassing areas at ground surface level and for identifying CO2 leakages from storage formations into the shallow subsurface, as well as CO2 releases into the atmosphere. As part of this integrative hierarchical monitoring concept, several methods and technologies from ground-based remote sensing (Open-path Fourier-transform infrared (OP-FTIR) spectroscopy), regional measurements (near-surface geophysics, chamber-based soil CO2 flux measurement) and local in-situ measurements (using shallow boreholes) will either be combined or used complementary to one another. The proposed combination is a suitable concept for investigating CO2 release sites. This also presents the possibility of adopting a modular monitoring concept whereby our monitoring approach can be expanded to incorporate other methods in various coverage scales at any temporal resolution. The link between information obtained from large-scale surveys and local in-situ monitoring can be realized by sufficient geophysical techniques for meso-scale monitoring, such as geoelectrical and self-potential (SP) surveys. These methods are useful for characterizing fluid flow and transport processes in permeable near-surface sedimentary layers and can yield important information concerning CO2-affected subsurface structures. Results of measurements carried out a natural analogue site in the Czech Republic indicate that the hierarchical monitoring approach represents a successful multidisciplinary modular concept that can be used to monitor both physical and chemical processes taking place during CO2 migration and seepage. The application of FTIR spectroscopy in combination with soil gas surveys and geophysical investigations results in a comprehensive site characterization, including atmospheric and near-surface CO2 distribution, as well as subsurface structural features. We observed a correlation of higher CO2 concentration and flux rates at the meso-scale that coincides with distinct geophysical anomalies. Here, we found prominent SP anomalies and zones of lower resistivity in the geoelectrical images compared to undisturbed regions nearby. This presentation will discuss the results we obtained and illustrate the influence of CO2 on electrical parameters measured under field conditions in relation to environmental parameters.

Vadose Zone and Surficial Monitoring a Controlled Release of Methane in the Borden Aquifer, Ontario.

NASA Astrophysics Data System (ADS)

Forde, O.; Mayer, K. U.; Cahill, A.; Parker, B. L.; Cherry, J. A.

2015-12-01

Development of shale gas resources and potential impacts on groundwater and fugitive gas emissions necessitates further research on subsurface methane gas (CH4) migration and fate. To address this issue, a controlled release experiment is undertaken at the Borden research aquifer, Ontario, Canada. Due to low solubility, it is expected that the injection will lead to gas exsolution and ebullition. Gas migration is expected to extend to the unsaturated zone and towards the ground surface, and may possibly be affected by CH4 oxidation. The project consists of multiple components targeting the saturated zone, unsaturated zone, and gas emissions at the ground surface. This presentation will focus on the analysis of surficial CO2 and CH4 effluxes and vadose zone gas composition to track the temporal and spatial evolution of fugitive gas. Surface effluxes are measured with flux chambers connected to a laser-based gas analyzer, and subsurface gas samples are being collected via monitoring wells equipped with sensors for oxygen, volumetric water content, electrical conductivity, and temperature to correlate with changes in gas composition. First results indicate rapid migration of CH4 to the ground surface in the vicinity of the injection locations. We will present preliminary data from this experiment and evaluate the distribution and rate of gas migration. This research specifically assesses environmental risks associated with fugitive gas emissions related to shale gas resource development.

Characterization and transcription of arsenic respiration and resistance genes during in situ uranium bioremediation

PubMed Central

Giloteaux, Ludovic; Holmes, Dawn E; Williams, Kenneth H; Wrighton, Kelly C; Wilkins, Michael J; Montgomery, Alison P; Smith, Jessica A; Orellana, Roberto; Thompson, Courtney A; Roper, Thomas J; Long, Philip E; Lovley, Derek R

2013-01-01

The possibility of arsenic release and the potential role of Geobacter in arsenic biogeochemistry during in situ uranium bioremediation was investigated because increased availability of organic matter has been associated with substantial releases of arsenic in other subsurface environments. In a field experiment conducted at the Rifle, CO study site, groundwater arsenic concentrations increased when acetate was added. The number of transcripts from arrA, which codes for the α-subunit of dissimilatory As(V) reductase, and acr3, which codes for the arsenic pump protein Acr3, were determined with quantitative reverse transcription-PCR. Most of the arrA (>60%) and acr3-1 (>90%) sequences that were recovered were most similar to Geobacter species, while the majority of acr3-2 (>50%) sequences were most closely related to Rhodoferax ferrireducens. Analysis of transcript abundance demonstrated that transcription of acr3-1 by the subsurface Geobacter community was correlated with arsenic concentrations in the groundwater. In contrast, Geobacter arrA transcript numbers lagged behind the major arsenic release and remained high even after arsenic concentrations declined. This suggested that factors other than As(V) availability regulated the transcription of arrA in situ, even though the presence of As(V) increased the transcription of arrA in cultures of Geobacter lovleyi, which was capable of As(V) reduction. These results demonstrate that subsurface Geobacter species can tightly regulate their physiological response to changes in groundwater arsenic concentrations. The transcriptomic approach developed here should be useful for the study of a diversity of other environments in which Geobacter species are considered to have an important influence on arsenic biogeochemistry. PMID:23038171

Characterization and Transcription of Arsenic Respiration and Resistance Genes During In Situ Uranium Bioremediation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Giloteaux, L.; Holmes, Dawn E.; Williams, Kenneth H.

2013-02-04

The possibility of arsenic release and the potential role of Geobacter in arsenic biogeochemistry during in situ uranium bioremediation was investigated because increased availability of organic matter has been associated with substantial releases of arsenic in other subsurface environments. In a field experiment conducted at the Rifle, CO study site, groundwater arsenic concentrations increased when acetate was added. The number of transcripts from arrA, which codes for the alpha subunit of dissimilatory As(V) reductase, and acr3, which codes for the arsenic pump protein Acr3, were determined with quantitative RT-PCR. Most of the arrA (> 60%) and acr3-1 (> 90%) sequencesmore » that were recovered were most similar to Geobacter species, while the majority of acr3-2 (>50%) sequences were most closely related to Rhodoferax ferrireducens. Analysis of transcript abundance demonstrated that transcription of acr3-1 by the subsurface Geobacter community was correlated with arsenic concentrations in the groundwater. In contrast, Geobacter arrA transcript numbers lagged behind the major arsenic release and remained high even after arsenic concentrations declined. This suggested that factors other than As(V) availability regulated transcription of arrA in situ even though the presence of As(V) increased transcription of arrA in cultures of G. lovleyi, which was capable of As(V) reduction. These results demonstrate that subsurface Geobacter species can tightly regulate their physiological response to changes in groundwater arsenic concentrations. The transcriptomic approach developed here should be useful for the study of a diversity of other environments in which Geobacter species are considered to have an important influence on arsenic biogeochemistry.« less

Methanogenesis-induced pH–Eh shifts drives aqueous metal(loid) mobility in sulfide mineral systems under CO2 enriched conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harvey, Omar R.; Qafoku, Nikolla; Cantrell, Kirk J.

2016-01-15

Accounting for microbially-mediated CO2 transformation is pivotal to assessing geochemical implications for elevated CO2 in subsurface environments. A series of batch-reactor experiments were conducted to decipher links between autotrophic methanogenesis, CO2 dynamics and aqueous Fe, As and Pb concentrations in the presence of sulfide minerals. Microbially-mediated solubility-trapping followed by pseudo-first order reduction of HCO3- to CH4 (k’ = 0.28-0.59 d-1) accounted for 95% of the CO2 loss from methanogenic experiments. Bicarbonate-to-methane reduction was pivotal in the mitigation of CO2-induced acidity (~1 pH unit) and enhancement of reducing conditions (Eh change from -0.215 to -0.332V ). Methanogenesis-associated shifts in pH-Eh valuesmore » showed no significant effect on aqueous Pb but favored, 1) increased aqueous As as a result of microbially-mediated dissolution of arsenopyrite and 2) decreased aqueous Fe due to mineral-trapping of CO2-mobilized Fe as Fe-carbonate. Its order of occurrence (and magnitude), relative to solubility- and mineral-trapping, highlighted the potential for autotrophic methanogenesis to modulate both carbon sequestration and contaminant mobility in CO2-impacted subsurface environments.« less

Using Heavy Noble Gases to Help Determine Mantle vs Lithospheric Contributions and CO2 Residence Times in Southwestern US Hot Springs

NASA Astrophysics Data System (ADS)

Whyte, C. J.; Karlstrom, K. E.; Crossey, L. J.; Darrah, T.

2017-12-01

Climate change has placed a particular importance on the understanding of carbon cycling, especially on continental scales, resulting in the necessity to quantify the rates and timing on which CO2 is released into the atmosphere by volcanic and tectonic processes. Recent studies have identified mantle-derived 3He and excess CO2 in springs and groundwaters across the conterminous US, suggesting that there may be great unknowns in the rates and scales of magmatic CO2 release in the global carbon budget. Further, it remains uncertain if these fluids are merely passive remnants of past magmatic events or instead result from ongoing mantle degassing. Understanding these processes and timescales by studying CO2 fluxes alone can be challenging because CO2 is highly reactive in the subsurface. CO2 is both formed and degraded by microbial processes, rapidly dissolves into waters, and can be readily released from carbonate-rich lithologies by water-rock interactions. By comparison, chemically-inert tracers such as noble gases provide one potential technique for identifying and constraining fluid sources and migration histories in the subsurface. Primordial isotopes (e.g., 3He and 129Xe) provide unambiguous indications of mantle-derived fluids, and heavier noble gases (e.g., Ne, Ar, Kr, Xe) provide a suite of potential tracers that can help de-convolve the extent of mixing between crust and mantle and discern between lithospheric and asthenospheric mantle fluids. Additionally, the low production rate of the radiogenic xenon isotopes (e.g., 134Xe, 136Xe) may help determine the relative residence time of mantle CO2 degassing in continental settings, providing important constraints on CO2 storage in the mantle and lithosphere in quiescent tectonic settings. To test these hypotheses, we analyzed a suite of noble gas isotopic compositions in hot springs in the Colorado Plateau and Rocky Mountains, US. Many samples display resolvable excesses in 3He and 129Xe relative to air-saturated water with variable excesses in 40Ar* and radiogenic xenon isotopes. Excess 3He and 129Xe are consistent with mantle contributions, while variable abundances of radiogenic gases reflect the relative mixtures of air-saturated water, mantle, lithosphere, and the crust providing insight on their history during crustal emplacement.

Monitoring Shallow Subsurface CO2 Migration using Electrical Imaging Technique, Pilot Site in Brazil

NASA Astrophysics Data System (ADS)

Oliva, A.; Chang, H. K.; Moreira, A.

2013-12-01

Carbon Capture and Geological Sequestration (CCGS or CCS) is one of the main technological strategies targeting Greenhouse Gases (GHG) emissions reduction, with special emphasis on carbon dioxide (CO2) coming from industrial sources. CCGS integrates the so called Carbon Management Strategies, as indicated by the Intergovernmental Panel on Climate Change (IPCC), and is the basis of main technical route likely to enable substantial emission reduction in a safe, quick and cost-effective way. Currently one of the main challenges in the area of CO2 storage research is to grant the development, testing and validation of accurate and efficient measuring, monitoring and verification (MMV) techniques to be deployed at the final storage site, targeting maximum storage efficiency at the minimal leakage risk levels. The implementation of the first CO2 MMV field lab in Brazil, located in Florianópolis, Santa Catarina state, offered an excellent opportunity for running controlled release experiments in a real open air environment. The purpose of this work is to present the results of a time lapse monitoring experiment of CO2 migration in both saturated and unsaturated sand-rich sediments, using electrical imaging technique. The experiment covered an area of approximately 6300 m2 and CO2 was continuously injected at depth of 8 m, during 12 days, at an average rate of 90 g/ day, totalizing 1080 g of injected CO2. 2D and 3D electrical images using Wenner array were acquired daily during 13 consecutive days. Comparison of post injection electrical imaging results with pre injection images shows change in resistivity values consistent with migration pathways of CO2. A pronounced increase in resistivity values (up to ~ 500 ohm.m) with respect to the pre-injection values occurs in the vicinity of the injection well. Background values of 530 ohm.m have changed to 1118 ohm.m, right after injection. Changes in resistivity values progressively diminish outward of the well, following groundwater flow path.

The effect of biogenic Fe(II) on the stability and sorption of Co(II)EDTA 2- to goethite and a subsurface sediment

NASA Astrophysics Data System (ADS)

Zachara, John M.; Smith, Steven C.; Fredrickson, James K.

2000-04-01

Laboratory experiments were conducted with suspensions of goethite (α-FeOOH) and a subsurface sediment to assess the influence of bacterial iron reduction on the fate of Co(II)EDTA 2-, a representative metal-ligand complex of intermediate stability (log K Co(II)EDTA = 17.97). The goethite was synthetic (ca. 55 m 2/g) and the sediment was a Pleistocene age, Fe(III) oxide-containing material from the Atlantic coastal plain (Milford). Shewanella alga strain BrY, a dissimilatory iron reducing bacterium (DIRB), was used to promote Fe(III) oxide reduction. Sorption isotherms and pH adsorption edges were measured for Co 2+, Fe 2+, Co(II)EDTA 2-, and Fe(II)EDTA 2- on the two sorbents in 0.001 mol/L Ca(ClO 4) 2 to aid in experiment interpretation. Anoxic suspensions of the sorbents in PIPES buffer at pH 6.5-7.0 were spiked with Co(II)EDTA 2- (10 -5 mol/L, 60Co and 14EDTA labeled), inoculated with BrY (1-6 × 10 8 organisms/mL), and the headspace filled with a N 2/H 2 gas mix. The experiments were conducted under non-growth conditions. The medium did not contain PO 43- (with one exception), trace elements, or vitamins. The tubes were incubated under anoxic conditions at 25°C for time periods in excess of 100 d. Replicate tubes were sacrificed and analyzed at desired time periods for pH, Fe(II) TOT, Fe (aq)2+, 60Co, and 14EDTA. Abiotic analogue experiments were conducted where Fe (aq)2+ was added in increasing concentration to Co(II)EDTA 2-/mineral suspensions to simulate the influence of bacterial Fe(II) evolution. The DIRB generated Fe(II) from both goethite and the Milford sediment that was strongly sorbed by mineral surfaces. Aqueous Fe 2+ increased during the experiment as surfaces became saturated; Fe (aq)2+ induced the dissociation of Co(II)EDTA 2- into a mixture of Co 2+, Co(II)EDTA 2-, and Fe(II)EDTA 2- (log K Fe(II)EDTA = 15.98). The extent of dissociation of Co(II)EDTA 2- was greater in the subsurface sediment because it sorbed Fe(II) less strongly than did goethite. The post dissociation sorption behavior of Co 2+ was dependent on pH and the intrinsic sorptivity of the solid phases. Dissociation generally lead to an increase in the sorption (e.g., K d) of Co 2+ relative to EDTA 4- (form unspecified). Sorbed biogenic Fe(II) competed with free Co (aq)2+and reduced its sorption relative to unreduced material. It is concluded that cationic radionuclides such as 60Co or 239/240Pu, which may be mobilized from disposed wastes by complexation with EDTA 4-, may become immobilized in groundwater zones where dissimilatory bacterial iron reduction is operative.

Mineral Influence on Microbial Survival During Carbon Sequestration

NASA Astrophysics Data System (ADS)

Santillan, E. U.; Shanahan, T. M.; Wolfe, W. W.; Bennett, P.

2012-12-01

CO2 sequestered in a deep saline aquifer will perturb subsurface biogeochemistry by acidifying the groundwater and accelerating mineral diagenesis. Subsurface microbial communities heavily influence geochemistry through their metabolic processes, such as with dissimilatory iron reducing bacteria (DIRB). However, CO2 also acts as a sterilant and will perturb these communities. We investigated the role of mineralogy and its effect on the survival of microbes at high PCO2 conditions using the model DIRB Shewanella oneidensis MR-1. Batch cultures of Shewanella were grown to stationary phase and exposed to high PCO2 using modified Parr reactors. Cell viability was then determined by plating cultures after exposure. Results indicate that at low PCO2 (2 bar), growth and iron reduction are decreased and cell death occurs within 1 hour when exposed to CO2 pressures of 10 bar or greater. Further, fatty acid analysis indicates microbial lipid degradation with C18 fatty acids being the slowest lipids to degrade. When cultures were grown in the presence of rocks or minerals representative of the deep subsurface such as carbonates and silicates and exposed to 25 bar CO2, survival lasted beyond 2 hours. The most effective protecting substratum was quartz sandstone, with cultures surviving beyond 8 hours of CO2 exposure. Scanning electron microscope images reveal biofilm formation on the mineral surfaces with copious amounts of extracellular polymeric substances (EPS) present. EPS from these biofilms acts as a reactive barrier to the CO2, slowing the penetration of CO2 into cells and resulting in increased survival. When biofilm cultures were grown with Al and As to simulate the release of toxic metals from minerals such as feldspars and clays, survival time decreased, indicating mineralogy may also enhance microbial death. Biofilms were then grown on iron-coated quartz sand to determine conversely what influence biofilms may have on mineral dissolution during CO2 perturbation. Growth media was allowed to flow through a sand-packed column at a constant flow rate with pulses of liquid CO2 injected directly into the column. Preliminary data of dissolved iron measured from the effluent indicates that biofilm columns show a slight increase in dissolved iron concentrations before and after CO2 exposure in comparison to abiotic columns. These findings imply the important relationship between microbes and minerals during CO2 sequestration. The ability minerals have to contribute to the selection of microbes has important consequences to the survival of different microbial populations in the subsurface and the consequent biogeochemical changes that may happen.

Investigation of the relationship between CO2 reservoir rock property change and the surface roughness change originating from the supercritical CO2-sandstone-groundwater geochemical reaction at CO2 sequestration condition

NASA Astrophysics Data System (ADS)

Lee, Minhee; Wang, Sookyun; Kim, Seyoon; Park, Jinyoung

2015-04-01

Lab scale experiments were performed to investigate the property changes of sandstone slabs and cores, resulting from the scCO2-rock-groundwater reaction for 180 days under CO2 sequestration conditions (100 bar and 50 °C). The geochemical reactions, including the surface roughness change of minerals in the slab, resulted from the dissolution and the secondary mineral precipitation for the sandstone reservoir of the Gyeongsang basin, Korea were reproduced in laboratory scale experiments and the relationship between the geochemical reaction and the physical rock property change was derived, for the consideration of successful subsurface CO2 sequestration. The use of the surface roughness value (SRrms) change rate and the physical property change rate to quantify scCO2-rock-groundwater reaction is the novel approach on the study area for CO2 sequestration in the subsurface. From the results of SPM (Scanning Probe Microscope) analyses, the SRrms for each sandstone slab was calculated at different reaction time. The average SRrms increased more than 3.5 times during early 90 days reaction and it continued to be steady after 90 days, suggesting that the surface weathering process of sandstone occurred in the early reaction time after CO2 injection into the subsurface reservoir. The average porosity of sandstone cores increased by 8.8 % and the average density decreased by 0.5 % during 90 days reaction and these values slightly changed after 90 days. The average P and S wave velocities of sandstone cores also decreased by 10 % during 90 days reaction. The trend of physical rock property change during the geochemical reaction showed in a logarithmic manner and it was also correlated to the logarithmic increase in SRrms, suggesting that the physical property change of reservoir rocks originated from scCO2 injection directly comes from the geochemical reaction process. Results suggested that the long-term estimation of the physical property change for reservoir rocks in CO2 injection site could be possible from the extrapolation process of SRrms and rocks property change rates, acquired from laboratory scale experiments. It will be aslo useful to determine the favorite CO2 injection site from the viewpoint of the safety.

When Magma Meets Carbonate: Explosive Criminals of Climate Change?

NASA Astrophysics Data System (ADS)

Carter, L. B.

2017-12-01

The natural carbon cycle is a key component of global climate change. Identifying and quantifying all processes in the cycle is essential to determine the effects of human greenhouse gas contributions and make future predictions. Volcanoes are the main natural source of carbon dioxide to the atmosphere [1]. In settings where carbonate rocks underlie the edifice, they can be consumed by magma passing through, which can release extra CO2, potentially explaining the extremely high emissions at Mount Etna in Italy [2-4]. We conduct laboratory experiments, mimicking conditions in the crust, to study how different carbonate rocks interact with hot magmas at pressure, and determine the amount of CO2 generated. We find that some types of magma can raise volcanic gas output and cause more explosive and dangerous eruptions [5-6]. Others are more likely to release hot fluids to the surrounding rocks, releasing CO2 by skarnification, which leaves economically important ores like in the western US [3,7] but can weaken the subsurface, potentially leading to landslides. Gas can also be released on the flanks of a volcano or in regions lacking an active volcano, due to the breakdown of certain carbonate rocks by heat [7], seen as bubbling springs in Yellowstone [8]. Our experiments indicate that if dolostone, not limestone, surrounds a magma chamber, over half the CO2 that was locked in the crust can escape even at lower temperatures a distance away. These processes are perhaps pertinent to why the Earth's climate was warm >50 million years ago, when more magma-carbonate interaction likely occurred than today [3] and thus contributed several times the current volcanic output [4] to the atmosphere. As significant parts of the long-term carbon cycle, it is necessary to include magma-carbonate reactions when considering climate changes before taking into account human input. [1] Aiuppa et al 2017 ESciRev (168) 24-47; [2] Ganino and Arndt 2009 Geol (37) 323-326; [3] Lee et al. 2013 Geosph (9) 21-36; [4] Burton et al. 2013 RiMG (75) 3232-254; [4] Chiodini et al. 2011 BullVolc (73) 531-542; [5] Carter and Dasgupta 2015 EPSL (427) 202-214; [6] Carter and Dasgupta 2016 G3 (17) 3893-3916; [7] Franzolin et al. 2011 CMP (161)213-227; [8] Werner and Brantley 2003 (4) 1061-1088.

Modeling of Near-Surface Leakage and Seepage of CO2 for Risk Characterization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oldenburg, Curtis M.; Unger, Andre A.J.

2004-02-18

The injection of carbon dioxide (CO2) into deep geologic carbon sequestration sites entails risk that CO2 will leak away from the primary storage formation and migrate upwards to the unsaturated zone from which it can seep out of the ground. We have developed a coupled modeling framework called T2CA for simulating CO2 leakage and seepage in the subsurface and in the atmospheric surface layer. The results of model simulations can be used to calculate the two key health, safety, and environmental (HSE) risk drivers, namely CO2 seepage flux and nearsurface CO2 concentrations. Sensitivity studies for a subsurface system with amore » thick unsaturated zone show limited leakage attenuation resulting in correspondingly large CO2 concentrations in the shallow subsurface. Large CO2 concentrations in the shallow subsurface present a risk to plant and tree roots, and to humans and other animals in subsurface structures such as basements or utility vaults. Whereas CO2 concentrations in the subsurface can be high, surfacelayer winds reduce CO2 concentrations to low levels for the fluxes investigated. We recommend more verification and case studies be carried out with T2CA, along with the development of extensions to handle additional scenarios such as calm conditions, topographic effects, and catastrophic surface-layer discharge events.« less

Microbial succession and stimulation following a test well injection simulating CO2 leakage into shallow Newark Basin aquifers

NASA Astrophysics Data System (ADS)

Dueker, M.; Clauson, K.; Yang, Q.; Umemoto, K.; Seltzer, A. M.; Zakharova, N. V.; Matter, J. M.; Stute, M.; Takahashi, T.; Goldberg, D.; O'Mullan, G. D.

2012-12-01

Despite growing appreciation for the importance of microbes in altering geochemical reactions in the subsurface, the microbial response to geological carbon sequestration injections and the role of microbes in altering metal mobilization following leakage scenarios in shallow aquifers remain poorly constrained. A Newark Basin test well was utilized in field experiments to investigate patterns of microbial succession following injection of CO2 saturated water into isolated aquifer intervals. Additionally, laboratory mesocosm experiments, including microbially-active and inactive (autoclave sterilized) treatments, were used to constrain the microbial role in mineral dissolution, trace metal release, and gas production (e.g. hydrogen and methane). Hydrogen production was detected in both sterilized and unsterilized laboratory mesocosm treatments, indicating abiotic hydrogen production may occur following CO2 leakage, and methane production was detected in unsterilized, microbially active mesocosms. In field experiments, a decrease in pH following injection of CO2 saturated aquifer water was accompanied by mobilization of trace elements (e.g. Fe and Mn), the production of hydrogen gas, and increased bacterial cell concentrations. 16S ribosomal RNA clone libraries, from samples collected before and after the test well injection, were compared in an attempt to link variability in geochemistry to changes in aquifer microbiology. Significant changes in microbial composition, compared to background conditions, were found following the test well injection, including a decrease in Proteobacteria, and an increased presence of Firmicutes, Verrucomicrobia, Acidobacteria and other microbes associated with iron reducing and syntrophic metabolism. The concurrence of increased microbial cell concentration, and rapid microbial community succession, with increased concentrations of hydrogen gas suggests that abiotically produced hydrogen may serve as an ecologically-relevant energy source stimulating changes in aquifer microbial communities immediately following CO2 leakage.

Release of Dissolved CO2 from Water in Laboratory Porous Media Following Rapid Depressurization

NASA Astrophysics Data System (ADS)

Crews, J. B.; Cooper, C. A.

2011-12-01

A bench-top laboratory study is undertaken to investigate the effects of seismic shocks on brine aquifers into which carbon dioxide has been injected for permanent storage. Long-term storage in deep saline aquifers has been proposed and studied as one of the most viable near-term options for sequestering fossil fuel-derived carbon dioxide from the atmosphere to curb anthropogenic climate change. Upon injection into the subsurface, it is expected that CO2, as either a gas or supercritical fluid, will mix convectively with the formation water. The possibility exists, however, that dissolved CO2 will come out of solution as a result of an earthquake. The effect is similar to that of slamming an unsealed container of carbonated beverage on a table; previously dissolved CO2 precipitates, forms bubbles, and rises due to buoyancy. In this study, we measure the change in gas-phase CO2 concentration as a function of the magnitude of the shock and the initial concentration of CO2. In addition, we investigate and seek to characterize the nucleation and transport of CO2 bubbles in a porous medium after a seismic shock. Experiments are conducted using a Hele-Shaw cell and a CCD camera to quantify the fraction of dissolved CO2 that comes out of solution as a result of a sharp mechanical impulse. The data are used to identify and constrain the conditions under which CO2 comes out of solution and, further, to understand the end-behavior of the precipitated gas-phase CO2 as it moves through or is immobilized in a porous medium.

Controls on Nitrous Oxide Emissions from the Hyporheic Zones of Streams.

PubMed

Quick, Annika M; Reeder, W Jeffery; Farrell, Tiffany B; Tonina, Daniele; Feris, Kevin P; Benner, Shawn G

2016-11-01

The magnitude and mechanisms of nitrous oxide (N 2 O) release from rivers and streams are actively debated. The complex interactions of hydrodynamic and biogeochemical controls on emissions of this important greenhouse gas preclude prediction of when and where N 2 O emissions will be significant. We present observations from column and large-scale flume experiments supporting an integrative model of N 2 O emissions from stream sediments. Our results show a distinct, replicable, pattern of nitrous oxide generation and consumption dictated by subsurface (hyporheic) residence times and biological nitrogen reduction rates. Within this model, N 2 O emission from stream sediments requires subsurface residence times (and microbially mediated reduction rates) be sufficiently long (and fast reacting) to produce N 2 O by nitrate reduction but also sufficiently short (or slow reacting) to limit N 2 O conversion to dinitrogen gas. Most subsurface exchange will not result in N 2 O emissions; only specific, intermediate, residence times (reaction rates) will both produce and release N 2 O to the stream. We also confirm previous observations that elevated nitrate and declining organic carbon reactivity increase N 2 O production, highlighting the importance of associated reaction rates in controlling N 2 O accumulation. Combined, these observations help constrain when N 2 O release will occur, providing a predictive link between stream geomorphology, hydrodynamics, and N 2 O emissions.

Subsurface plasma in beam of continuous CO2-laser

NASA Astrophysics Data System (ADS)

Danytsikov, Y. V.; Dymshakov, V. A.; Lebedev, F. V.; Pismennyy, V. D.; Ryazanov, A. V.

1986-03-01

Experiments performed at the Institute of Atomic Energy established the conditions for formation of subsurface plasma in substances by laser radiation and its characteristics. A quasi-continuous CO2 laser emitting square pulses of 0.1 to 1.0 ms duration and 1 to 10 kW power as well as a continuous CO2 laser served as radiation sources. Radiation was focused on spots 0.1 to 0.5 mm in diameter and maintained at levels ensuring constant power density during the interaction time, while the temperature of the target surface was measured continuously. Metals, graphite and dielectric materials were tested with laser action taking place in air N2 + O2 mixtures, Ar or He atmosphere under pressures of 0.01 to 1.0 atm. Data on radiation intensity thresholds for evaporation and plasma formation were obtained. On the basis of these thresholds, combined with data on energy balance and the temperature profile in plasma layers, a universal state diagram was constructed for subsurface plasma with nonquantified surface temperature and radiation intensity coordinates.

Soil CO2 concentrations and efflux dynamics of a tree island in the Pantanal wetland

NASA Astrophysics Data System (ADS)

Lathuillière, Michael J.; Pinto, Osvaldo B.; Johnson, Mark S.; Jassal, Rachhpal S.; Dalmagro, Higo J.; Leite, Nei K.; Speratti, Alicia B.; Krampe, Daniela; Couto, Eduardo G.

2017-08-01

The Pantanal is the largest tropical wetland on the planet, and yet little information is available on the biome's carbon cycle. We used an automatic station to measure soil CO2 concentrations and oxidation-reduction potential over the 2014 and 2015 flood cycles of a tree island in the Pantanal that is immune to inundation during the wetland's annual flooding. The soil CO2 concentration profile was then used to estimate soil CO2 efflux over the two periods. In 2014, subsurface soil saturation at 0.30 m depth created conditions in that layer that led to CO2 buildup close to 200,000 ppm and soil oxidation-reduction potential below -300 mV, conditions that were not repeated in 2015 due to annual variability in soil saturation at the site. Mean CO2 efflux over the 2015 flood cycle was 0.023 ± 0.103 mg CO2-C m-2 s-1 representing a total annual efflux of 593 ± 2690 mg CO2-C m-2 y-1. Unlike a nearby tree island site that experiences full inundation during the wet season, here the soil dried quickly following repeated rain events throughout the year, which led to the release of CO2 pulses from the soil. This study highlights not only the complexity and heterogeneity in the Pantanal's carbon balance based on differences in topography, flood cycles, and vegetation but also the challenges of applying the gradient method in the Pantanal due to deviations from steady state conditions.

Subsurface Growth Of Silicide Structures In Silicon

NASA Technical Reports Server (NTRS)

Fathauer, Robert W.; George, Thomas; Pike, William T.; Schowalter, Leo

1993-01-01

Technique shows promise for fabrication of novel electronic, optoelectronic, and electro-optical devices. Experiments demonstrated feasibility of growing microscopic single-crystal CoSi2 structures beneath surfaces of Si substrates.

Methane and benzene in drinking-water wells overlying the Eagle Ford, Fayetteville, and Haynesville Shale hydrocarbon production areas

USGS Publications Warehouse

McMahon, Peter B.; Barlow, Jeannie R.; Engle, Mark A.; Belitz, Kenneth; Ging, Patricia B.; Hunt, Andrew G.; Jurgens, Bryant; Kharaka, Yousif K.; Tollett, Roland W.; Kresse, Timothy M.

2017-01-01

Water wells (n = 116) overlying the Eagle Ford, Fayetteville, and Haynesville Shale hydrocarbon production areas were sampled for chemical, isotopic, and groundwater-age tracers to investigate the occurrence and sources of selected hydrocarbons in groundwater. Methane isotopes and hydrocarbon gas compositions indicate most of the methane in the wells was biogenic and produced by the CO2 reduction pathway, not from thermogenic shale gas. Two samples contained methane from the fermentation pathway that could be associated with hydrocarbon degradation based on their co-occurrence with hydrocarbons such as ethylbenzene and butane. Benzene was detected at low concentrations (<0.15 μg/L), but relatively high frequencies (2.4–13.3% of samples), in the study areas. Eight of nine samples containing benzene had groundwater ages >2500 years, indicating the benzene was from subsurface sources such as natural hydrocarbon migration or leaking hydrocarbon wells. One sample contained benzene that could be from a surface release associated with hydrocarbon production activities based on its age (10 ± 2.4 years) and proximity to hydrocarbon wells. Groundwater travel times inferred from the age-data indicate decades or longer may be needed to fully assess the effects of potential subsurface and surface releases of hydrocarbons on the wells.

Methane and Benzene in Drinking-Water Wells Overlying the Eagle Ford, Fayetteville, and Haynesville Shale Hydrocarbon Production Areas.

PubMed

McMahon, Peter B; Barlow, Jeannie R B; Engle, Mark A; Belitz, Kenneth; Ging, Patricia B; Hunt, Andrew G; Jurgens, Bryant C; Kharaka, Yousif K; Tollett, Roland W; Kresse, Timothy M

2017-06-20

Water wells (n = 116) overlying the Eagle Ford, Fayetteville, and Haynesville Shale hydrocarbon production areas were sampled for chemical, isotopic, and groundwater-age tracers to investigate the occurrence and sources of selected hydrocarbons in groundwater. Methane isotopes and hydrocarbon gas compositions indicate most of the methane in the wells was biogenic and produced by the CO 2 reduction pathway, not from thermogenic shale gas. Two samples contained methane from the fermentation pathway that could be associated with hydrocarbon degradation based on their co-occurrence with hydrocarbons such as ethylbenzene and butane. Benzene was detected at low concentrations (<0.15 μg/L), but relatively high frequencies (2.4-13.3% of samples), in the study areas. Eight of nine samples containing benzene had groundwater ages >2500 years, indicating the benzene was from subsurface sources such as natural hydrocarbon migration or leaking hydrocarbon wells. One sample contained benzene that could be from a surface release associated with hydrocarbon production activities based on its age (10 ± 2.4 years) and proximity to hydrocarbon wells. Groundwater travel times inferred from the age-data indicate decades or longer may be needed to fully assess the effects of potential subsurface and surface releases of hydrocarbons on the wells.

Soil Carbon Dioxide Production and Surface Fluxes: Subsurface Physical Controls

NASA Astrophysics Data System (ADS)

Risk, D.; Kellman, L.; Beltrami, H.

Soil respiration is a critical determinant of landscape carbon balance. Variations in soil temperature and moisture patterns are important physical processes controlling soil respiration which need to be better understood. Relationships between soil respi- ration and physical controls are typically addressed using only surface flux data but other methods also exist which permit more rigorous interpretation of soil respira- tion processes. Here we use a combination of subsurface CO_{2} concentrations, surface CO_{2} fluxes and detailed physical monitoring of the subsurface envi- ronment to examine physical controls on soil CO_{2} production at four climate observatories in Eastern Canada. Results indicate that subsurface CO_{2} produc- tion is more strongly correlated to the subsurface thermal environment than the surface CO_{2} flux. Soil moisture was also found to have an important influence on sub- surface CO_{2} production, particularly in relation to the soil moisture - soil profile diffusivity relationship. Non-diffusive profile CO_{2} transport appears to be im- portant at these sites, resulting in a de-coupling of summertime surface fluxes from subsurface processes and violating assumptions that surface CO_{2} emissions are the result solely of diffusion. These results have implications for the study of soil respiration across a broad range of terrestrial environments.

A fundamental study of gas formation and migration during leakage of stored carbon dioxide in subsurface formations

NASA Astrophysics Data System (ADS)

Sakaki, T.; Plampin, M. R.; Lassen, R. N.; Pawar, R. J.; Komatsu, M.; Jensen, K. H.; Illangasekare, T. H.

2011-12-01

Geologic sequestration of CO2 has received significant attention as a potential method for reducing the release of greenhouse gases into the atmosphere. Potential risk of leakage of the stored CO2 to the shallow zones of the subsurface is one of the critical issues that is needed to be addressed to design effective field storage systems. If a leak occurs, gaseous CO2 reaching shallow zones of the subsurface can potentially impact the surface and groundwater sources and vegetation. With a goal of developing models that can predict these impacts, a research study is underway to improve our understanding of the fundamental processes of gas-phase formation and multi-phase flow dynamics during CO2 migration in shallow porous media. The approach involves conducting a series of highly controlled experiments in soil columns and tanks to study the effects of soil properties, temperature, pressure gradients and heterogeneities on gas formation and migration. This paper presents the results from a set of column studies. A 3.6m long column was instrumented with 16 soil moisture sensors, 15 of which were capable of measuring electrical conductivity (EC) and temperature, eight water pressure, and two gas pressure sensors. The column was filled with test sands with known hydraulic and retention characteristics with predetermined packing configurations. Deionized water saturated with CO2 under ~0.3 kPa (roughly the same as the hydrostatic pressure at the bottom of the column) was injected at the bottom of the column using a peristaltic pump. Water and gas outflow at the top of the column were monitored continuously. The results, in general, showed that 1) gas phase formation can be triggered by multiple factors such as water pressure drop, temperature rise, and heterogeneity, 2) transition to gas phase tends to occur rather within a short period of time, 3) gas phase fraction was as high as ~40% so that gas flow was not via individual bubble movement but two-phase flow, 4) water outflow that was initially equal to the inflow rate increased when gas-phase started to form (i.e., water gets displaced), and 5) gas starts to flow upward after gas phase fraction stabilizes (i.e., buoyant force overcomes). These results suggest that the generation and migration processes of gas phase CO2 can be modelled as a traditional two-phase flow with source (when CO2 gas exsolved due to complex factors) as well as sink (when gas dissolved) terms. The experimental data will be used to develop and test the conceptual models that will guide the development of numerical simulators for applications involving CO2 storage and leakage.

Microbial Life Driving Low-Temperature Basalt Alteration in the Subsurface: Decoupling Abiotic Processes from Biologically-Mediated Rock Alteration

NASA Astrophysics Data System (ADS)

Moore, R.; Lecoeuvre, A.; Stephant, S.; Dupraz, S.; Ranchou-Peyruse, M.; Ranchou-Peyruse, A.; Gérard, E.; Ménez, B.

2017-12-01

Microorganisms are involved with specific rock alteration processes in the deep subsurface. It is a challenge to link any contribution microbial life may have on rock alteration with specific functions or phyla because many alteration features and secondary minerals produced by metabolic processes can also produce abiotically. Here, two flow-through experiments were designed to mimic the circulation of a CO2-rich fluid through crystalline basalt. In order to identify microbially-mediated alteration and be able to link it with specific metabolisms represented in the subsurface, a relatively fresh crystalline basalt substrate was subsampled, sterilized and used as the substrate for both experiments. In one experiment, the substrate was left sterile, and in the other it was inoculated with an enrichment culture derived from the same aquifer as the rock substrate. Initial results show that the inoculum contained Proteobacteria and Firmicutes, which have diverse metabolic potentials. Fluid and rock analyses before, during, and after the experiments show that mineralogy, fluid chemistry, and dissolution processes differ between the sterile and inoculated systems. In the inoculated experiment iron-rich orthopyroxenes were preferentially dissolved while in the sterile system clinopyroxenes and plagioclases both exhibited a higher degree of dissolution. Additionally, the patterns of CO2 consumption and production over the duration of both experiments is different. This suggest that in a low-temperature basalt system with microorganisms CO2 is either consumed to produce biomass, or that carbonates are produced and then subsequently preserved. This suite of results combined with molecular ecology analyses can be used to conclude that in low-temperature basalts microorganisms play an intrinsic role in rock alteration.

Impact of CO 2 on the Evolution of Microbial Communities Exposed to Carbon Storage Conditions, Enhanced Oil Recovery, and CO 2 Leakage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gulliver, Djuna M.; Gregory, Kelvin B.; Lowry, Gregory V.

Geologic carbon storage (GCS) is a crucial part of a proposed mitigation strategy to reduce the anthropogenic carbon dioxide (CO 2) emissions to the atmosphere. During this process, CO 2 is injected as super critical carbon dioxide (SC-CO 2) in confined deep subsurface storage units, such as saline aquifers and depleted oil reservoirs. The deposition of vast amounts of CO 2 in subsurface geologic formations could unintentionally lead to CO 2 leakage into overlying freshwater aquifers. Introduction of CO 2 into these subsurface environments will greatly increase the CO 2 concentration and will create CO 2 concentration gradients that drivemore » changes in the microbial communities present. While it is expected that altered microbial communities will impact the biogeochemistry of the subsurface, there is no information available on how CO 2 gradients will impact these communities. The overarching goal of this project is to understand how CO 2 exposure will impact subsurface microbial communities at temperatures and pressures that are relevant to GCS and CO 2 leakage scenarios. To meet this goal, unfiltered, aqueous samples from a deep saline aquifer, a depleted oil reservoir, and a fresh water aquifer were exposed to varied concentrations of CO 2 at reservoir pressure and temperature. The microbial ecology of the samples was examined using molecular, DNA-based techniques. The results from these studies were also compared across the sites to determine any existing trends. Results reveal that increasing CO 2 leads to decreased DNA concentrations regardless of the site, suggesting that microbial processes will be significantly hindered or absent nearest the CO 2 injection/leakage plume where CO 2 concentrations are highest. At CO 2 exposures expected downgradient from the CO 2 plume, selected microorganisms emerged as dominant in the CO 2 exposed conditions. Results suggest that the altered microbial community was site specific and highly dependent on pH. The site-dependent results suggest a limited ability to predict the emerging dominant species for other CO 2-exposed environments. This study improves the understanding of how a subsurface microbial community may respond to conditions expected from GCS and CO 2 leakage. This is the first step for understanding how a CO 2-altered microbial community may impact injectivity, permanence of stored CO 2, and subsurface water quality. Future work with microbial communities from new subsurface sites would increase the current understanding of this project. Additionally, incorporation of metagenomic methods would increase understanding of potential microbial processes that may be prevalent in CO 2 exposed environments.« less

Viability of modelling gas transport in shallow injection-monitoring experiment field at Maguelone, France

NASA Astrophysics Data System (ADS)

Basirat, Farzad; Perroud, Hervé; Lofi, Johanna; Denchik, Nataliya; Lods, Gérard; Fagerlund, Fritjof; Sharma, Prabhakar; Pezard, Philippe; Niemi, Auli

2015-04-01

In this study, TOUGH2/EOS7CA model is used to simulate the shallow injection-monitoring experiment carried out at Maguelone, France, during 2012 and 2013. The possibility of CO2 leakage from storage reservoir to upper layers is one of the issues that need to be addressed in CCS projects. Developing reliable monitoring techniques to detect and characterize CO2 leakage is necessary for the safety of CO2 storage in reservoir formations. To test and cross-validate different monitoring techniques, a series of shallow gas injection-monitoring experiments (SIMEx) has been carried out at the Maguelone. The experimental site is documented in Lofi et al [2013]. At the site, a series of nitrogen and one CO2 injection experiment have been carried out during 2012-2013 and different monitoring techniques have been applied. The purpose of modelling is to acquire understanding of the system performance as well as to further develop and validate modelling approaches for gas transport in the shallow subsurface, against the well-controlled data sets. The preliminary simulation of the experiment including the simulation for the Nitrogen injection test in 2012 was presented in Basirat et al [2013]. In this work, the simulations represent the gaseous CO2 distribution and dissolved CO2 within range obtained by monitoring approaches. The Multiphase modelling in combination with geophysical monitoring can be used for process understanding of gas phase migration- and mass transfer processes resulting from gaseous CO2 injection. Basirat, F., A. Niemi, H. Perroud, J. Lofi, N. Denchik, G. Lods, P. Pezard, P. Sharma, and F. Fagerlund (2013), Modeling Gas Transport in the Shallow Subsurface in Maguelone Field Experiment, Energy Procedia, 40, 337-345. Lofi, J., P. Pezard, F. Bouchette, O. Raynal, P. Sabatier, N. Denchik, A. Levannier, L. Dezileau, and R. Certain (2013), Integrated Onshore-Offshore Investigation of a Mediterranean Layered Coastal Aquifer, Groundwater, 51(4), 550-561.

Fundamental Study on the Dynamics of Heterogeneity-Enhanced CO2 Gas Evolution in the Shallow Subsurface During Possible Leakage from Deep Geologic Storage Sites

NASA Astrophysics Data System (ADS)

Plampin, M. R.; Lassen, R. N.; Sakaki, T.; Pawar, R.; Jensen, K.; Illangasekare, T. H.

2013-12-01

A concern for geologic carbon sequestration is the potential for CO2 stored in deep geologic formations to leak upward into shallow freshwater aquifers where it can have potentially detrimental impacts to the environment and human health. Understanding the mechanisms of CO2 exsolution, migration and accumulation (collectively referred to as 'gas evolution') in the shallow subsurface is critical to predict and mitigate the environmental impacts. During leakage, CO2 can move either as free-phase or as a dissolved component of formation brine. CO2 dissolved in brine may travel upward into shallow freshwater systems, and the gas may be released from solution. In the shallow aquifer, the exsolved gas may accumulate near interfaces between soil types, and/or create flow paths that allow the gas to escape through the vadose zone to the atmosphere. The process of gas evolution in the shallow subsurface is controlled by various factors, including temperature, dissolved CO2 concentration, water pressure, background water flow rate, and geologic heterogeneity. However, the conditions under which heterogeneity controls gas phase evolution have not yet been precisely defined and can therefore not yet be incorporated into models used for environmental risk assessment. The primary goal of this study is to conduct controlled laboratory experiments to help fill this knowledge gap. With this as a goal, a series of intermediate-scale laboratory experiments were conducted to observe CO2 gas evolution in porous media at multiple scales. Deionized water was saturated with dissolved CO2 gas under a specified pressure (the saturation pressure) before being injected at a constant volumetric flow rate into the bottom of a 1.7 meter-tall by 5.7 centimeter-diameter column or a 2.4 meter-tall by 40 centimeter-wide column that were both filled with sand in various heterogeneous packing configurations. Both test systems were initially saturated with fresh water and instrumented with soil moisture sensors to monitor the evolution of gas phase through time by measuring the average water content in small sampling volumes of soil. Tensiometers allowed for observation of water pressure through space and time in the test systems, and a computer-interfaced electronic scale continuously monitored the outflow of water from the top of the two test columns. Several packing configurations with five different types of sands were used in order to test the effects of various pore size contrasts and interface shapes on the evolution of the gas phase near soil texture transitions in the heterogeneous packings. Results indicate that: (1) heterogeneity affects gas phase evolution patterns within a predictable range of conditions quantified by the newly introduced term 'oversaturation,' (2) soil transition interfaces where less permeable material overlies more permeable material have a much more pronounced effect on gas evolution than interfaces with opposite orientations, and (3) anticlines (or stratigraphic traps) cause significantly greater gas accumulation than horizontal interfaces. Further work is underway to apply these findings to more realistic, two-dimensional scenarios, and to assess how well existing numerical models can capture these processes.

Impact of CO 2 on the Evolution of Microbial Communities Exposed to Carbon Storage Conditions, Enhanced Oil Recovery, and CO 2 Leakage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gulliver, Djuna; Gregory, Kelvin B.; Lowry, Gregorgy V.

Geologic carbon storage (GCS) is a crucial part of a proposed mitigation strategy to reduce the anthropogenic carbon dioxide (CO 2) emissions to the atmosphere. During this process, CO 2 is injected as super critical carbon dioxide (SC-CO 2) in confined deep subsurface storage units, such as saline aquifers and depleted oil reservoirs. The deposition of vast amounts of CO 2 in subsurface geologic formations could unintentionally lead to CO 2 leakage into overlying freshwater aquifers. Introduction of CO 2 into these subsurface environments will greatly increase the CO 22 concentration and will create CO 2 concentration gradients that drivemore » changes in the microbial communities present. While it is expected that altered microbial communities will impact the biogeochemistry of the subsurface, there is no information available on how CO 2 gradients will impact these communities. The overarching goal of this project is to understand how CO 2 exposure will impact subsurface microbial communities at temperatures and pressures that are relevant to GCS and CO 2 leakage scenarios. To meet this goal, unfiltered, aqueous samples from a deep saline aquifer, a depleted oil reservoir, and a fresh water aquifer were exposed to varied concentrations of CO 2 at reservoir pressure and temperature. The microbial ecology of the samples was examined using molecular, DNA-based techniques. The results from these studies were also compared across the sites to determine any existing trends. Results reveal that increasing CO 2 leads to decreased DNA concentrations regardless of the site, suggesting that microbial processes will be significantly hindered or absent nearest the CO 2 injection/leakage plume where CO 2 concentrations are highest. At CO 2 exposures expected downgradient from the CO 2 plume, selected microorganisms emerged as dominant in the CO 2 exposed conditions. Results suggest that the altered microbial community was site specific and highly dependent on pH. The site-dependent results suggest a limited ability to predict the emerging dominant species for other CO 2 exposed environments. This study improves the understanding of how a subsurface microbial community may respond to conditions expected from GCS and CO 2 leakage. This is the first step for understanding how a CO 2-altered microbial community may impact injectivity, permanence of stored CO 2, and subsurface water quality. Future work with microbial communities from new subsurface sites would increase the current understanding of this project. Additionally, incorporation of metagenomic methods would increase understanding of potential microbial processes that may be prevalent in CO 2 exposed environments.« less

Investigating the Hydro-geochemical Impact of Fugitive Methane on Groundwater: The Borden Aquifer Controlled Release Study

NASA Astrophysics Data System (ADS)

Cahill, A. G.; Parker, B. L.; Cherry, J. A.; Mayer, K. U.; Mayer, B.; Ryan, C.

2014-12-01

Shale gas development by hydraulic fracturing is believed by many to have the potential to transform the world's energy economy. The propensity of this technique to cause significant environmental impact is strongly contested and lacks evidence. Fugitive methane (CH4), potentially mobilized during well drilling, the complex extraction process and/or leaking well seals over time is arguably the greatest concern. Advanced understanding of CH4 mobility and fate in the subsurface is needed in order to assess risks, design suitable monitoring systems and gain public trust. Currently knowledge on subsurface CH4 mobilization and migration at scales relevant to shale gas development is lacking. Consequently a shallow aquifer controlled CH4 release experiment is being conducted at the Borden aquifer research facility (an unconfined, unconsolidated silicate sand aquifer) in Ontario, Canada. During the experiment, 100 m3 of gas phase CH4 was injected into the saturated zone over approximately 60 days through 2 inclined sparging wells (4.5 and 9 m depth) at rates relevant to natural gas well casing vent flows. The gas mobility and fate is being comprehensively monitored temporally and spatially in both the saturated and unsaturated zones considering; aqueous chemistry (including stable isotopes), soil gas characterization, surface efflux, geophysics (GPR and ERT), real time sensors (total dissolved gas pressure, soil moisture content, CH4 and CO2), mineralogical and microbiological characterization before, during and after injection. An overview of this unique study will be given including experimental design, monitoring system configuration and preliminary results. This multidisciplinary study will provide important insights regarding the mechanisms and rates for shallow CH4 migration, attenuation and water quality impacts that will inform baseline groundwater monitoring programs and retrospective forensic studies.

Investigating the Hydro-geochemical Impact of Fugitive Methane on Groundwater: The Borden Aquifer Controlled Release Study

NASA Astrophysics Data System (ADS)

Cahill, A. G.; Parker, B. L.; Cherry, J. A.; Mayer, K. U.; Mayer, B.; Ryan, C.

2015-12-01

Shale gas development by hydraulic fracturing is believed by many to have the potential to transform the world's energy economy. The propensity of this technique to cause significant environmental impact is strongly contested and lacks evidence. Fugitive methane (CH4), potentially mobilized during well drilling, the complex extraction process and/or leaking well seals over time is arguably the greatest concern. Advanced understanding of CH4 mobility and fate in the subsurface is needed in order to assess risks, design suitable monitoring systems and gain public trust. Currently knowledge on subsurface CH4 mobilization and migration at scales relevant to shale gas development is lacking. Consequently a shallow aquifer controlled CH4 release experiment is being conducted at the Borden aquifer research facility (an unconfined, unconsolidated silicate sand aquifer) in Ontario, Canada. During the experiment, 100 m3 of gas phase CH4 was injected into the saturated zone over approximately 60 days through 2 inclined sparging wells (4.5 and 9 m depth) at rates relevant to natural gas well casing vent flows. The gas mobility and fate is being comprehensively monitored temporally and spatially in both the saturated and unsaturated zones considering; aqueous chemistry (including stable isotopes), soil gas characterization, surface efflux, geophysics (GPR and ERT), real time sensors (total dissolved gas pressure, soil moisture content, CH4 and CO2), mineralogical and microbiological characterization before, during and after injection. An overview of this unique study will be given including experimental design, monitoring system configuration and preliminary results. This multidisciplinary study will provide important insights regarding the mechanisms and rates for shallow CH4 migration, attenuation and water quality impacts that will inform baseline groundwater monitoring programs and retrospective forensic studies.

Genome-to-Watershed Predictive Understanding of Terrestrial Environments

NASA Astrophysics Data System (ADS)

Hubbard, S. S.; Agarwal, D.; Banfield, J. F.; Beller, H. R.; Brodie, E.; Long, P.; Nico, P. S.; Steefel, C. I.; Tokunaga, T. K.; Williams, K. H.

2014-12-01

Although terrestrial environments play a critical role in cycling water, greenhouse gasses, and other life-critical elements, the complexity of interactions among component microbes, plants, minerals, migrating fluids and dissolved constituents hinders predictive understanding of system behavior. The 'Sustainable Systems 2.0' project is developing genome-to-watershed scale predictive capabilities to quantify how the microbiome affects biogeochemical watershed functioning, how watershed-scale hydro-biogeochemical processes affect microbial functioning, and how these interactions co-evolve with climate and land-use changes. Development of such predictive capabilities is critical for guiding the optimal management of water resources, contaminant remediation, carbon stabilization, and agricultural sustainability - now and with global change. Initial investigations are focused on floodplains in the Colorado River Basin, and include iterative model development, experiments and observations with an early emphasis on subsurface aspects. Field experiments include local-scale experiments at Rifle CO to quantify spatiotemporal metabolic and geochemical responses to O2and nitrate amendments as well as floodplain-scale monitoring to quantify genomic and biogeochemical response to natural hydrological perturbations. Information obtained from such experiments are represented within GEWaSC, a Genome-Enabled Watershed Simulation Capability, which is being developed to allow mechanistic interrogation of how genomic information stored in a subsurface microbiome affects biogeochemical cycling. This presentation will describe the genome-to-watershed scale approach as well as early highlights associated with the project. Highlights include: first insights into the diversity of the subsurface microbiome and metabolic roles of organisms involved in subsurface nitrogen, sulfur and hydrogen and carbon cycling; the extreme variability of subsurface DOC and hydrological controls on carbon and nitrogen cycling; geophysical identification of floodplain hotspots that are useful for model parameterization; and GEWaSC demonstration of how incorporation of identified microbial metabolic processes improves prediction of the larger system biogeochemical behavior.

Pathways and transformations of dissolved methane and dissolved inorganic carbon in Arctic tundra watersheds: Evidence from analysis of stable isotopes

DOE PAGES

Throckmorton, Heather M.; Heikoop, Jeffrey M.; Newman, Brent D.; ...

2015-11-08

Arctic soils contain a large pool of terrestrial C and are of interest due to their potential for releasing significant carbon dioxide (CO 2) and methane (CH 4) to the atmosphere. Due to substantial landscape heterogeneity, predicting ecosystem-scale CH 4 and CO 2 production is challenging. This study assessed dissolved inorganic carbon (DIC = Σ (total) dissolved CO 2) and CH 4 in watershed drainages in Barrow, Alaska as critical convergent zones of regional geochemistry, substrates, and nutrients. In July and September of 2013, surface waters and saturated subsurface pore waters were collected from 17 drainages. Based on simultaneous DICmore » and CH 4 cycling, we synthesized isotopic and geochemical methods to develop a subsurface CH 4 and DIC balance by estimating mechanisms of CH 4 and DIC production and transport pathways and oxidation of subsurface CH 4. We observed a shift from acetoclastic (July) toward hydrogenotropic (September) methanogenesis at sites located toward the end of major freshwater drainages, adjacent to salty estuarine waters, suggesting an interesting landscape-scale effect on CH 4 production mechanism. The majority of subsurface CH 4 was transported upward by plant-mediated transport and ebullition, predominantly bypassing the potential for CH 4 oxidation. Thus, surprisingly, CH 4 oxidation only consumed approximately 2.51± 0.82% (July) and 0.79 ± 0.79% (September) of CH 4 produced at the frost table, contributing to <0.1% of DIC production. DIC was primarily produced from respiration, with iron and organic matter serving as likely e- acceptors. Furthermore, this work highlights the importance of spatial and temporal variability of CH 4 production at the watershed scale and suggests broad scale investigations are required to build better regional or pan-Arctic representations of CH 4 and CO 2 production.« less

Microbial production and oxidation of methane in deep subsurface

NASA Astrophysics Data System (ADS)

Kotelnikova, Svetlana

2002-10-01

The goal of this review is to summarize present studies on microbial production and oxidation of methane in the deep subterranean environments. Methane is a long-living gas causing the "greenhouse" effect in the planet's atmosphere. Earlier, the deep "organic carbon poor" subsurface was not considered as a source of "biogenic" methane. Evidence of active methanogenesis and presence of viable methanogens including autotrophic organisms were obtained for some subsurface environments including water-flooded oil-fields, deep sandy aquifers, deep sea hydrothermal vents, the deep sediments and granitic groundwater at depths of 10 to 2000 m below sea level. As a rule, the deep subterranean microbial populations dwell at more or less oligotrophic conditions. Molecular hydrogen has been found in a variety of subsurface environments, where its concentrations were significantly higher than in the tested surface aquatic environments. Chemolithoautotrophic microorganisms from deep aquifers that could grow on hydrogen and carbon dioxide can act as primary producers of organic carbon, initiating heterotrophic food chains in the deep subterranean environments independent of photosynthesis. "Biogenic" methane has been found all over the world. On the basis of documented occurrences, gases in reservoirs and older sediments are similar and have the isotopic character of methane derived from CO 2 reduction. Groundwater representing the methanogenic end member are characterized by a relative depletion of dissolved organic carbon (DOC) in combination with an enrichment in 13C in inorganic carbon, which is consistent with the preferential reduction of 12CO 2 by autotrophic methanogens or acetogens. The isotopic composition of methane formed via CO 2 reduction is controlled by the δ13C of the original CO 2 substrate. Literature data shows that CH 4 as heavy as -40‰ or -50‰ can be produced by the microbial reduction of isotopically heavy CO 2. Produced methane may be oxidized microbially to carbon dioxide. Microbial methane oxidation is a biogeochemical process that limits the release of methane, a greenhouse gas from anaerobic environments. Anaerobic methane oxidation plays an important role in marine sediments. Similar processes may take place in deep subsurface and thus fuel the deep microbial community. Organisms or consortia responsible for anaerobic methane oxidation have not yet been cultured, although diverse aerobic methanotrophs have been isolated from a variety of underground niches. The presence of aerobic methanotrophs in the anoxic subsurface remains to be explained. The presence of methane in the deep subsurface have been shown all over the world. The flux of gases between the deep subsurface and the atmosphere is driven by the concentration gradient from depth to the atmosphere. However, methane is consumed by methanotrophs on the way of its evolution in oxidized environments and is transformed to organic form, available for further microbial processing. When the impact of subsurface environments to global warming is estimated, it is necessary to take into account the activity of methane-producing Archaea and methane-oxidizing biofilters in groundwater. Microbial production and oxidation of methane is involved in the carbon cycle in the deep subsurface environments.

An experimental study of basaltic glass-H2O-CO2 interaction at 22 and 50 °C: Implications for subsurface storage of CO2

NASA Astrophysics Data System (ADS)

Galeczka, Iwona; Wolff-Boenisch, Domenik; Oelkers, Eric H.; Gislason, Sigurdur R.

2014-02-01

A novel high pressure column flow reactor was used to investigate the evolution of solute chemistry along a 2.3 m flow path during pure water- and CO2-charged water-basaltic glass interaction experiments at 22 and 50 °C and 10-5.7 to 22 bars partial pressure of CO2. Experimental results and geochemical modelling showed the pH of injected pure water evolved rapidly from 6.7 to 9-9.5 and most of the iron released to the fluid phase was subsequently consumed by secondary minerals, similar to natural meteoric water-basalt systems. In contrast to natural systems, however, the aqueous aluminium concentration remained relatively high along the entire flow path. The aqueous fluid was undersaturated with respect to basaltic glass and carbonate minerals, but supersaturated with respect to zeolites, clays, and Fe hydroxides. As CO2-charged water replaced the alkaline fluid within the column, the fluid briefly became supersaturated with respect to siderite. Basaltic glass dissolution in the column reactor, however, was insufficient to overcome the pH buffer capacity of CO2-charged water. The pH of this CO2-charged water rose from an initial 3.4 to only 4.5 in the column reactor. This acidic reactive fluid was undersaturated with respect to carbonate minerals but supersaturated with respect to clays and Fe hydroxides at 22 °C, and with respect to clays and Al hydroxides at 50 °C. Basaltic glass dissolution in the CO2-charged water was closer to stoichiometry than in pure water. The mobility and aqueous concentration of several metals increased significantly with the addition of CO2 to the inlet fluid, and some metals, including Mn, Cr, Al, and As exceeded the allowable drinking water limits. Iron became mobile and the aqueous Fe2+/Fe3+ ratio increased along the flow path. Although carbonate minerals did not precipitate in the column reactor in response to CO2-charged water-basaltic glass interaction, once this fluid exited the reactor, carbonates precipitated as the fluid degassed at the outlet. Substantial differences were found between the results of geochemical modelling calculations and the observed chemical evolution of the fluids during the experiments. These differences underscore the need to improve the models before they can be used to predict with confidence the fate and consequences of carbon dioxide injected into the subsurface. The pH increase from 3.4 to 4.5 of the CO2-rich inlet fluid does not immobilize toxic elements at ambient temperature but immobilizes Al and Cr at 50 °C. This indicates that further neutralization of CO2-charged water is required for decreased toxic element mobility. The CO2-charged water injection enhances the mobility of redox sensitive Fe2+ significantly making it available for the storage of injected carbon as iron carbonate minerals. The precipitation of aluminosilicates likely occurred at a pH of 4.2-4.5 in CO2-charged waters. These secondary phases can (1) fill the available pore space and therefore clog the host rock in the vicinity of the injection well, and (2) incorporate some divalent cations limiting their availability for carbon storage. The inability of simple reactive transport models to describe accurately the fluid evolution in this well constrained one dimensional flow system suggests that significant improvements need to be made to such models before we can predict with confidence the fate and consequences of injecting carbon dioxide into the subsurface. Column reactors such as that used in this study could be used to facilitate ex situ carbon mineral storage. Carbonate precipitation at the outlet of the reactor suggests that the harvesting of divalent metals from rocks using CO2-charged waters could potentially be upscaled to an industrial carbonation process.

SUBSURFACE PROPERTY RIGHTS: IMPLICATIONS FOR GEOLOGIC CO2 STORAGE

EPA Science Inventory

The paper discusses subsurface property rights as they apply to geologic sequestration (GS) of carbon dioxide (CO2). GS projects inject captured CO2 into deep (greater than ~1 km) geologic formations for the explicit purpose of avoiding atmospheric emission of CO2. Because of the...

SUBSURFACE PROPERTY RIGHTS: IMPLICATIONS FOR GEOLOGIC CO2 SEQUESTRATION

EPA Science Inventory

The chapter discusses subsurface property rights as they apply to geologic sequestration (GS) of carbon dioxide (CO2). GS projects inject captured CO2 into deep (greater than ~1 km) geologic formations for the explicit purpose of avoiding atmospheric emission of CO2. Because of t...

The Monitoring of Sallow CO2 Leakage From the CO2 Release Experiment in South Korea

NASA Astrophysics Data System (ADS)

Kim, H. J.; Han, S. H.; Kim, S.; Son, Y.

2017-12-01

This study was conducted to analyze the in-soil CO2 gas diffusion from the K-COSEM shallow CO2 release experiment. The study site consisting of five zones was built in Eumseong, South Korea, and approximately 1.8 t CO2 were injected from the perforated release well at Zones 1 to 4 from June 1 to 30, 2016. In-soil CO2 concentrations were measured once a day at 15 cm and 60 cm depths at 0 m, 2.5 m, 5.0 m, and 10.0 m away from the CO2 releasing well using a portable gas analyzer (GA5000) from May 11 to July 27, 2016. On June 4, CO2 leakage was simultaneously detected at 15 cm (8.8 %) and 60 cm (44.0 %) depths at 0 m from the well at Zone 3, and were increased up to about 30 % and 70 %, respectively. During the CO2 injection period, CO2 concentrations measured at 15 cm depth were significantly lower than those measured at 60 cm depth because of the atmospheric pressure effect. After stopping the CO2 injection, CO2 concentrations gradually decreased until July 27, but were still higher than the natural background concentration. This result suggested the possibility of long-term CO2 leakage. In addition, low levels of CO2 leakage were determined using CO2 regression analysis and CO2:O2 ratio. CO2 concentrations measured at 60 cm depth at 0 m from the well at Zones 1 to 4 consistently showed sigmoid increasing patterns with the injection time (R2=0.60-0.99). O2 concentrations at 15 cm and 60 cm depths from the CO2 release experiment were reached 0 % at about 76 % and 84 % of CO2 concentrations, respectively, whereas, those from biological reaction approached 0 % when CO2 increased to about 21 %. Therefore, deep underground monitoring would be able to detect CO2 leakage faster than near-surface monitoring, and CO2 regression and CO2:O2 ratio analyses seemed to be useful as clear indicators of CO2 leakage.

ESTIMATION OF NEAR SUBSURFACE COAL FIRE GAS EMISSIONS BASED ON GEOPHYSICAL INVESTIGATIONS

NASA Astrophysics Data System (ADS)

Chen-Brauchler, D.; Meyer, U.; Schlömer, S.; Kus, J.; Gundelach, V.; Wuttke, M.; Fischer, C.; Rueter, H.

2009-12-01

Spontaneous and industrially caused subsurface coal fires are worldwide disasters that destroy coal resources, cause air pollution and emit a large amount of green house gases. Especially in developing countries, such as China, India and Malaysia, this problem has intensified over the last 15 years. In China alone, 10 to 20 million tons of coal are believed to be lost in uncontrolled coal fires. The cooperation of developing countries and industrialized countries is needed to enforce internationally concerted approaches and political attention towards the problem. The Clean Development Mechanism (CDM) under the framework of the Kyoto Protocol may provide an international stage for financial investment needed to fight the disastrous situation. A Sino-German research project for coal fire exploration, monitoring and extinction applied several geophysical approaches in order to estimate the annual baseline especially of CO2 emissions from near subsurface coal fires. As a result of this project, we present verifiable methodologies that may be used in the CDM framework to estimate the amount of CO2 emissions from near subsurface coal fires. We developed three possibilities to approach the estimation based on (1) thermal energy release, (2) geological and geometrical determinations as well as (3) direct gas measurement. The studies involve the investigation of the physical property changes of the coal seam and bedrock during different burning stages of a underground coal fire. Various geophysical monitoring methods were applied from near surface to determine the coal volume, fire propagation, temperature anomalies, etc.

FIELD-DRIVEN APPROACHES TO SUBSURFACE CONTAMINANT TRANSPORT MODELING.

EPA Science Inventory

Observations from field sites provide a means for prioritizing research activities. In the case of petroleum releases, observations may include spiking of concentration distributions that may be related to water table fluctuation, co-location of contaminant plumes with geochemi...

SUBSURFACE PROPERTY RIGHTS: IMPLICATIONS FOR GEOLOGIC CO2 SEQUESTRATION (PRESENTATION)

EPA Science Inventory

The paper discusses subsurface property rights as they apply to geologic sequestration (GS) of carbon dioxide (CO2). GS projects inject captured CO2 into deep (greater than ~1 km) geologic formations for the explicit purpose of avoiding atmospheric emission of CO2. Because of the...

Microbial monitoring during CO2 storage in deep subsurface saline aquifers in Ketzin, Germany

NASA Astrophysics Data System (ADS)

Wuerdemann, H.; Wandrey, M.; Fischer, S.; Zemke, K.; Let, D.; Zettlitzer, M.; Morozova, D.

2010-12-01

Investigations on subsurface saline aquifers have shown an active biosphere composed of diverse groups of microorganisms in the subsurface. Since microorganisms represent very effective geochemical catalysts, they may influence the process of CO2 storage significantly. In the frames of the EU Project CO2SINK a field laboratory to study CO2 storage into saline aquifer was operated. Our studies aim at monitoring of biological and biogeochemical processes and their impact on the technical effectiveness of CO2 storage technique. The interactions between microorganisms and the minerals of both the reservoir and the cap rock may cause changes to the structure and chemical composition of the rock formations, which may influence the reservoir permeability locally. In addition, precipitation and corrosion may be induced around the well affecting the casing and the casing cement. Therefore, analyses of the composition of microbial communities and its changes should contribute to an evaluation of the effectiveness and reliability of the long-term CO2 storage technique. In order to investigate processes in the deep biosphere caused by the injection of supercritical CO2, genetic fingerprinting (PCR SSCP Single-Strand-Conformation Polymorphism) and FISH (Fluorescence in situ Hybridisation) were used for identification and quantification of microorganisms. Although saline aquifers could be characterised as an extreme habitat for microorganisms due to reduced conditions, high pressure and salinity, a high number of diverse groups of microorganisms were detected with downhole sampling in the injection and observation wells at a depth of about 650m depth. Of great importance was the identification of the sulphate reducing bacteria, which are known to be involved in corrosion processes. Microbial monitoring during CO2 injection has shown that both quantity and diversity of microbial communities were strongly influenced by the CO2 injection. In addition, the indigenous microbial communities revealed a high adaptability to the changed environments after CO2 injection. In order to investigate processes in the rock substrate, long term CO2 exposure experiments on freshly drilled, pristine Ketzin reservoir core samples were accomplished for 24 months using sterile synthetic brine under in situ pressure and temperature conditions. The composition of the microbial community dominated by chemoorganotrophic bacteria and hydrogen oxidizing bacteria changed slightly under CO2 exposure. In addition, changes in porosities were observed with time. During the experiments porosity first increased due to mineral dissolution but then tend to decrease due to mineral precipitation. These mineralogical changes are consistent with changes in fluid composition during the course of the experiments that indicate notably increased K+, Ca2+, Mg2+, and SO4 2- concentrations. K+, Ca2+, Mg2+ concentrations exceeded the reservoir brine composition significantly and can be attributed to the CO2 exposure.

Rates of CO2 Mineralization in Geological Carbon Storage.

PubMed

Zhang, Shuo; DePaolo, Donald J

2017-09-19

Geologic carbon storage (GCS) involves capture and purification of CO 2 at industrial emission sources, compression into a supercritical state, and subsequent injection into geologic formations. This process reverses the flow of carbon to the atmosphere with the intention of returning the carbon to long-term geologic storage. Models suggest that most of the injected CO 2 will be "trapped" in the subsurface by physical means, but the most risk-free and permanent form of carbon storage is as carbonate minerals (Ca,Mg,Fe)CO 3 . The transformation of CO 2 to carbonate minerals requires supply of the necessary divalent cations by dissolution of silicate minerals. Available data suggest that rates of transformation are highly uncertain and difficult to predict by standard approaches. Here we show that the chemical kinetic observations and experimental results, when they can be reduced to a single cation-release time scale that describes the fractional rate at which cations are released to solution by mineral dissolution, show sufficiently systematic behavior as a function of pH, fluid flow rate, and time that the rates of mineralization can be estimated with reasonable certainty. The rate of mineralization depends on both the abundance (determined by the reservoir rock mineralogy) and the rate at which cations are released from silicate minerals by dissolution into pore fluid that has been acidified with dissolved CO 2 . Laboratory-measured rates and field observations give values spanning 8 to 10 orders of magnitude, but when they are evaluated in the context of a reservoir-scale reactive transport simulation, this range becomes much smaller. The reservoir scale simulations provide limits on the applicable conditions under which silicate mineral dissolution and subsequent carbonate mineral precipitation are likely to occur (pH 4.5 to 6, fluid flow velocity less than 5 m/year, and 50-100 years or more after the start of injection). These constraints lead to estimates of 200 to 2000 years for conversion of 60-90% of injected CO 2 when the reservoir rock has a sufficient volume fraction of divalent cation-bearing silicate minerals and confirms that when reservoir rock mineralogy is not favorable the fraction of CO 2 converted to carbonate minerals is minimal over 10 4 years. A sufficient amount of reactive minerals is typically about 20% by volume. Our approach may allow for rapid evaluation of mineralization potential of subsurface storage reservoirs and illustrates how reservoir scale modeling can be integrated with other observations to address key issues relating to engineering of geologic systems.

Assessing Induced Seismicity Risk at CO 2 Storage Projects: Recent Progress and Remaining Challenges

DOE PAGES

White, Joshua A.; Foxall, William

2016-04-13

It is well established that fluid injection has the potential to induce earthquakes—from microseismicity to magnitude 5+ events—by altering state-of-stress conditions in the subsurface. This paper reviews recent lessons learned regarding induced seismicity at carbon storage sites. While similar to other subsurface injection practices, CO 2 injection has distinctive features that should be included in a discussion of its seismic hazard. Induced events have been observed at CO 2 injection projects, though to date it has not been a major operational issue. Nevertheless, the hazard exists and experience with this issue will likely grow as new storage operations come online.more » This review paper focuses on specific technical difficulties that can limit the effectiveness of current risk assessment and risk management approaches, and highlights recent research aimed at overcoming them. Finally, these challenges form the heart of the induced seismicity problem, and novel solutions to them will advance our ability to responsibly deploy large-scale CO 2 storage.« less

Intermediate-Scale Experimental Study to Improve Fundamental Understanding of Attenuation Capacity for Leaking CO2 in Heterogeneous Shallow Aquifers

NASA Astrophysics Data System (ADS)

Plampin, Michael R.; Porter, Mark L.; Pawar, Rajesh J.; Illangasekare, Tissa H.

2017-12-01

To assess the risks of Geologic Carbon Sequestration (GCS), it is crucial to understand the fundamental physicochemical processes that may occur if and when stored CO2 leaks upward from a deep storage reservoir into the shallow subsurface. Intermediate-scale experiments allow for improved understanding of the multiphase evolution processes that control CO2 migration behavior in the subsurface, because the boundary conditions, initial conditions, and porous media parameters can be better controlled and monitored in the laboratory than in field settings. For this study, a large experimental test bed was designed to mimic a cross section of a shallow aquifer with layered geologic heterogeneity. As water with aqueous CO2 was injected into the system to mimic a CO2-charged water leakage scenario, the spatiotemporal evolution of the multiphase CO2 plume was monitored. Similar experiments were performed with two different sand combinations to assess the relative effects of different types of geologic facies transitions on the CO2 evolution processes. Significant CO2 attenuation was observed in both scenarios, but by fundamentally different mechanisms. When the porous media layers had very different permeabilities, attenuation was caused by local accumulation (structural trapping) and slow redissolution of gas phase CO2. When the permeability difference between the layers was relatively small, on the other hand, gas phase continually evolved over widespread areas near the leading edge of the aqueous plume, which also attenuated CO2 migration. This improved process understanding will aid in the development of models that could be used for effective risk assessment and monitoring programs for GCS projects.

Intermediate-Scale Experimental Study to Improve Fundamental Understanding of Attenuation Capacity for Leaking CO 2 in Heterogeneous Shallow Aquifers

DOE PAGES

Plampin, Michael R.; Porter, Mark L.; Pawar, Rajesh J.; ...

2017-11-15

In order to assess the risks of Geologic Carbon Sequestration (GCS), it is crucial to understand the fundamental physicochemical processes that may occur if and when stored CO 2 leaks upward from a deep storage reservoir into the shallow subsurface. Intermediate-scale experiments allow for improved understanding of the multiphase evolution processes that control CO 2 migration behaviour in the subsurface, because the boundary conditions, initial conditions, and porous media parameters can be better controlled and monitored in the laboratory than in field settings. For this study, a large experimental test bed was designed to mimic a cross-section of a shallowmore » aquifer with layered geologic heterogeneity. As water with aqueous CO 2 was injected into the system to mimic a CO 2-charged water leakage scenario, the spatiotemporal evolution of the multiphase CO 2 plume was monitored. Similar experiments were performed with two different sand combinations to assess the relative effects of different types of geologic facies transitions on the CO 2 evolution processes. Significant CO 2 attenuation was observed in both scenarios, but by fundamentally different mechanisms. When the porous media layers had very different permeabilities, attenuation was caused by local accumulation (structural trapping) and slow re-dissolution of gas phase CO 2. When the permeability difference between the layers was relatively small, on the other hand, gas phase continually evolved over widespread areas near the leading edge of the aqueous plume, which also attenuated CO 2 migration. In conclusion, this improved process understanding will aid in the development of models that could be used for effective risk assessment and monitoring programs for GCS projects.« less

Intermediate-Scale Experimental Study to Improve Fundamental Understanding of Attenuation Capacity for Leaking CO 2 in Heterogeneous Shallow Aquifers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Plampin, Michael R.; Porter, Mark L.; Pawar, Rajesh J.

In order to assess the risks of Geologic Carbon Sequestration (GCS), it is crucial to understand the fundamental physicochemical processes that may occur if and when stored CO 2 leaks upward from a deep storage reservoir into the shallow subsurface. Intermediate-scale experiments allow for improved understanding of the multiphase evolution processes that control CO 2 migration behaviour in the subsurface, because the boundary conditions, initial conditions, and porous media parameters can be better controlled and monitored in the laboratory than in field settings. For this study, a large experimental test bed was designed to mimic a cross-section of a shallowmore » aquifer with layered geologic heterogeneity. As water with aqueous CO 2 was injected into the system to mimic a CO 2-charged water leakage scenario, the spatiotemporal evolution of the multiphase CO 2 plume was monitored. Similar experiments were performed with two different sand combinations to assess the relative effects of different types of geologic facies transitions on the CO 2 evolution processes. Significant CO 2 attenuation was observed in both scenarios, but by fundamentally different mechanisms. When the porous media layers had very different permeabilities, attenuation was caused by local accumulation (structural trapping) and slow re-dissolution of gas phase CO 2. When the permeability difference between the layers was relatively small, on the other hand, gas phase continually evolved over widespread areas near the leading edge of the aqueous plume, which also attenuated CO 2 migration. In conclusion, this improved process understanding will aid in the development of models that could be used for effective risk assessment and monitoring programs for GCS projects.« less

Surface Degassing Rates of Carbon Dioxide, Helium and Hydrogen at Tenerife, Canary Islands

NASA Astrophysics Data System (ADS)

Salazar, P.; Morales, A.; Lima, R.; Castro, L.; Galindo, I.; Salazar, J.; Hernandez, P.; Perez, N.

2001-12-01

Tenerife is the largest island of the Canarian archipelago (2,034 Km2), and its most recent eruption took place along the NW rift-zone in 1909, Chinyero volcano. Water supply is mainly obtained from its ground water reservoir which is reached by thousands of well and galleries. Some galleries showed an enriched-CO2 inner atmosphere because of a continuous magmatic degassing process, which is also affecting the ground water chemistry. Gas emission studies through galleries could provide a 3-D picture of the degassing model for Tenerife. An in situ method was applied for measuring CO2, He and H2 fluxes from a horizontal drilling "gallery" by means of a tracer gas method. Methane (99.995%) was applied as a tracer and injected into the gallery "Fuente del Valle" at known flow, 38 mL/min. Well mixed gas and tracer were regularly analyzed, every 5 minutes, by means of a VARIAN 2002P microGC from April 27 to May 2, 2000. CO2 and CH4 measurements were performed by means of a 10 m Poraplot Q column at 40° C, a TCD, and He as gas carrier. He, Ne and H2 measurements were analyzed by means of a 20 m high resolution Molecular Sieve 5Å column at 60° C, a TCD, and Ar as gas carrier. (CH4)gas/(CH4)air ratio was >1000 during this experiment. CO2 concentrations seem to be affected by short-term meteorological fluctuations and showed a range from 23 to 30%. An strong correlation is observed between CO2 content and He/Ne ratios, which ranged from 0.320 to 0.390. CO2 flux ranged from 1.5 to 5.5 Kg/d showing an average of 2.9 +/- 0.7 Kg/d. Secular variations of CO2 flux showed regularly peak levels almost every 12 hours. Assuming that a number of 100 galleries at Tenerife might release this level of CO2, the island subsurface degassing rate of CO2 could account for 300 Kg/d. Observed He flux ranged 2.8 to 9.0 mg/d showing an average of 5.0 +/- 1.2 mg/d. In the case of H2, flux levels ranged from 2.5 to 7.0 mg/d showing an average of 4.5 +/- 0.9 mg/d. Subsurface degassing rate monitoring could be a potential geochemical tool for seismic-volcanic surveillance at Tenerife.

The response of abyssal organisms to low pH conditions during a series of CO2-release experiments simulating deep-sea carbon sequestration

NASA Astrophysics Data System (ADS)

Barry, J. P.; Buck, K. R.; Lovera, C.; Brewer, P. G.; Seibel, B. A.; Drazen, J. C.; Tamburri, M. N.; Whaling, P. J.; Kuhnz, L.; Pane, E. F.

2013-08-01

The effects of low-pH, high-pCO2 conditions on deep-sea organisms were examined during four deep-sea CO2 release experiments simulating deep-ocean C sequestration by the direct injection of CO2 into the deep sea. We examined the survival of common deep-sea, benthic organisms (microbes; macrofauna, dominated by Polychaeta, Nematoda, Crustacea, Mollusca; megafauna, Echinodermata, Mollusca, Pisces) exposed to low-pH waters emanating as a dissolution plume from pools of liquid carbon dioxide released on the seabed during four abyssal CO2-release experiments. Microbial abundance in deep-sea sediments was unchanged in one experiment, but increased under environmental hypercapnia during another, where the microbial assemblage may have benefited indirectly from the negative impact of low-pH conditions on other taxa. Lower abyssal metazoans exhibited low survival rates near CO2 pools. No urchins or holothurians survived during 30-42 days of exposure to episodic, but severe environmental hypercapnia during one experiment (E1; pH reduced by as much as ca. 1.4 units). These large pH reductions also caused 75% mortality for the deep-sea amphipod, Haploops lodo, near CO2 pools. Survival under smaller pH reductions (ΔpH<0.4 units) in other experiments (E2, E3, E5) was higher for all taxa, including echinoderms. Gastropods, cephalopods, and fish were more tolerant than most other taxa. The gastropod Retimohnia sp. and octopus Benthoctopus sp. survived exposure to pH reductions that episodically reached -0.3 pH units. Ninety percent of abyssal zoarcids (Pachycara bulbiceps) survived exposure to pH changes reaching ca. -0.3 pH units during 30-42 day-long experiments.

Phosphorus Release to Floodwater from Calcareous Surface Soils and Their Corresponding Subsurface Soils under Anaerobic Conditions.

PubMed

Jayarathne, P D K D; Kumaragamage, D; Indraratne, S; Flaten, D; Goltz, D

2016-07-01

Enhanced phosphorus (P) release from soils to overlying water under flooded, anaerobic conditions has been well documented for noncalcareous and surface soils, but little information is available for calcareous and subsurface soils. We compared the magnitude of P released from 12 calcareous surface soils and corresponding subsurface soils to overlying water under flooded, anaerobic conditions and examined the reasons for the differences. Surface (0-15 cm) and subsurface (15-30 cm) soils were packed into vessels and flooded for 8 wk. Soil redox potential and concentrations of dissolved reactive phosphorus (DRP) and total dissolved Ca, Mg, Fe, and Mn in floodwater and pore water were measured weekly. Soil test P was significantly smaller in subsurface soils than in corresponding surface soils; thus, the P release to floodwater from subsurface soils was significantly less than from corresponding surface soils. Under anaerobic conditions, floodwater DRP concentration significantly increased in >80% of calcareous surface soils and in about 40% of subsurface soils. The increase in floodwater DRP concentration was 2- to 17-fold in surface soils but only 4- to 7-fold in subsurface soils. With time of flooding, molar ratios of Ca/P and Mg/P in floodwater increased, whereas Fe/P and Mn/P decreased, suggesting that resorption and/or reprecipitation of P took place involving Fe and Mn. Results indicate that P release to floodwater under anaerobic conditions was enhanced in most calcareous soils. Surface and subsurface calcareous soils in general behaved similarly in releasing P under flooded, anaerobic conditions, with concentrations released mainly governed by initial soil P concentrations. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Investigation of CO2 release pressures in pipeline cracks

NASA Astrophysics Data System (ADS)

Gorenz, Paul; Herzog, Nicoleta; Egbers, Christoph

2013-04-01

The CCS (Carbon Capture and Storage) technology can prevent or reduce the emissions of carbon dioxide. The main idea of this technology is the segregation and collection of CO2 from facilities with a high emission of that greenhouse gas, i.e. power plants which burn fossil fuels. To segregate CO2 from the exhaust gas the power plant must be upgraded. Up to now there are three possible procedures to segregate the carbon dioxide with different advantages and disadvantages. After segregation the carbon dioxide will be transported by pipeline to a subsurface storage location. As CO2 is at normal conditions (1013,25 Pa; 20 °C) in a gaseous phase state it must be set under high pressure to enter denser phase states to make a more efficient pipeline transport possible. Normally the carbon dioxide is set into the liquid or supercritical phase state by compressor stations which compress the gas up to 15 MPa. The pressure drop makes booster stations along the pipeline necessary which keep the CO2 in a dens phase state. Depending on the compression pressure CO2 can be transported over 300km without any booster station. The goal of this work is the investigation of release pressures in pipeline cracks. The high pressurised pipeline system consists of different parts with different failure probabilities. In most cases corrosion or obsolescence is the reason for pipeline damages. In case of a crack CO2 will escape from the pipeline and disperse into the atmosphere. Due to its nature CO2 can remain unattended for a long time. There are some studies of the CO2 dispersion process, e.g. Mazzoldi et al. (2007, 2008 and 2011) and Wang et al. (2008), but with different assumptions concerning the pipeline release pressures. To give an idea of realistic release pressures investigations with the CFD tool OpenFOAM were carried out and are presented within this work. To cover such a scenario with an accidental release of carbon dioxide a pipeline section with different diameters and leakage release holes were modelled. This pipeline section is 10m long with the leakage hole in the middle. Additionally a small environment subdomain is simulated around the crack. For computation a multiphase solver was utilised. In a first step incompressible and isothermal fluids with no phase change were assumed.

Ocean Data Assimilation Systems for GODAE

DTIC Science & Technology

2009-09-01

we describe some of the ocean data assimilation systems that have been developed within the Global Ocean Data Assimilation Experiment (GODAE...assimilation systems in the post-GODAF. time period beyond 2008. 15. SUBJECT TERMS Global Ocean Data Assimilation Experiment, ARGO, subsurface...E. R. Franchi , 7000 Public Affairs (Unclassified/ Unlimited Only), Code 703o 4 yj ?>-* i o’ 1. Release of this paper is approved. 2. To the

Carbon mineralization in surface and subsurface soils in a subtropical mixed forest in central China

NASA Astrophysics Data System (ADS)

Liu, F.; Tian, Q.

2014-12-01

About a half of soil carbon is stored in subsurface soil horizons, their dynamics have the potential to significantly affect carbon balancing in terrestrial ecosystems. However, the main factors regulating subsurface soil carbon mineralization are poorly understood. As affected by mountain humid monsoon, the subtropical mountains in central China has an annual precipitation of about 2000 mm, which causes strong leaching of ions and nutrition. The objectives of this study were to monitor subsurface soil carbon mineralization and to determine if it is affected by nutrient limitation. We collected soil samples (up to 1 m deep) at three locations in a small watershed with three soil layers (0-10 cm, 10-30 cm, below 30 cm). For the three layers, soil organic carbon (SOC) ranged from 35.8 to 94.4 mg g-1, total nitrogen ranged from 3.51 to 8.03 mg g-1, microbial biomass carbon (MBC) ranged from 170.6 to 718.4 μg g-1 soil. We measured carbon mineralization with the addition of N (100 μg N/g soil), P (50 μg P/g soil), and liable carbon (glucose labeled by 5 atom% 13C, at five levels: control, 10% MBC, 50% MBC, 100% MBC, 200% MBC). The addition of N and P had negligible effects on CO2 production in surface soil layers; in the deepest soil layer, the addition of N and P decreased CO2 production from 4.32 to 3.20 μg C g-1 soil carbon h-1. Glucose addition stimulated both surface and subsurface microbial mineralization of SOC, causing priming effects. With the increase of glucose addition rate from 10% to 200% MBC, the primed mineralization rate increased from 0.19 to 3.20 μg C g-1 soil carbon h-1 (fifth day of glucose addition). The magnitude of priming effect increased from 28% to 120% as soil layers go deep compare to the basal CO2 production (fifth day of 200% MBC glucose addition, basal CO2 production rate for the surface and the deepest soil was 11.17 and 2.88 μg C g-1 soil carbon h-1). These results suggested that the mineralization of subsurface carbon is more sensitive to nutrient addition, and carbon mineralization in this layer is likely limited by carbon availability. Thus, any changes in environment conditions (global warming, nitrogen deposition, precipitation pattern change etc.) that affect the distribution of fresh carbon in soil profiles could then stimulate the release of deep soil carbon.

Geo-material microfluidics at reservoir conditions for subsurface energy resource applications.

PubMed

Porter, Mark L; Jiménez-Martínez, Joaquín; Martinez, Ricardo; McCulloch, Quinn; Carey, J William; Viswanathan, Hari S

2015-10-21

Microfluidic investigations of flow and transport in porous and fractured media have the potential to play a significant role in the development of future subsurface energy resource technologies. However, the majority of experimental systems to date are limited in applicability due to operating conditions and/or the use of engineered material micromodels. We have developed a high pressure and temperature microfluidic experimental system that allows for direct observations of flow and transport within geo-material micromodels (e.g. rock, cement) at reservoir conditions. In this manuscript, we describe the experimental system, including our novel micromodel fabrication method that works in both geo- and engineered materials and utilizes 3-D tomography images of real fractures as micromodel templates to better represent the pore space and fracture geometries expected in subsurface formations. We present experimental results that highlight the advantages of using real-rock micromodels and discuss potential areas of research that could benefit from geo-material microfluidic investigations. The experiments include fracture-matrix interaction in which water imbibes into the shale rock matrix from etched fractures, supercritical CO2 (scCO2) displacing brine in idealized and realistic fracture patterns, and three-phase flow involving scCO2-brine-oil.

Impact of Elevated CO2 on Trace Element Release from Aquifer Sediments of the San Joaquin Valley, CA

NASA Astrophysics Data System (ADS)

Fox, P. M.; Nico, P. S.; Davis, J. A.; Spycher, N.

2014-12-01

Carbon capture and storage (CCS) is a promising technique for mitigating climate change by storing large volumes of carbon dioxide in deep saline aquifers. In California, the thick marine sediments of the Central and Salinas Valleys have been identified as prime targets for future CO2 storage. However, the potential impacts on water quality of overlying drinking-water aquifers must be studied before CCS can be implemented. In this study, we compare trace element release from San Joaquin Valley aquifer sediments with a wide range of textural and redox properties. Kinetic batch experiments were performed with artificial groundwater continuously equilibrated under CO2-saturated (at 1 atm) and background CO2 (0.002-0.006 atm) conditions, resulting in a shift of nearly 3 pH units. In addition, the reversibility of trace element release was studied by sequentially lowering the CO2 from 1.0 atm to 0.5 atm to background concentrations (0.002-0.006 atm) for CO2-saturated systems in order to mimic the dissipation of a CO2 plume in the aquifer. During exposure to high CO2, a number of elements displayed enhanced release compared to background CO2 experiments (Ca, Mg, Li, Si, B, As, Sr, Ni, Fe, Mn, V, Ti, and Co) with concentrations of As, Fe, and Mn exceeding EPA maximum contaminant levels in some cases. On the other hand, Mo and U showed suppressed release. Most intriguing, many of the elements showing enhanced release displayed at least some degree of irreversibility when CO2 concentrations were decreased to background levels. In fact, in some cases (i.e., for V), an element showed further release when CO2 concentrations were decreased. These results suggest that there may be longer-term effects on groundwater quality that persist even after the CO2 plume has dissipated. Several different mechanisms of trace element release including ion exchange, desorption, and carbonate mineral dissolution are explored. Preliminary modeling results suggest that carbonate mineral dissolution can play a key role in driving trace element release even in sediments where carbonates are in low abundance.

Biological CO2 conversion to acetate in subsurface coal-sand formation using a high-pressure reactor system

NASA Astrophysics Data System (ADS)

Ohtomo, Y.; Ijiri, A.; Ikegawa, Y.; Tsutsumi, M.; Imachi, H.; Uramoto, G.; Hoshino, T.; Morono, Y.; Tanikawa, W.; Hirose, T.; Inagaki, F.

2013-12-01

The geological CO2 sequestration into subsurface unmineable oil/gas fields and coal formations has been considered as one of the possible ways to reduce dispersal of anthropogenic greenhouse gasses into the atmosphere. However, feasibility of CO2 injection largely depends on a variety of geological and economical settings, and its ecological consequences have remained largely unpredictable. To address these issues, we developed a new flow-through-type CO2 injection system designated as the 'geobio-reactor system' to examine possible geophysical, geochemical and microbiological impact caused by CO2 injection under in-situ pressure (0-100 MPa) and temperature (0-70°C) conditions. In this study, we investigated Eocene bituminous coal-sandstones in the northwestern Pacific coast, Hokkaido, Japan, using the geobio-reactor system. Anaerobic artificial fluid and CO2 (flow rate: 0.002 and 0.00001 mL/min, respectively) were continuously supplemented into the coal-sand column under the pore pressure of 40 MPa (confined pressure: 41 MPa) at 40°C for 56 days. Molecular analysis of bacterial 16S rRNA genes showed that predominant bacterial components were physically dispersed from coal to sand as the intact form during experiment. Cultivation experiments from sub-sampling fluids indicated that some terrestrial microbes could preserve their survival in subsurface condition. Molecular analysis of archaeal 16S rRNA genes also showed that no methanogens were activated during experiment. We also anaerobically incubated the coal sample using conventional batch-type cultivation technique with a medium for methanogens. After one year of the batch incubation at 20°C, methane could be detected from the cultures except for the acetate-fed culture. The sequence of archaeal 16S rRNA genes via PCR amplification obtained from the H2 plus formate-fed culture was affiliated with a hydrogenotrophic methanogen within the genus Methanobacterium, whereas the methanol plus trimethylamine culture belonged to a methylotrophic methanogen within the genus Methanosarcina. For the acetate-fed culture, no cell proliferation and methane-production were observed after two-years incubation. During the injection of CO2 and fluid, increase of dissolved CH4 concentration was observed, of which δ13CCH4 were constantly similar to those of the absorbed coal-bed methane (δ13CCBM, ~70‰), suggesting the enhanced gas recovery with fluid flow. The output volume of CO2 (ΣCO2out, 22.1 to 125.6 mM) was smaller than initial concentration (ΣCO2in, 138.38 mM), which can be explained by either adsorption on coal, formation of carbonate minerals, or microbial consumption. Increase of acetate concentration in the fluids was also observed, whereas δ13Cacetate depleted during experiment. Considering with the decrease of additive H2, it is most likely that homo-acetogenesis would occur during experiments, which is consistent with detection of Sporomusa-related 16S rRNA genes, homo-acetogenic bacterium, in cloning analysis of sandstone after experiment. Decrease of formate concentrations and increase of δ13Cformate indicate bacterial consumption of formate and isotopic fractionation. Our results suggest that CO2 injection to natural coal-sand formation stimulates homo-acetogenesis rather than methanogenesis, accompanied by biogenic CO2 conversion to acetate.

Roles of Nano- and Micro-Scale Subsurface Geochemical Reactions on Environmentally Sustainable Geologic Carbon Dioxide Sequestration

NASA Astrophysics Data System (ADS)

Hu, Yandi

Geologic CO2 sequestration (GCS) is a promising approach to reduce anthropogenic CO2 emissions into the atmosphere. At GCS sites, injected CO2 is kept in formation rock by an overlying low permeability caprock. During and after CO2 injection, geochemical reactions can affect the porosity, permeability, and pollutant transport in aquifers. Despite their importance, nano- and micro-scale subsurface geochemical reactions are far from well-understood. Clay mobilization has been reported to decrease aquifer permeability during water flooding, and clay minerals are abundant in caprock. Thus, we studied CO2-brine-clay interactions under varied conditions relevant to different GCS sites (at 35-95°C and under 35-120 atm CO2, in water, NaCl, MgCl2, or CaCl2 solutions). Biotite, Fe-bearing mica, was used as a model clay mineral. We observed numerous fibrous illite precipitates on mica after reaction for only 3 h, which had not been previously reported. A few hours later, the mica surface cracked and fibrous illite detached. The mobilization of fibrous illite can decrease the aquifer's permeability greatly and affect the safety and efficiency of GCS. Mechanisms related to ion exchange, mica swelling, and CO2 intercalation were explored. Oriented aggregation of illite nanoparticles forming the fibrous illite was directly observed, suggesting a new mechanism for fibrous illite formation. Interestingly, besides the pH effect, aqueous CO2 enhances mica cracking over N2. These findings can help to achieve safer subsurface operations. At GCS field sites, Fe concentration increased near the injection sites and originally adsorbed pollutants were released. As the brine flows, Fe re-precipitated because of pH increase. To better predict the fate and transport of aqueous pollutants, the nucleation and growth of Fe(III) (hydr)oxides were studied. New information about sizes and volumes of the Fe(III) (hydr)oxide nanoparticles precipitated in solution and on quartz, mica, and sapphire were provided using small angle X-ray scattering, in the presence of different ions (Al 3+, Cl-, NO3-, and SO 42-). Using complementary techniques, the controlling mechanisms related to surface charge, bond formation, and interfacial energies were explored. These new findings can help better predict pollutant transport in aquifers not only at GCS sites, but also in managed aquifer recharge and acid mine drainage sites.

Estimating geological CO2 storage security to deliver on climate mitigation.

PubMed

Alcalde, Juan; Flude, Stephanie; Wilkinson, Mark; Johnson, Gareth; Edlmann, Katriona; Bond, Clare E; Scott, Vivian; Gilfillan, Stuart M V; Ogaya, Xènia; Haszeldine, R Stuart

2018-06-12

Carbon capture and storage (CCS) can help nations meet their Paris CO 2 reduction commitments cost-effectively. However, lack of confidence in geologic CO 2 storage security remains a barrier to CCS implementation. Here we present a numerical program that calculates CO 2 storage security and leakage to the atmosphere over 10,000 years. This combines quantitative estimates of geological subsurface CO 2 retention, and of surface CO 2 leakage. We calculate that realistically well-regulated storage in regions with moderate well densities has a 50% probability that leakage remains below 0.0008% per year, with over 98% of the injected CO 2 retained in the subsurface over 10,000 years. An unrealistic scenario, where CO 2 storage is inadequately regulated, estimates that more than 78% will be retained over 10,000 years. Our modelling results suggest that geological storage of CO 2 can be a secure climate change mitigation option, but we note that long-term behaviour of CO 2 in the subsurface remains a key uncertainty.

Reducing Risk in CO2 Sequestration: A Framework for Integrated Monitoring of Basin Scale Injection

NASA Astrophysics Data System (ADS)

Seto, C. J.; Haidari, A. S.; McRae, G. J.

2009-12-01

Geological sequestration of CO2 is an option for stabilization of atmospheric CO2 concentrations. Technical ability to safely store CO2 in the subsurface has been demonstrated through pilot projects and a long history of enhanced oil recovery and acid gas disposal operations. To address climate change, current injection operations must be scaled up by a factor of 100, raising issues of safety and security. Monitoring and verification is an essential component in ensuring safe operations and managing risk. Monitoring provides assurance that CO2 is securely stored in the subsurface, and the mechanisms governing transport and storage are well understood. It also provides an early warning mechanism for identification of anomalies in performance, and a means for intervention and remediation through the ability to locate the CO2. Through theoretical studies, bench scale experiments and pilot tests, a number of technologies have demonstrated their ability to monitor CO2 in the surface and subsurface. Because the focus of these studies has been to demonstrate feasibility, individual techniques have not been integrated to provide a more robust method for monitoring. Considering the large volumes required for injection, size of the potential footprint, length of time a project must be monitored and uncertainty, operational considerations of cost and risk must balance safety and security. Integration of multiple monitoring techniques will reduce uncertainty in monitoring injected CO2, thereby reducing risk. We present a framework for risk management of large scale injection through model based monitoring network design. This framework is applied to monitoring CO2 in a synthetic reservoir where there is uncertainty in the underlying permeability field controlling fluid migration. Deformation and seismic data are used to track plume migration. A modified Ensemble Kalman filter approach is used to estimate flow properties by jointly assimilating flow and geomechanical observations. Issues of risk, cost and uncertainty are considered.

Simplified models of rates of CO2 mineralization in Geologic Carbon Storage

NASA Astrophysics Data System (ADS)

DePaolo, D. J.; Zhang, S.

2017-12-01

Geologic carbon storage (GCS) reverses the flow of carbon to the atmosphere, returning the carbon to long-term geologic storage. Models suggest that most of the injected CO2 will be "trapped" in the subsurface by physical means, but the most risk-free and permanent form of carbon storage is as carbonate minerals (Ca,Mg,Fe)CO3. The transformation of CO2 to carbonate minerals requires supply of divalent cations by dissolution of silicate minerals. Available data suggest that rates of transformation are difficult to predict. We show that the chemical kinetic observations and experimental results, when reduced to a single timescale that describes the fractional rate at which cations are released to solution by mineral dissolution, show sufficiently systematic behavior that the rates of mineralization can be estimated with reasonable certainty. Rate of mineralization depends on both the abundance (determined by the reservoir rock mineralogy) and the rate at which cations are released by dissolution into pore fluid that has been acidified with dissolved CO2. Laboratory-measured rates and field observations give values spanning 8 to 10 orders of magnitude, but when evaluated in the context of reservoir-scale reactive transport simulations, this range becomes much smaller. Reservoir scale simulations indicate that silicate mineral dissolution and subsequent carbonate mineral precipitation occur at pH 4.5 to 6, fluid flow velocity less than 5m/yr, and 50-100 years or more after the start of injection. These constraints lead to estimates of 200 to 2000 years for conversion of 60-90% of injected CO2 when the reservoir rock has a sufficient volume fraction of divalent cation-bearing silicate minerals (ca. 20%), and confirms that when reservoir rock mineralogy is not favorable the fraction of CO2 converted to carbonate minerals is minimal over 104 years. A sufficient amount of reactive minerals represents the condition by which the available cations per volume of rock plus pore space exceeds the locally trapped CO2 by a factor of two or more. Our approach may allow for rapid evaluation of mineralization potential of subsurface storage reservoirs, and illustrates how reservoir scale modeling can be integrated with other observations to address key issues for engineering geologic systems.

Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO 2 on Copper?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garza, Alejandro J.; Bell, Alexis T.; Head-Gordon, Martin

It has recently been proposed that subsurface oxygen is crucial for the adsorption and subsequent electroreduction of CO 2 on copper. Using density functional theory, we have studied the stability and diffusion of subsurface oxygen in single crystals of copper exposing (111) and (100) facets. Oxygen is at least 1.5 eV more stable on the surface than beneath it for both crystal orientations; interstitial sites are too small to accommodate oxygen. Here, the rate of atomic oxygen diffusion from one layer below a Cu(111) surface to the surface is 5 × 10 3 s –1. Oxygen can survive longer inmore » deeper layers, but it does not promote CO 2 adsorption there. Diffusion of subsurface oxygen is easier to the less-dense Cu(100) surface, even from lower layers (rate ≈ 1 × 107 s–1). Finally, once the applied voltage and dispersion forces are properly modeled, we find that subsurface oxygen is unnecessary for CO 2 adsorption on copper.« less

Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO 2 on Copper?

DOE PAGES

Garza, Alejandro J.; Bell, Alexis T.; Head-Gordon, Martin

2018-01-17

It has recently been proposed that subsurface oxygen is crucial for the adsorption and subsequent electroreduction of CO 2 on copper. Using density functional theory, we have studied the stability and diffusion of subsurface oxygen in single crystals of copper exposing (111) and (100) facets. Oxygen is at least 1.5 eV more stable on the surface than beneath it for both crystal orientations; interstitial sites are too small to accommodate oxygen. Here, the rate of atomic oxygen diffusion from one layer below a Cu(111) surface to the surface is 5 × 10 3 s –1. Oxygen can survive longer inmore » deeper layers, but it does not promote CO 2 adsorption there. Diffusion of subsurface oxygen is easier to the less-dense Cu(100) surface, even from lower layers (rate ≈ 1 × 107 s–1). Finally, once the applied voltage and dispersion forces are properly modeled, we find that subsurface oxygen is unnecessary for CO 2 adsorption on copper.« less

Review of the impacts of leaking CO 2 gas and brine on groundwater quality

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qafoku, Nikolla P.; Lawter, Amanda R.; Bacon, Diana H.

2017-06-01

This review paper provides a synthetic view of the existing knowledge and summarizes data and findings of the recent literature on the subject of the potential leaking of CO2 from the deep subsurface storage reservoirs and the effects on aquifer quality. New ideas and concepts are developed and insights are also provided. The objectives of this paper are to: 1) present and discuss potential risks for groundwater degradation due to CO2 gas and brine exposure; 2) identify the set of geochemical data required to assess and predict aquifer responses to CO2 and brine leakage. Specifically, this paper will discuss themore » following issues: 1) Aquifer responses (such as changes in aqueous phase/groundwater chemical composition; changes in solid phase chemistry and mineralogy; changes in the extent and rate of reactions and processes and possible establishment of a new network of reactions and processes affecting or controlling overall mobility of major, minor, and trace elements; development of conceptual and reduced order models (ROMs) to describe and predict aquifer responses); 2) The degree of impact such as significant or insignificant changes in pH and major, minor, and trace element release that depend on the following controlling variables; the effect of leaking plume characteristics (gas composition, pure CO2 and/or CO2 -CH4 -H2S mixtures and brine concentration and composition (trace metals); aquifer properties [such as initial aqueous phase conditions and mineralogy: minerals controlling sediments’ response (e.g., calcite, Si bearing minerals, etc.)]; overview of relevant hydrogeological and geochemical processes related to the impact of CO2 gas and brine on groundwater quality; the fate of the elements released from sediments or transported with brine (such as precipitation/incorporation into minerals (calcite and other minerals), adsorption, electron transfer reactions, the role of natural attenuation; whether or not the release of metals following exposure to CO2 harmful (risk assessment).« less

Diffuse CO2 degassing at Vesuvio, Italy

NASA Astrophysics Data System (ADS)

Frondini, Francesco; Chiodini, Giovanni; Caliro, Stefano; Cardellini, Carlo; Granieri, Domenico; Ventura, Guido

2004-10-01

At Vesuvio, a significant fraction of the rising hydrothermal-volcanic fluids is subjected to a condensation and separation process producing a CO2-rich gas phase, mainly expulsed through soil diffuse degassing from well defined areas called diffuse degassing structures (DDS), and a liquid phase that flows towards the outer part of the volcanic cone. A large amount of thermal energy is associated with the steam condensation process and subsequent cooling of the liquid phase. The total amount of volcanic-hydrothermal CO2 discharged through diffuse degassing has been computed through a sequential Gaussian simulation (sGs) approach based on several hundred accumulation chamber measurements and, at the time of the survey, amounted to 151 t d-1. The steam associated with the CO2 output, computed assuming that the original H2O/CO2 ratio of hydrothermal fluids is preserved in fumarolic effluents, is 553 t d-1, and the energy produced by the steam condensation and cooling of the liquid phase is 1.47×1012 J d-1 (17 MW). The location of the CO2 and temperature anomalies show that most of the gas is discharged from the inner part of the crater and suggests that crater morphology and local stratigraphy exert strong control on CO2 degassing and subsurface steam condensation. The amounts of gas and energy released by Vesuvio are comparable to those released by other volcanic degassing areas of the world and their estimates, through periodic surveys of soil CO2 flux, can constitute a useful tool to monitor volcanic activity.

Synthetic seismic monitoring using reverse-time migration and Kirchhoff migration for CO2 sequestration in Korea

NASA Astrophysics Data System (ADS)

Kim, W.; Kim, Y.; Min, D.; Oh, J.; Huh, C.; Kang, S.

2012-12-01

During last two decades, CO2 sequestration in the subsurface has been extensively studied and progressed as a direct tool to reduce CO2 emission. Commercial projects such as Sleipner, In Salah and Weyburn that inject more than one million tons of CO2 per year are operated actively as well as test projects such as Ketzin to study the behavior of CO2 and the monitoring techniques. Korea also began the CCS (CO2 capture and storage) project. One of the prospects for CO2 sequestration in Korea is the southwestern continental margin of Ulleung basin. To monitor the behavior of CO2 underground for the evaluation of stability and safety, several geophysical monitoring techniques should be applied. Among various geophysical monitoring techniques, seismic survey is considered as the most effective tool. To verify CO2 migration in the subsurface more effectively, seismic numerical simulation is an essential process. Furthermore, the efficiency of the seismic migration techniques should be investigated for various cases because numerical seismic simulation and migration test help us accurately interpret CO2 migration. In this study, we apply the reverse-time migration and Kirchhoff migration to synthetic seismic monitoring data generated for the simplified model based on the geological structures of Ulleung basin in Korea. Synthetic seismic monitoring data are generated for various cases of CO2 migration in the subsurface. From the seismic migration images, we can investigate CO2 diffusion patterns indirectly. From seismic monitoring simulation, it is noted that while the reverse-time migration generates clear subsurface images when subsurface structures are steeply dipping, Kirchhoff migration has an advantage in imaging horizontal-layered structures such as depositional sediments appearing in the continental shelf. The reverse-time migration and Kirchhoff migration present reliable subsurface images for the potential site characterized by stratigraphical traps. In case of vertical CO2 migration at injection point, the reverse time migration yields better images than Kirchhoff migration does. On the other hand, Kirchhoff migration images horizontal CO2 migration clearer than the reverse time migration does. From these results, we can conclude that the reverse-time migration and Kirchhoff migration can complement with each other to describe the behavior of CO2 in the subsurface. Acknowledgement This work was financially supported by the Brain Korea 21 project of Energy Systems Engineering, the "Development of Technology for CO2 Marine Geological Storage" program funded by the Ministry of Land, Transport and Maritime Affairs (MLTM) of Korea and the Korea CCS R&D Center (KCRC) grant funded by the Korea government (Ministry of Education, Science and Technology) (No. 2012-0008926).

Advancing Knowledge on Fugitive Natural Gas from Energy Resource Development at a Controlled Release Field Observatory

NASA Astrophysics Data System (ADS)

Cahill, A. G.; Chao, J.; Forde, O.; Prystupa, E.; Mayer, K. U.; Black, T. A.; Tannant, D. D.; Crowe, S.; Hallam, S.; Mayer, B.; Lauer, R. M.; van Geloven, C.; Welch, L. A.; Salas, C.; Levson, V.; Risk, D. A.; Beckie, R. D.

2017-12-01

Fugitive gas, comprised primarily of methane, can be unintentionally released from upstream oil and gas development either at surface from leaky infrastructure or in the subsurface through failure of energy well bore integrity. For the latter, defective cement seals around energy well casings may permit buoyant flow of natural gas from the deeper subsurface towards shallow aquifers, the ground surface and potentially into the atmosphere. Concerns associated with fugitive gas release at surface and in the subsurface include contributions to greenhouse gas emissions, subsurface migration leading to accumulation in nearby infrastructure and impacts to groundwater quality. Current knowledge of the extent of fugitive gas leakage including how to best detect and monitor over time, and particularly its migration and fate in the subsurface, is incomplete. We have established an experimental field observatory for evaluating fugitive gas leakage in an area of historic and ongoing hydrocarbon resource development within the Montney Resource Play of the Western Canadian Sedimentary Basin, British Columbia, Canada. Natural gas will be intentionally released at surface and up to 25 m below surface at various rates and durations. Resulting migration patterns and impacts will be evaluated through examination of the geology, hydrogeology, hydro-geochemistry, isotope geochemistry, hydro-geophysics, vadose zone and soil gas processes, microbiology, and atmospheric conditions. The use of unmanned aerial vehicles and remote sensors for monitoring and detection of methane will also be assessed for suitability as environmental monitoring tools. Here we outline the experimental design and describe initial research conducted to develop a detailed site conceptual model of the field observatory. Subsequently, results attained from pilot surface and sub-surface controlled natural gas releases conducted in late summer 2017 will be presented as well as results of numerical modelling conducted to plan methane release experiments in 2018 and onwards. This research will create knowledge which informs strategies to detect and monitor fugitive gas fluxes at the surface and in groundwater; as well as guide associated regulatory and technical policies.

Final Report for Wetlands as a Source of Atmospheric Methane: A Multiscale and Multidisciplinary Approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

McFarlane, Karis J.

Boreal peatlands contain large amounts of old carbon, protected by anaerobic and cold conditions. Climate change could result in favorable conditions for the microbial decomposition and release of this old peat carbon as CO2 or CH4 back into the atmosphere. Our goal was to test the potential for this positive biological feedback to climate change at SPRUCE (Spruce and Peatland Response Under Climatic and Environmental Change), a manipulation experiment funded by DOE and occurring in a forested bog in Minnesota. Taking advantage of LLNL’s capabilities and expertise in chemical and isotopic signatures we found that carbon emissions from peat weremore » dominated by recently fixed photosynthates, even after short-term experimental warming. We also found that subsurface hydrologic transport was surprisingly rapid at SPRUCE, supplying microbes with young dissolved organic carbon (DOC). We also identified which microbes oxidize CH4 to CO2 at SPRUCE and found that the most active of these also fix N2 (which means they can utilize atmospheric N, making it accessible for other microbes and plants). These results reflect important interactions between hydrology, carbon cycling, and nitrogen cycling present at the bog and relevant to interpreting experimental results and modeling the wetland response to experimental treatments. LLNL involvement at SPRUCE continues through collaborations and a small contract with ORNL, the lead lab for the SPRUCE experiment.« less

Extraction of Seabed/Subsurface Features in a Potential CO2 Sequestration Site in the Southern Baltic Sea, Using Wavelet Transform of High-resolution Sub-Bottom Profiler Data

NASA Astrophysics Data System (ADS)

Tegowski, J.; Zajfert, G.

2014-12-01

Carbon Capture & Storage (CCS) efficiently prevents the release of anthropogenic CO2 into the atmosphere. We investigate a potential site in the Polish Sector of the Baltic Sea (B3 field site), consisting in a depleted oil and gas reservoir. An area ca. 30 x 8 km was surveyed along 138 acoustic transects, realised from R/V St. Barbara in 2012 and combining multibeam echosounder, sidescan sonar and sub-bottom profiler. Preparation of CCS sites requires accurate knowledge of the subsurface structure of the seafloor, in particular deposit compactness. Gas leaks in the water column were monitored, along with the structure of upper sediment layers. Our analyses show the shallow sub-seabed is layered, and quantified the spatial distribution of gas diffusion chimneys and seabed effusion craters. Remote detection of gas-containing surface sediments can be rather complex if bubbles are not emitted directly into the overlying water and thus detectable acoustically. The heterogeneity of gassy sediments makes conventional bottom sampling methods inefficient. Therefore, we propose a new approach to identification, mapping, and monitoring of potentially gassy surface sediments, based on wavelet analysis of echo signal envelopes of a chirp sub-bottom profiler (EdgeTech SB-0512). Each echo envelope was subjected to wavelet transformation, whose coefficients were used to calculate wavelet energies. The set of echo envelope parameters was input to fuzzy logic and c-means algorithms. The resulting classification highlights seafloor areas with different subsurface morphological features, which can indicate gassy sediments. This work has been conducted under EC FP7-CP-IP project No. 265847: Sub-seabed CO2 Storage: Impact on Marine Ecosystems (ECO2).

Seasonal Variability in Vadose zone biodegradation at a crude oil pipeline rupture site

USGS Publications Warehouse

Sihota, Natasha J.; Trost, Jared J.; Bekins, Barbara; Berg, Andrew M.; Delin, Geoffrey N.; Mason, Brent E.; Warren, Ean; Mayer, K. Ulrich

2016-01-01

Understanding seasonal changes in natural attenuation processes is critical for evaluating source-zone longevity and informing management decisions. The seasonal variations of natural attenuation were investigated through measurements of surficial CO2 effluxes, shallow soil CO2 radiocarbon contents, subsurface gas concentrations, soil temperature, and volumetric water contents during a 2-yr period. Surficial CO2 effluxes varied seasonally, with peak values of total soil respiration (TSR) occurring in the late spring and summer. Efflux and radiocarbon data indicated that the fractional contributions of natural soil respiration (NSR) and contaminant soil respiration (CSR) to TSR varied seasonally. The NSR dominated in the spring and summer, and CSR dominated in the fall and winter. Subsurface gas concentrations also varied seasonally, with peak values of CO2 and CH4 occurring in the fall and winter. Vadose zone temperatures and subsurface CO2 concentrations revealed a correlation between contaminant respiration and temperature. A time lag of 5 to 7 mo between peak subsurface CO2 concentrations and peak surface efflux is consistent with travel-time estimates for subsurface gas migration. Periods of frozen soils coincided with depressed surface CO2 effluxes and elevated CO2 concentrations, pointing to the temporary presence of an ice layer that inhibited gas transport. Quantitative reactive transport simulations demonstrated aspects of the conceptual model developed from field measurements. Overall, results indicated that source-zone natural attenuation (SZNA) rates and gas transport processes varied seasonally and that the average annual SZNA rate estimated from periodic surface efflux measurements is 60% lower than rates determined from measurements during the summer.

Comparative Study of Effects of CO 2 Concentration and pH on Microbial Communities from a Saline Aquifer, a Depleted Oil Reservoir, and a Freshwater Aquifer

DOE PAGES

Gulliver, Djuna M.; Lowry, Gregory V.; Gregory, Kelvin B.

2016-08-09

Injected CO 2 from geologic carbon storage is expected to impact the microbial communities of proposed storage sites, such as depleted oil reservoirs and deep saline aquifers, as well as overlying freshwater aquifers at risk of receiving leaking CO 2. Microbial community change in these subsurface sites may affect injectivity of CO 2, permanence of stored CO 2, and shallow subsurface water quality. The effect of CO 2 concentration on the microbial communities in fluid collected from a depleted oil reservoir and a freshwater aquifer was examined at subsurface pressures and temperatures. The community was exposed to 0%, 1%, 10%,more » and 100% pCO 2 for 56 days. Bacterial community structure was analyzed through 16S rRNA gene clone libraries, and total bacterial abundance was estimated through quantitative polymerase chain reaction. Changes in the microbial community observed in the depleted oil reservoir samples and freshwater samples were compared to previous results from CO 2-exposed deep saline aquifer fluids. Overall, results suggest that CO 2 exposure to microbial communities will result in pH-dependent population change, and the CO 2-selected microbial communities will vary among sites. In conclusion, this is the first study to compare the response of multiple subsurface microbial communities at conditions expected during geologic carbon storage, increasing the understanding of environmental drivers for microbial community changes in CO 2-exposed environments.« less

Comparative Study of Effects of CO 2 Concentration and pH on Microbial Communities from a Saline Aquifer, a Depleted Oil Reservoir, and a Freshwater Aquifer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gulliver, Djuna M.; Lowry, Gregory V.; Gregory, Kelvin B.

Injected CO 2 from geologic carbon storage is expected to impact the microbial communities of proposed storage sites, such as depleted oil reservoirs and deep saline aquifers, as well as overlying freshwater aquifers at risk of receiving leaking CO 2. Microbial community change in these subsurface sites may affect injectivity of CO 2, permanence of stored CO 2, and shallow subsurface water quality. The effect of CO 2 concentration on the microbial communities in fluid collected from a depleted oil reservoir and a freshwater aquifer was examined at subsurface pressures and temperatures. The community was exposed to 0%, 1%, 10%,more » and 100% pCO 2 for 56 days. Bacterial community structure was analyzed through 16S rRNA gene clone libraries, and total bacterial abundance was estimated through quantitative polymerase chain reaction. Changes in the microbial community observed in the depleted oil reservoir samples and freshwater samples were compared to previous results from CO 2-exposed deep saline aquifer fluids. Overall, results suggest that CO 2 exposure to microbial communities will result in pH-dependent population change, and the CO 2-selected microbial communities will vary among sites. In conclusion, this is the first study to compare the response of multiple subsurface microbial communities at conditions expected during geologic carbon storage, increasing the understanding of environmental drivers for microbial community changes in CO 2-exposed environments.« less

TMAP-7 simulation of D2 thermal release data from Be co-deposited layers

NASA Astrophysics Data System (ADS)

Baldwin, M. J.; Schwarz-Selinger, T.; Yu, J. H.; Doerner, R. P.

2013-07-01

The efficacy of (1) bake-out at 513 K and 623 K, and (2) thermal transient (10 ms) loading to up to 1000 K, is explored for reducing D inventory in 1 μm thick Be-D (D/Be ˜0.1) co-deposited layers formed at 323 K for experiment (1) and ˜500 K for experiment (2). D release data from co-deposits are obtained by thermal desorption and used to validate a model input into the Tritium Migration & Analysis Program 7 (TMAP). In (1), good agreement with experiment is found for a TMAP model encorporating traps of activation energies, 0.80 eV and 0.98 eV, whereas an additional 2 eV trap was required to model experiment (2). Thermal release is found to be trap limited, but simulations are optimal when surface recombination is taken into account. Results suggest that thick built-up co-deposited layers will hinder ITER inventory control, and that bake periods (˜1 day) will be more effective in inventory reduction than transient thermal loading.

Formation and Release of Cobalt(II) Sorption and Precipitation Products in Aging Kaolinite-Water Slurries.

PubMed

Thompson; Parks; Brown

2000-02-15

The uptake and release behavior of cobalt(II) was studied over thousands of hours in CO(2)-free aqueous suspensions of kaolinite under three pairs of total cobalt concentration (Co(T)) and near-neutral pH (7.5-7.8) conditions. Dissolved cobalt, aluminum, and silicon concentrations were monitored by ICPMS, and cobalt-containing products were identified by EXAFS spectroscopy. In each uptake experiment, cobalt sorbed to kaolinite as a mixture of surface-adsorbed monomers or polymers and hydrotalcite-like precipitates of the approximate composition Co(x)Al(OH)(2x+2)(A(n-))(1/n), where 2

How secure is subsurface CO2 storage? Controls on leakage in natural CO2 reservoirs

NASA Astrophysics Data System (ADS)

Miocic, Johannes; Gilfillan, Stuart; McDermott, Christopher; Haszeldine, Stuart

2014-05-01

Carbon Capture and Storage (CCS) is the only industrial scale technology available to directly reduce carbon dioxide (CO2) emissions from fossil fuelled power plants and large industrial point sources to the atmosphere. The technology includes the capture of CO2 at the source and transport to subsurface storage sites, such as depleted hydrocarbon reservoirs or saline aquifers, where it is injected and stored for long periods of time. To have an impact on the greenhouse gas emissions it is crucial that there is no or only a very low amount of leakage of CO2 from the storage sites to shallow aquifers or the surface. CO2 occurs naturally in reservoirs in the subsurface and has often been stored for millions of years without any leakage incidents. However, in some cases CO2 migrates from the reservoir to the surface. Both leaking and non-leaking natural CO2 reservoirs offer insights into the long-term behaviour of CO2 in the subsurface and on the mechanisms that lead to either leakage or retention of CO2. Here we present the results of a study on leakage mechanisms of natural CO2 reservoirs worldwide. We compiled a global dataset of 49 well described natural CO2 reservoirs of which six are leaking CO2 to the surface, 40 retain CO2 in the subsurface and for three reservoirs the evidence is inconclusive. Likelihood of leakage of CO2 from a reservoir to the surface is governed by the state of CO2 (supercritical vs. gaseous) and the pressure in the reservoir and the direct overburden. Reservoirs with gaseous CO2 is more prone to leak CO2 than reservoirs with dense supercritical CO2. If the reservoir pressure is close to or higher than the least principal stress leakage is likely to occur while reservoirs with pressures close to hydrostatic pressure and below 1200 m depth do not leak. Additionally, a positive pressure gradient from the reservoir into the caprock averts leakage of CO2 into the caprock. Leakage of CO2 occurs in all cases along a fault zone, indicating that faults play a major role when it comes to fluid migration from a reservoir. However, nearly 50% of the non-leaking studied reservoirs are also fault bound, demonstrating that faults are not always necessarily leakage pathways.

40 CFR 98.440 - Definition of the source category.

Code of Federal Regulations, 2011 CFR

2011-07-01

... comprises any well or group of wells that inject a CO2 stream for long-term containment in subsurface... where a CO2 stream is being injected in subsurface geologic formations to enhance the recovery of oil or natural gas unless one of the following applies: (1) The owner or operator injects the CO2 stream for long...

40 CFR 98.440 - Definition of the source category.

Code of Federal Regulations, 2013 CFR

2013-07-01

... comprises any well or group of wells that inject a CO2 stream for long-term containment in subsurface... where a CO2 stream is being injected in subsurface geologic formations to enhance the recovery of oil or natural gas unless one of the following applies: (1) The owner or operator injects the CO2 stream for long...

40 CFR 98.440 - Definition of the source category.

Code of Federal Regulations, 2014 CFR

2014-07-01

... comprises any well or group of wells that inject a CO2 stream for long-term containment in subsurface... where a CO2 stream is being injected in subsurface geologic formations to enhance the recovery of oil or natural gas unless one of the following applies: (1) The owner or operator injects the CO2 stream for long...

40 CFR 98.440 - Definition of the source category.

Code of Federal Regulations, 2012 CFR

2012-07-01

... comprises any well or group of wells that inject a CO2 stream for long-term containment in subsurface... where a CO2 stream is being injected in subsurface geologic formations to enhance the recovery of oil or natural gas unless one of the following applies: (1) The owner or operator injects the CO2 stream for long...

Geo-material microfluidics at reservoir conditions for subsurface energy resource applications

DOE PAGES

Porter, Mark L.; Jiménez-Martínez, Joaquín; Martinez, Ricardo Martin; ...

2015-08-20

Microfluidic investigations of flow and transport in porous and fractured media have the potential to play a significant role in the development of future subsurface energy resource technologies. However, the majority of experimental systems to date are limited in applicability due to operating conditions and/or the use of engineered material micromodels. In this paper, we have developed a high pressure and temperature microfluidic experimental system that allows for direct observations of flow and transport within geo-material micromodels (e.g. rock, cement) at reservoir conditions. In this manuscript, we describe the experimental system, including our novel micromodel fabrication method that works inmore » both geo- and engineered materials and utilizes 3-D tomography images of real fractures as micromodel templates to better represent the pore space and fracture geometries expected in subsurface formations. We present experimental results that highlight the advantages of using real-rock micromodels and discuss potential areas of research that could benefit from geo-material microfluidic investigations. Finally, the experiments include fracture–matrix interaction in which water imbibes into the shale rock matrix from etched fractures, supercritical CO 2 (scCO 2) displacing brine in idealized and realistic fracture patterns, and three-phase flow involving scCO 2–brine–oil.« less

Atmospheric and soil-gas monitoring for surface leakage at the San Juan Basin CO{sub 2} pilot test site at Pump Canyon New Mexico, using perfluorocarbon tracers, CO{sub 2} soil-gas flux and soil-gas hydrocarbons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wells, Arthur W; Diehl, J Rodney; Strazisar, Brian R

2012-05-01

Near-surface monitoring and subsurface characterization activities were undertaken in collaboration with the Southwest Regional Carbon Sequestration Partnership on their San Juan Basin coal-bed methane pilot test site near Navajo City, New Mexico. Nearly 18,407 short tons (1.670 × 107 kg) of CO{sub 2} were injected into 3 seams of the Fruitland coal between July 2008 and April 2009. Between September 18 and October 30, 2008, two additions of approximately 20 L each of perfluorocarbon (PFC) tracers were mixed with the CO{sub 2} at the injection wellhead. PFC tracers in soil-gas and in the atmosphere were monitored over a period ofmore » 2 years using a rectangular array of permanent installations. Additional monitors were placed near existing well bores and at other locations of potential leakage identified during the pre-injection site survey. Monitoring was conducted using sorbent containing tubes to collect any released PFC tracer from soil-gas or the atmosphere. Near-surface monitoring activities also included CO{sub 2} surface flux and carbon isotopes, soil-gas hydrocarbon levels, and electrical conductivity in the soil. The value of the PFC tracers was demonstrated when a significant leakage event was detected near an offset production well. Subsurface characterization activities, including 3D seismic interpretation and attribute analysis, were conducted to evaluate reservoir integrity and the potential that leakage of injected CO{sub 2} might occur. Leakage from the injection reservoir was not detected. PFC tracers made breakthroughs at 2 of 3 offset wells which were not otherwise directly observable in produced gases containing 20–30% CO{sub 2}. These results have aided reservoir geophysical and simulation investigations to track the underground movement of CO{sub 2}. 3D seismic analysis provided a possible interpretation for the order of appearance of tracers at production wells.« less

Structural, electronic and optical properties of CO adsorbed on the defective anatase TiO2 (101) surface; a DFT study

NASA Astrophysics Data System (ADS)

Rafique, Muhammad; Shuai, Yong; Hassan, Muhammad

2017-08-01

This paper illustrates the study of stable structural, electronic and optical properties of carbon mono oxide (CO) molecule adsorbed on pure anatase TiO2 (101) surface and CO molecule adsorbed on defective anatase TiO2 (101) surface containing oxygen (O) atom subsurface vacancy using first-principles study calculations based on density functional theory (DFT) method. A foreign molecule CO was added in the interstitial space of anatase TiO2 (101) surface. It was observed that, adsorption of CO molecule is not favorable on pure anatase TiO2 (101) surface, however adsorption process is improved when subsurface contains O atom vacancy defect. In case of anatase TiO2 (101) surface containing subsurface vacancy, adsorption process is exothermic, resulting in stable structures. The adsorption energies calculated for CO molecules adsorbed at O2c site, at defect site and at Ti5c site of anatase surface containing subsurface O vacancy are 0.16 eV (at O2c), 0.32 eV (at defect site) and 0.43 eV (at Ti5c) site. DOS and PDOS plots are calculated for all the structures. Results indicated that CO molecule adsorption introduces surface states at the Fermi energy level (EF) as shown in partial density of states (PDOS) plots. The dielectric matrix and absorption coefficient (α) for defective anatase TiO2 (101) surface, CO adsorbed at O2c site, at defect site and at Ti5C site of anatase TiO2 (101) surface containing O atom subsurface vacancy has been calculated within the random phase approximation (RPA) using VASP (Vienna ab-initio simulation package) code. It was observed that upon CO adsorption at defective anatase surface, real and imaginary dielectric function peaks were shifted towards lower energy level and a small absorption peak was observed at 1.1 eV energy level which is not present in case of defective anatase (101) surface. CO adsorption produces a red shift in the absorption spectrum of anatase TiO2 (101) surface containing subsurface O atom vacancy.

High pressure-elevated temperature x-ray micro-computed tomography for subsurface applications.

PubMed

Iglauer, Stefan; Lebedev, Maxim

2018-06-01

Physical, chemical and mechanical pore-scale (i.e. micrometer-scale) mechanisms in rock are of key importance in many, if not all, subsurface processes. These processes are highly relevant in various applications, e.g. hydrocarbon recovery, CO 2 geo-sequestration, geophysical exploration, water production, geothermal energy production, or the prediction of the location of valuable hydrothermal deposits. Typical examples are multi-phase flow (e.g. oil and water) displacements driven by buoyancy, viscous or capillary forces, mineral-fluid interactions (e.g. mineral dissolution and/or precipitation over geological times), geo-mechanical rock behaviour (e.g. rock compaction during diagenesis) or fines migration during water production, which can dramatically reduce reservoir permeability (and thus reservoir performance). All above examples are 3D processes, and 2D experiments (as traditionally done for micro-scale investigations) will thus only provide qualitative information; for instance the percolation threshold is much lower in 3D than in 2D. However, with the advent of x-ray micro-computed tomography (μCT) - which is now routinely used - this limitation has been overcome, and such pore-scale processes can be observed in 3D at micrometer-scale. A serious complication is, however, the fact that in the subsurface high pressures and elevated temperatures (HPET) prevail, due to the hydrostatic and geothermal gradients imposed upon it. Such HPET-reservoir conditions significantly change the above mentioned physical and chemical processes, e.g. gas density is much higher at high pressure, which strongly affects buoyancy and wettability and thus gas distributions in the subsurface; or chemical reactions are significantly accelerated at increased temperature, strongly affecting fluid-rock interactions and thus diagenesis and deposition of valuable minerals. It is thus necessary to apply HPET conditions to the aforementioned μCT experiments, to be able to mimic subsurface conditions in a realistic way, and thus to obtain reliable results, which are vital input parameters required for building accurate larger-scale reservoir models which can predict the overall reservoir-scale (hectometer-scale) processes (e.g. oil production or diagenesis of a formation). We thus describe here the basic workflow of such HPET-μCT experiments, equipment requirements and apparatus design; and review the literature where such HPET-μCT experiments were used and which phenomena were investigated (these include: CO 2 geo-sequestration, oil recovery, gas hydrate formation, hydrothermal deposition/reactive flow). One aim of this paper is to give a guideline to users how to set-up a HPET-μCT experiment, and to provide a quick overview in terms of what is possible and what not, at least up to date. As a conclusion, HPET-μCT is a valuable tool when it comes to the investigation of subsurface micrometer-scaled processes, and we expect a rapidly expanding usage of HPET-μCT in subsurface engineering and the subsurface sciences. Copyright © 2018 Elsevier B.V. All rights reserved.

Proof-of-feasibility of using well bore deformation as a diagnostic tool to improve CO 2 sequestration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Murdoch, Larry; Moysey, Stephen; Germanovich, Leonid

Injecting CO 2 raises pore pressure and this causes subsurface formations to deform. The pattern and amount of deformation will reflect the distribution of pressure and formation properties in the subsurface, two quantities of interest during CO 2 storage. The hypothesis underlying this research is that the small deformation accompanying CO 2 storage can be measured and interpreted to improve the storage process.

Numerical modeling of experimental observations on gas formation and multi-phase flow of carbon dioxide in subsurface formations

NASA Astrophysics Data System (ADS)

Pawar, R.; Dash, Z.; Sakaki, T.; Plampin, M. R.; Lassen, R. N.; Illangasekare, T. H.; Zyvoloski, G.

2011-12-01

One of the concerns related to geologic CO2 sequestration is potential leakage of CO2 and its subsequent migration to shallow groundwater resources leading to geochemical impacts. Developing approaches to monitor CO2 migration in shallow aquifer and mitigate leakage impacts will require improving our understanding of gas phase formation and multi-phase flow subsequent to CO2 leakage in shallow aquifers. We are utilizing an integrated approach combining laboratory experiments and numerical simulations to characterize the multi-phase flow of CO2 in shallow aquifers. The laboratory experiments involve a series of highly controlled experiments in which CO2 dissolved water is injected in homogeneous and heterogeneous soil columns and tanks. The experimental results are used to study the effects of soil properties, temperature, pressure gradients and heterogeneities on gas formation and migration. We utilize the Finite Element Heat and Mass (FEHM) simulator (Zyvoloski et al, 2010) to numerically model the experimental results. The numerical models capture the physics of CO2 exsolution, multi-phase fluid flow as well as sand heterogeneity. Experimental observations of pressure, temperature and gas saturations are used to develop and constrain conceptual models for CO2 gas-phase formation and multi-phase CO2 flow in porous media. This talk will provide details of development of conceptual models based on experimental observation, development of numerical models for laboratory experiments and modelling results.

The Mars Express - NASA Project at JPL

NASA Technical Reports Server (NTRS)

Thompson, Thomas W.; Horttor, Richard L.; Acton, C. H., Jr.; Zamani, P.; Johnson, W. T. K.; Plaut, J. J.; Holmes, D. P.; No, S.; Asmar, S. W.; Goltz, G.

2006-01-01

This viewgraph presentation gives a general overview of the Mars Express NASA Project at JPL. The contents include: 1) Mars Express/NASA Project Overview; 2) Experiment-Investigator Matrix; 3) Mars Express Support of NASA's Mars Exploration Objectives; 4) U.S./NASA Support of Mars Express; 5) Mars Express Schedule (2003-2007); 6) Mars Express Data Rates; 7) MARSIS Overview Results; 8) MARSIS with Antennas Deployed; 9) MARSIS Science Objectives; 10) Mars Advanced Radar for Subsurface and Ionospheric Sounding (MARSIS) Experiment Overview; 11) Mars Express Orbit Evolution; 12) MARSIS Science - Subsurface Sounding; 13) MARSIS-North Polar Ice Cap; 14) MARSIS Data-Buried Basin; 15) MARSIS over a Crater Basin; 16) MARSIS-Buried Basin; 17) Ionogram - Orbit 2032 (example from Science paper); 18) Ionogram-Orbit 2018 (example from Science paper); and 19) Recent MARSIS Results ESA Press Releases.

Hyperspectral Geobotanical Remote Sensing for Monitoring and Verifying CO 2 Containment Final Report CRADA No. TC-2036-02

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pickles, W. L.; Ebrom, D. A.

This collaborative effort was in support of the CO 2 Capture Project (CCP), to develop techniques that integrate overhead images of plant species, plant health, geological formations, soil types, aquatic, and human use spatial patterns for detection and discrimination of any CO 2 releases from underground storage formations. The goal of this work was to demonstrate advanced hyperspectral geobotanical remote sensing methods to assess potential leakage of CO 2 from underground storage. The timeframes and scales relevant to the long-term storage of CO 2 in the subsurface make remote sensing methods attractive. Moreover, it has been shown that individual fieldmore » measurements of gas composition are subject to variability on extremely small temporal and spatial scales. The ability to verify ultimate reservoir integrity and to place individual surface measurements into context will be crucial to successful long-term monitoring and verification activities. The desired results were to produce a defined and tested procedure that could be easily used for long-term monitoring of possible CO 2 leakage from underground CO 2 sequestration sites. This testing standard will be utilized on behalf of the oil industry.« less

The Role of Subsurface Oxygen on Cu Surfaces for CO 2 Electrochemical Reduction

DOE PAGES

Fields, Meredith; Hong, Xin; Norskov, Jens K.; ...

2018-06-12

Under ambient conditions, copper with oxygen near the surface displays strengthened CO 2 and CO adsorption energies. This finding is often used to rationalize differences seen in product distributions between Cu-oxide and pure Cu electrodes during electrochemical CO 2 reduction. However, little evidence exists to confirm the presence of oxygen within first few layers of the Cu matrix under relevant experimental reducing conditions. As a result, using density functional theory calculations, we discuss the stability of subsurface oxygen from thermodynamic and kinetic perspectives, and show that under reducing potentials, subsurface oxygen alone should have negligible effects on the activity ofmore » crystalline Cu.« less

The Role of Subsurface Oxygen on Cu Surfaces for CO 2 Electrochemical Reduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fields, Meredith; Hong, Xin; Norskov, Jens K.

Under ambient conditions, copper with oxygen near the surface displays strengthened CO 2 and CO adsorption energies. This finding is often used to rationalize differences seen in product distributions between Cu-oxide and pure Cu electrodes during electrochemical CO 2 reduction. However, little evidence exists to confirm the presence of oxygen within first few layers of the Cu matrix under relevant experimental reducing conditions. As a result, using density functional theory calculations, we discuss the stability of subsurface oxygen from thermodynamic and kinetic perspectives, and show that under reducing potentials, subsurface oxygen alone should have negligible effects on the activity ofmore » crystalline Cu.« less

CO2 exposure at pressure impacts metabolism and stress responses in the model sulfate-reducing bacterium Desulfovibrio vulgaris strain Hildenborough

PubMed Central

Wilkins, Michael J.; Hoyt, David W.; Marshall, Matthew J.; Alderson, Paul A.; Plymale, Andrew E.; Markillie, L. Meng; Tucker, Abby E.; Walter, Eric D.; Linggi, Bryan E.; Dohnalkova, Alice C.; Taylor, Ron C.

2014-01-01

Geologic carbon dioxide (CO2) sequestration drives physical and geochemical changes in deep subsurface environments that impact indigenous microbial activities. The combined effects of pressurized CO2 on a model sulfate-reducing microorganism, Desulfovibrio vulgaris, have been assessed using a suite of genomic and kinetic measurements. Novel high-pressure NMR time-series measurements using 13C-lactate were used to track D. vulgaris metabolism. We identified cessation of respiration at CO2 pressures of 10 bar, 25 bar, 50 bar, and 80 bar. Concurrent experiments using N2 as the pressurizing phase had no negative effect on microbial respiration, as inferred from reduction of sulfate to sulfide. Complementary pressurized batch incubations and fluorescence microscopy measurements supported NMR observations, and indicated that non-respiring cells were mostly viable at 50 bar CO2 for at least 4 h, and at 80 bar CO2 for 2 h. The fraction of dead cells increased rapidly after 4 h at 80 bar CO2. Transcriptomic (RNA-Seq) measurements on mRNA transcripts from CO2-incubated biomass indicated that cells up-regulated the production of certain amino acids (leucine, isoleucine) following CO2 exposure at elevated pressures, likely as part of a general stress response. Evidence for other poorly understood stress responses were also identified within RNA-Seq data, suggesting that while pressurized CO2 severely limits the growth and respiration of D. vulgaris cells, biomass retains intact cell membranes at pressures up to 80 bar CO2. Together, these data show that geologic sequestration of CO2 may have significant impacts on rates of sulfate reduction in many deep subsurface environments where this metabolism is a key respiratory process. PMID:25309528

CO2 exposure at pressure impacts metabolism and stress responses in the model sulfate-reducing bacterium Desulfovibrio vulgaris strain Hildenborough

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilkins, Michael J.; Hoyt, David W.; Marshall, Matthew J.

Geologic carbon dioxide (CO2) sequestration drives physical and geochemical changes in deep subsurface environments that impact indigenous microbial activities. The combined effects of pressurized CO2 on a model sulfate-reducing microorganism, Desulfovibrio vulgaris, have been assessed using a suite of genomic and kinetic measurements. Novel high-pressure NMR time-series measurements using 13C-lactate were used to track D. vulgaris metabolism. We identified cessation of respiration at CO2 pressures of 10 bar, 25 bar, 50 bar, and 80 bar. Concurrent experiments using N2 as the pressurizing phase had no negative effect on microbial respiration, as inferred from reduction of sulfate to sulfide. Complementary pressurizedmore » batch incubations and fluorescence microscopy measurements supported NMR observations, and indicated that non-respiring cells were mostly viable at 50 bar CO2 for at least four hours, and at 80 bar CO2 for two hours. The fraction of dead cells increased rapidly after four hours at 80 bar CO2. Transcriptomic (RNA-Seq) measurements on mRNA transcripts from CO2-incubated biomass indicated that cells up-regulated the production of certain amino acids (leucine, isoleucine) following CO2 exposure at elevated pressures, likely as part of a general stress response. Evidence for other poorly understood stress responses were also identified within RNA-Seq data, suggesting that while pressurized CO2 severely limits the growth and respiration of D. vulgaris cells, biomass retains intact cell membranes at pressures up to 80 bar CO2. Together, these data show that geologic sequestration of CO2 may have significant impacts on rates of sulfate reduction in many deep subsurface environments where this metabolism is a key respiratory process.« less

The combined effects of acidification and hypoxia on pH and aragonite saturation in the coastal waters of the California current ecosystem and the northern Gulf of Mexico

NASA Astrophysics Data System (ADS)

Feely, Richard A.; Okazaki, Remy R.; Cai, Wei-Jun; Bednaršek, Nina; Alin, Simone R.; Byrne, Robert H.; Fassbender, Andrea

2018-01-01

Inorganic carbon chemistry data from the surface and subsurface waters of the West Coast of North America have been compared with similar data from the northern Gulf of Mexico to demonstrate how future changes in CO2 emissions will affect chemical changes in coastal waters affected by respiration-induced hypoxia ([O2] ≤ 60 μmol kg-1). In surface waters, the percentage change in the carbon parameters due to increasing CO2 emissions are very similar for both regions even though the absolute decrease in aragonite saturation is much higher in the warmer waters of the Gulf of Mexico. However, in subsurface waters the changes are enhanced due to differences in the initial oxygen concentration and the changes in the buffer capacity (i.e., increasing Revelle Factor) with increasing respiration from the oxidation of organic matter, with the largest impacts on pH and CO2 partial pressure (pCO2) occurring in the colder West Coast waters. As anthropogenic CO2 concentrations begin to build up in subsurface waters, increased atmospheric CO2 will expose organisms to hypercapnic conditions (pCO2 >1000 μatm) within subsurface depths. Since the maintenance of the extracellular pH appears as the first line of defense against external stresses, many biological response studies have been focused on pCO2-induced hypercapnia. The extent of subsurface exposure will occur sooner and be more widespread in colder waters due to their capacity to hold more dissolved oxygen and the accompanying weaker acid-base buffer capacity. Under present conditions, organisms in the West Coast are exposed to hypercapnic conditions when oxygen concentrations are near 100 μmol kg-1 but will experience hypercapnia at oxygen concentrations of 260 μmol kg-1 by year 2100 under the highest elevated-CO2 conditions. Hypercapnia does not occur at present in the Gulf of Mexico but will occur at oxygen concentrations of 170 μmol kg-1 by the end of the century under similar conditions. The aragonite saturation horizon is currently above the hypoxic zone in the West Coast. With increasing atmospheric CO2, it is expected to shoal up close to surface waters under the IPCC Representative Concentration Pathway (RCP) 8.5 in West Coast waters, while aragonite saturation state will exhibit steeper gradients in the Gulf of Mexico. This study demonstrates how different biological thresholds (e.g., hypoxia, CaCO3 undersaturation, hypercapnia) will vary asymmetrically because of local initial conditions that are affected differently with increasing atmospheric CO2. The direction of change in amplitude of hypercapnia will be similar in both ecosystems, exposing both biological communities from the West Coast and Gulf of Mexico to intensification of stressful conditions. However, the region of lower Revelle factors (i.e., the Gulf of Mexico), currently provides an adequate refuge habitat that might no longer be the case under the most severe RCP scenarios.

DOE Office of Scientific and Technical Information (OSTI.GOV)

James P. Barry; Peter G. Brewer

OAK-B135 This report summarizes activities and results of investigations of the potential environmental consequences of direct injection of carbon dioxide into the deep-sea as a carbon sequestration method. Results of field experiments using small scale in situ releases of liquid CO2 are described in detail. The major conclusions of these experiments are that mortality rates of deep sea biota will vary depending on the concentrations of CO2 in deep ocean waters that result from a carbon sequestration project. Large changes in seawater acidity and carbon dioxide content near CO2 release sites will likely cause significant harm to deep-sea marine life.more » Smaller changes in seawater chemistry at greater distances from release sites will be less harmful, but may result in significant ecosystem changes.« less

[Preparation of ibuprofen/EC-PVP sustained-release composite particles by supercritical CO2 anti-solvent technology].

PubMed

Cai, Jin-Yuan; Huang, De-Chun; Wang, Zhi-Xiang; Dang, Bei-Lei; Wang, Qiu-Ling; Su, Xin-Guang

2012-06-01

Ibuprofen/ethyl-cellulose (EC)-polyvinylpyrrolidone (PVP) sustained-release composite particles were prepared by using supercritical CO2 anti-solvent technology. With drug loading as the main evaluation index, orthogonal experimental design was used to optimize the preparation process of EC-PVP/ibuprofen composite particles. The experiments such as encapsulation efficiency, particle size distribution, electron microscope analysis, infrared spectrum (IR), differential scanning calorimetry (DSC) and in vitro dissolution were used to analyze the optimal process combination. The orthogonal experimental optimization process conditions were set as follows: crystallization temperature 40 degrees C, crystallization pressure 12 MPa, PVP concentration 4 mgmL(-1), and CO2 velocity 3.5 Lmin(-1). Under the optimal conditions, the drug loading and encapsulation efficiency of ibuprofen/EC-PVP composite particles were 12.14% and 52.21%, and the average particle size of the particles was 27.621 microm. IR and DSC analysis showed that PVP might complex with EC. The experiments of in vitro dissolution showed that ibuprofen/EC-PVP composite particles had good sustained-release effect. Experiment results showed that, ibuprofen/EC-PVP sustained-release composite particles can be prepared by supercritical CO2 anti-solvent technology.

The influence of DOM and microbial processes on arsenic release from karst during ASR operations in the Floridan Aquifer

NASA Astrophysics Data System (ADS)

Jin, J.; Zimmerman, A. R.

2011-12-01

The mobilization of subsurface As poses a serious threat to human health, particularly in a region such as Florida where population is heavily dependent on highly porous karstic aquifers for drinking water. Injection water used in aquifer storage and recovery (ASR) or aquifer recharge (AR) operations is commonly high in dissolved organic matter (DOM) and OM can also be present in the subsurface carbonate rock. Using batch incubation experiments, this study examined the role of core preservation methods, as well as the influence of labile and more refractory DOM on the mobilization of As from carbonate rock. Incubation experiments used sealed reaction vessels with preserved and homogenized core materials collected via coring the Suwannee Formation in southwest Florida and treatment additions consisting of 1) source water (SW) enriched in sterilized soil DOM, 2) SW enriched in soil DOM and microbes, and 3) SW enriched in sodium acetate. During an initial equilibration phase in native groundwater (NGW) with low dissolved oxygen (DO; Phase 1), we found the greatest As release of the whole incubation. In the beginning of Phase 2 (N2 headspace) in which NGW was replaced with treatment solutions, there was little As release except in the vessel with Na-acetate added, which also had the lowest ORP. At the start of Phase 3, when incubations were exposed to air, most vessels saw more ion (including As) release into solution. Vessel with Na-acetate had less As release in Phase 3 than in Phase 2. During all experimental phases, treatments of DOM or microbe additions had no apparent effect on the amount of As release. The core materials was found contain significant amount of indigenous DOM (about 8 g OC/kg core) which was released during the incubation so DOC concentrations displayed no clear pattern among different treatments. At least three abiotic As mobilization mechanisms may play a role in As released during different stages of the experiment. Desorption of As from iron oxyhydroxides may have occurred, particularly at the beginning of each experimental phase. Reductive dissolution and oxidative dissolution likely lead to As release during phase 2 and 3, respectively. While not directly implicated, the presence of labile OM clearly fueled microbial alteration of redox conditions, leading to further As release. Addition of microbes had no effect as indigenous microbes were just as active in untreated cores.

Influences of pH and CO2 on the formation of Metasilicate mineral water in Changbai Mountain, Northeast China

NASA Astrophysics Data System (ADS)

Yan, Baizhong; Xiao, Changlai; Liang, Xiujuan; Wu, Shili

2017-07-01

Mineral dissolution reactions actively participate in controlling the composition of mineral water. In this study, water soluble, acidic-alkaline and carbonated solution experiments were designed, and mineral reaction mechanisms were researched using chemical kinetics and the minimum free-energy method. The results showed that the release of metasilicate was controlled by pH, CO2, and rock characteristics. In the water soluble experiment, the release process of metasilicate in powdered rocks reached equilibrium after 40 days, while metasilicate in solid rocks took 170 days. The release process of metasilicate in solid rocks satisfied an asymptotic model, while in powdered rocks it accorded with the Stanford reaction kinetic model. In the acidic-alkaline experiment, metasilicate was released earlier under acidic conditions (2.46 < pH < 7) than under alkaline conditions (7 < pH < 10.61). The release process of metasilicate under acidic conditions reached equilibrium in 40 days, compared with 60 days for alkaline conditions. The addition of CO2 to the water solution was beneficial to the formation of metasilicate. Under neutral pH conditions, the reaction barely occurred. Under alkaline conditions, metasilicate was produced by the hydrolysis of metasilicate minerals. Under acidic and additional CO2 conditions, metasilicate formation was mainly via the reaction of H+, CO2, and metasilicate minerals. From these results, we concluded that the metasilicate mineral water from the Changbai Mountains, Jingyu County, is generated by a combination of the hydrolysis of metasilicate minerals and the reaction of H+, CO2, and metasilicate minerals. These results can contribute to a better development and protection of the mineral water resources in the Changbai Mountains.

Peroxide-modified titanium dioxide: a chemical analog of putative Martian soil oxidants

NASA Technical Reports Server (NTRS)

Quinn, R. C.; Zent, A. P.

1999-01-01

Hydrogen peroxide chemisorbed on titanium dioxide (peroxide-modified titanium dioxide) is investigated as a chemical analog to the putative soil oxidants responsible for the chemical reactivity seen in the Viking biology experiments. When peroxide-modified titanium dioxide (anatase) was exposed to a solution similar to the Viking labeled release (LR) experiment organic medium, CO2 gas was released into the sample cell headspace. Storage of these samples at 10 degrees C for 48 hr prior to exposure to organics resulted in a positive response while storage for 7 days did not. In the Viking LR experiment, storage of the Martian surface samples for 2 sols (approximately 49 hr) resulted in a positive response while storage for 141 sols essentially eliminated the initial rapid release of CO2. Heating the peroxide-modified titanium dioxide to 50 degrees C prior to exposure to organics resulted in a negative response. This is similar to, but not identical to, the Viking samples where heating to approximately 46 degrees C diminished the response by 54-80% and heating to 51.5 apparently eliminated the response. When exposed to water vapor, the peroxide-modified titanium dioxide samples release O2 in a manner similar to the release seen in the Viking gas exchange experiment (GEx). Reactivity is retained upon heating at 50 degrees C for three hours, distinguishing this active agent from the one responsible for the release of CO2 from aqueous organics. The release of CO2 by the peroxide-modified titanium dioxide is attributed to the decomposition of organics by outer-sphere peroxide complexes associated with surface hydroxyl groups, while the release of O2 upon humidification is attributed to more stable inner-sphere peroxide complexes associated with Ti4+ cations. Heating the peroxide-modified titanium dioxide to 145 degrees C inhibited the release of O2, while in the Viking experiments heating to this temperature diminished but did not eliminated the response. Although the thermal stability of the titanium-peroxide complexes in this work is lower than the stability seen in the Viking experiments, it is expected that similar types of complexes will form in titanium containing minerals other than anatase and the stability of these complexes will vary with surface hydroxylation and mineralogy.

Electrochemical characterization of cerium-based conversion coatings on aluminum alloy 7075-T6

NASA Astrophysics Data System (ADS)

Joshi, Simon

This research used electrochemical techniques to characterize the deposition and corrosion protection behavior of cerium-based conversion coatings on Al 7075-T6. Alkaline activation decreased native oxide impedance (5.9 kO-cm2) by ˜25% promoting deposition of 250--500 nm coatings. Activation in NaOH solutions deposited coatings with large cracks and craters, whereas Na2CO3 activation resulted in uniform coatings, i.e., fewer cracks and almost no craters. Uniformly deposited coatings exhibited better cathodic inhibition and higher impedance (˜200 kO-cm 2) than on NaOH activated substrates (˜100 kO-cm 2). Subsurface crevices, caused by Cl- and H 2O2 in the deposition solution, were found under large cracks and craters. Thus, Na2CO3 activation produced fewer subsurface crevices. To reduce subsurface crevice formation, Ce(NO3) 3 and CeCl3 were used in different ratios. Coatings made using 100% Ce(NO3)3 solutions were ˜60 nm thick without subsurface crevices, but the coatings offered little corrosion protection. Despite formation of subsurface crevices, Cl- was necessary as impedance increased linearly with Cl- concentration in the deposition solution. To characterize the different non-uniform features of the coatings, microelectrochemical testing was performed and it showed three distinct regions: active, intermediate, and passive. Humidity experiments were performed to understand the effect of moisture during salt spray testing and showed an increase in coating impedance by making the exposed substrate oxide more passive. However, this passive oxide could not provide corrosion resistance in a chloride environment. Dissolution studies showed that cerium migration was only possible at pH ≤2. Overall, deposition of uniform 250--500 nm thick outings was essential to make it an effective barrier to Cl - attach and prevent subsurface crevices on Al 7075-T6.

The footprint of CO2 leakage in the water-column: Insights from numerical modeling based on a North Sea gas release experiment

NASA Astrophysics Data System (ADS)

Vielstädte, L.; Linke, P.; Schmidt, M.; Sommer, S.; Wallmann, K.; McGinnis, D. F.; Haeckel, M.

2013-12-01

Assessing the environmental impact of potential CO2 leakage from offshore carbon dioxide storage sites necessitates the investigation of the corresponding pH change in the water-column. Numerical models have been developed to simulate the buoyant rise and dissolution of CO2 bubbles in the water-column and the subsequent near-field dispersion of dissolved CO2 in seawater under ocean current and tidal forcing. In order to test and improve numerical models a gas release experiment has been conducted at 80 m water-depth within the Sleipner area (North Sea). CO2 and Kr (used as inert tracer gas) were released on top of a benthic lander at varying gas flows (<140 kg/day) and bubble sizes (de: 1-6 mm). pCO2 and pH were measured by in situ sensors to monitor the spread of the solute in different vertical heights and distances downstream of the artificial leak. The experiment and numerical analysis show that the impact of such leakage rates is limited to the near-field bottom waters, due to the rapid dissolution of CO2 bubbles in seawater (CO2 is being stripped within the first two to five meters of bubble rise). In particular, small bubbles, which will dissolve close to the seafloor, may cause a dangerous low-pH environment for the marine benthos. However, on the larger scale, the advective transport by e.g. tidal currents, dominates the CO2 dispersal in the North Sea and dilutes the CO2 peak quickly. The model results show that at the small scales (<100 m) of the CO2 plume the lateral eddy diffusion (~0.01 m2/s) has only a negligible effect. Overall, we can postulate that CO2 leakage at a rate of ~ 100 kg per day as in our experiment will only have a localized impact on the marine environment, thereby reducing pH substantially (by 0.4 units) within a diameter of less than 50 m around the release spot (depending on the duration of leakage and the current velocities). Strong currents and tidal cycles significantly reduce the spreading of low-pH water masses into the far-field by efficiently diluting the amount of CO2 in ambient seawater.

Subsurface Contamination Control

DOE Office of Scientific and Technical Information (OSTI.GOV)

Y. Yuan

There are two objectives of this report, ''Subsurface Contamination Control''. The first is to provide a technical basis for recommending limiting radioactive contamination levels (LRCL) on the external surfaces of waste packages (WP) for acceptance into the subsurface repository. The second is to provide an evaluation of the magnitude of potential releases from a defective WP and the detectability of the released contents. The technical basis for deriving LRCL has been established in ''Retrieval Equipment and Strategy for Wp on Pallet'' (CRWMS M and O 2000g, 6.3.1). This report updates the derivation by incorporating the latest design information of themore » subsurface repository for site recommendation. The derived LRCL on the external surface of WPs, therefore, supercede that described in CRWMS M and O 2000g. The derived LRCL represent the average concentrations of contamination on the external surfaces of each WP that must not be exceeded before the WP is to be transported to the subsurface facility for emplacement. The evaluation of potential releases is necessary to control the potential contamination of the subsurface repository and to detect prematurely failed WPs. The detection of failed WPs is required in order to provide reasonable assurance that the integrity of each WP is intact prior to MGR closure. An emplaced WP may become breached due to manufacturing defects or improper weld combined with failure to detect the defect, by corrosion, or by mechanical penetration due to accidents or rockfall conditions. The breached WP may release its gaseous and volatile radionuclide content to the subsurface environment and result in contaminating the subsurface facility. The scope of this analysis is limited to radioactive contaminants resulting from breached WPs during the preclosure period of the subsurface repository. This report: (1) documents a method for deriving LRCL on the external surfaces of WP for acceptance into the subsurface repository; (2) provides a table of derived LRCL for nuclides of radiological importance; (3) Provides an as low as is reasonably achievable (ALARA) evaluation of the derived LRCL by comparing potential onsite and offsite doses to documented ALARA requirements; (4) Provides a method for estimating potential releases from a defective WP; (5) Provides an evaluation of potential radioactive releases from a defective WP that may become airborne and result in contamination of the subsurface facility; and (6) Provides a preliminary analysis of the detectability of a potential WP leak to support the design of an airborne release monitoring system.« less

[Preparation of curcumin-EC sustained-release composite particles by supercritical CO2 anti-solvent technology].

PubMed

Bai, Wei-li; Yan, Ting-yuan; Wang, Zhi-xiang; Huang, De-chun; Yan, Ting-xuan; Li, Ping

2015-01-01

Curcumin-ethyl-cellulose (EC) sustained-release composite particles were prepared by using supercritical CO2 anti-solvent technology. With drug loading and yield of inclusion complex as evaluation indexes, on the basis of single factor tests, orthogonal experimental design was used to optimize the preparation process of curcumin-EC sustained-release composite particles. The experiments such as drug loading, yield, particle size distribution, electron microscope analysis (SEM) , infrared spectrum (IR), differential scanning calorimetry (DSC) and in vitro dissolution were used to analyze the optimal process combination. The orthogonal experimental optimization process conditions were set as follows: crystallization temperature 45 degrees C, crystallization pressure 10 MPa, curcumin concentration 8 g x L(-1), solvent flow rate 0.9 mL x min(-1), and CO2 velocity 4 L x min(-1). Under the optimal conditions, the average drug loading and yield of curcumin-EC sustained-release composite particles were 33.01% and 83.97%, and the average particle size of the particles was 20.632 μm. IR and DSC analysis showed that curcumin might complex with EC. The experiments of in vitro dissolution showed that curcumin-EC composite particles had good sustained-release effect. Curcumin-EC sustained-release composite particles can be prepared by supercritical CO2 anti-solvent technology.

Subsurface Nitrogen-Cycling Microbial Communities at Uranium Contaminated Sites in the Colorado River Basin

NASA Astrophysics Data System (ADS)

Cardarelli, E.; Bargar, J.; Williams, K. H.; Dam, W. L.; Francis, C.

2015-12-01

Throughout the Colorado River Basin (CRB), uranium (U) persists as a relic contaminant of former ore processing activities. Elevated solid-phase U levels exist in fine-grained, naturally-reduced zone (NRZ) sediments intermittently found within the subsurface floodplain alluvium of the following Department of Energy-Legacy Management sites: Rifle, CO; Naturita, CO; and Grand Junction, CO. Coupled with groundwater fluctuations that alter the subsurface redox conditions, previous evidence from Rifle, CO suggests this resupply of U may be controlled by microbially-produced nitrite and nitrate. Nitrification, the two-step process of archaeal and bacterial ammonia-oxidation followed by bacterial nitrite oxidation, generates nitrate under oxic conditions. Our hypothesis is that when elevated groundwater levels recede and the subsurface system becomes anoxic, the nitrate diffuses into the reduced interiors of the NRZ and stimulates denitrification, the stepwise anaerobic reduction of nitrate/nitrite to dinitrogen gas. Denitrification may then be coupled to the oxidation of sediment-bound U(IV) forming mobile U(VI), allowing it to resupply U into local groundwater supplies. A key step in substantiating this hypothesis is to demonstrate the presence of nitrogen-cycling organisms in U-contaminated, NRZ sediments from the upper CRB. Here we investigate how the diversity and abundances of nitrifying and denitrifying microbial populations change throughout the NRZs of the subsurface by using functional gene markers for ammonia-oxidation (amoA, encoding the α-subunit of ammonia monooxygenase) and denitrification (nirK, nirS, encoding nitrite reductase). Microbial diversity has been assessed via clone libraries, while abundances have been determined through quantitative polymerase chain reaction (qPCR), elucidating how relative numbers of nitrifiers (amoA) and denitrifiers (nirK, nirS) vary with depth, vary with location, and relate to uranium release within NRZs in sediment cores spanning the upper CRB. Early findings from Rifle, CO indicate elevated abundances of ammonia-oxidizers seem to correlate with elevated uranium concentrations emphasizing the critical need to understand how nitrogen-cycling organisms influence subsurface U redox chemistry and mobility.

An Evaluation of Subsurface Microbial Activity Conditional to Subsurface Temperature, Porosity, and Permeability at North American Carbon Sequestration Sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilson, B.; Mordensky, S.; Verba, Circe

Several nations, including the United States, recognize global climate change as a force transforming the global ecosphere. Carbon dioxide (CO 2) is a greenhouse gas that contributes to the evolving climate. Reduction of atmospheric CO 2 levels is a goal for many nations and carbon sequestration which traps CO 2 in the Earth’s subsurface is one method to reduce atmospheric CO 2 levels. Among the variables that must be considered in developing this technology to a national scale is microbial activity. Microbial activity or biomass can change rock permeability, alter artificial seals around boreholes, and play a key role inmore » biogeochemistry and accordingly may determine how CO 2 is sequestered underground. Certain physical parameters of a reservoir found in literature (e.g., temperature, porosity, and permeability) may indicate whether a reservoir can host microbial communities. In order to estimate which subsurface formations may host microbes, this report examines the subsurface temperature, porosity, and permeability of underground rock formations that have high potential to be targeted for CO 2 sequestration. Of the 268 North American wellbore locations from the National Carbon Sequestration Database (NATCARB; National Energy and Technology Laboratory, 2015) and 35 sites from Nelson and Kibler (2003), 96 sequestration sites contain temperature data. Of these 96 sites, 36 sites have temperatures that would be favorable for microbial survival, 48 sites have mixed conditions for supporting microbial populations, and 11 sites would appear to be unfavorable to support microbial populations. Future studies of microbe viability would benefit from a larger database with more formation parameters (e.g. mineralogy, structure, and groundwater chemistry), which would help to increase understanding of where CO 2 sequestration could be most efficiently implemented.« less

Borehole Muon Detector Development

NASA Astrophysics Data System (ADS)

Bonneville, A.; Flygare, J.; Kouzes, R.; Lintereur, A.; Yamaoka, J. A. K.; Varner, G. S.

2015-12-01

Increasing atmospheric CO2 concentrations have spurred investigation into carbon sequestration methods. One of the possibilities being considered, storing super-critical CO2 in underground reservoirs, has drawn more attention and pilot projects are being supported worldwide. Monitoring of the post-injection fate of CO2 is of utmost importance. Generally, monitoring options are active methods, such as 4D seismic reflection or pressure measurements in monitoring wells. We propose here to develop a 4-D density tomography of subsurface CO2 reservoirs using cosmic-ray muon detectors deployed in a borehole. Muon detection is a relatively mature field of particle physics and there are many muon detector designs, though most are quite large and not designed for subsurface measurements. The primary technical challenge preventing deployment of this technology in the subsurface is the lack of miniaturized muon-tracking detectors capable of fitting in standard boreholes and that will resist the harsh underground conditions. A detector with these capabilities is being developed by a collaboration supported by the U.S. Department of Energy. Current simulations based on a Monte Carlo modeling code predict that the incoming muon angle can be resolved with an error of approximately two degrees, using either underground or sea level spectra. The robustness of the design comes primarily from the use of scintillating rods as opposed to drift tubes. The rods are arrayed in alternating layers to provide a coordinate scheme. Preliminary testing and measurements are currently being performed to test and enhance the performance of the scintillating rods, in both a laboratory and a shallow underground facility. The simulation predictions and data from the experiments will be presented.

Measurement and modeling of CO2 mass transfer in brine at reservoir conditions

NASA Astrophysics Data System (ADS)

Shi, Z.; Wen, B.; Hesse, M. A.; Tsotsis, T. T.; Jessen, K.

2018-03-01

In this work, we combine measurements and modeling to investigate the application of pressure-decay experiments towards delineation and interpretation of CO2 solubility, uptake and mass transfer in water/brine systems at elevated pressures of relevance to CO2 storage operations in saline aquifers. Accurate measurements and modeling of mass transfer in this context are crucial to an improved understanding of the longer-term fate of CO2 that is injected into the subsurface for storage purposes. Pressure-decay experiments are presented for CO2/water and CO2/brine systems with and without the presence of unconsolidated porous media. We demonstrate, via high-resolution numerical calculations in 2-D, that natural convection will complicate the interpretation of the experimental observations if the particle size is not sufficiently small. In such settings, we demonstrate that simple 1-D interpretations can result in an overestimation of the uptake (diffusivity) by two orders of magnitude. Furthermore, we demonstrate that high-resolution numerical calculations agree well with the experimental observations for settings where natural convection contributes substantially to the overall mass transfer process.

Low temperature-pressure batch experiments and field push-pull tests: Assessing potential effects of an unintended CO2 release from CCUS projects on groundwater chemistry

NASA Astrophysics Data System (ADS)

Mickler, P. J.; Yang, C.; Lu, J.; Reedy, R. C.; Scanlon, B. R.

2012-12-01

Carbon Capture Utilization and Storage projects (CCUS), where CO2 is captured at point sources such as power stations and compressed into a supercritical liquid for underground storage, has been proposed to reduce atmospheric CO2 and mitigate global climate change. Problems may arise from CO2 releases along discreet pathways such as abandoned wells and faults, upwards and into near surface groundwater. Migrating CO2 may inversely impact fresh water resources by increasing mineral solubility and dissolution rates and mobilizing harmful trace elements including As and Pb. This study addresses the impacts on fresh water resources through a combination of laboratory batch experiments, where aquifer sediment are reacted in their corresponding groundwater in 100% CO2 environments, and field push-pull tests where groundwater is equilibrated with 100% CO2, reacted in-situ in the groundwater system, and pulled out for analyses. Batch experiments were performed on aquifer material from carbonate dominated, mixed carbonate/silicalstic, and siliclastic dominated systems. A mixed silicalstic/carbonate system was chosen for the field based push-pull test. Batch experiment results suggest carbonate dissolution increased the concentration of Ca, Mg, Sr, Ba, Mn, U and HCO3- in groundwater. In systems with significant carbonate content, dissolution continued until carbonate saturation was achieved at approximately 1000 hr. Silicate dissolution increased the conc. of Si, K Ni and Co, but at much lower rates than carbonate dissolution. The elements As, Mo, V, Zn, Se and Cd generally show similar behavior where concentrations initially increase but soon drop to levels at or below the background concentrations (~48 hours). A Push-Pull test on one aquifer system produced similar geochemical behavior but observed reaction rates are higher in batch experiments relative to push-pull tests. Release of CO2 from CCUS sites into overlying aquifer systems may adversely impact groundwater quality primarily through carbonate dissolution which releases Ca and elements that substitute for Ca in crystal lattices. Silicate weathering releases primarily Si and K at lower rates. Chemical changes with the addition of CO2 may initially mobilize As, Mo, V, Zn, Se and Cd but these elements become immobile in the lowered pH water and sorb onto aquifer minerals. A combined laboratory batch experiment and field push-pull test in fresh water aquifers overlying CCUS projects will best characterize the response of the aquifer to increased pCO2. The long experimental duration of the batch experiments may allow reactions to reach equilibrium however; reaction rates may be artificially high due to increased mineral surface areas. Field based push-pull tests offer a more realistic water rock ratio and test a much larger volume of aquifer material but the test must be shorter in duration because the high pCO2 water is subject to mixing with low pCO2 background water and migration away from the test well with groundwater flow. A comparison of the two methods best characterizes the potential effects on groundwater chemistry

Influence of acidic and alkaline waste solution properties on uranium migration in subsurface sediments.

PubMed

Szecsody, Jim E; Truex, Mike J; Qafoku, Nikolla P; Wellman, Dawn M; Resch, Tom; Zhong, Lirong

2013-08-01

This study shows that acidic and alkaline wastes co-disposed with uranium into subsurface sediments have significant impact on changes in uranium retardation, concentration, and mass during downward migration. For uranium co-disposal with acidic wastes, significant rapid (i.e., hours) carbonate and slow (i.e., 100 s of hours) clay dissolution resulted, releasing significant sediment-associated uranium, but the extent of uranium release and mobility change was controlled by the acid mass added relative to the sediment proton adsorption capacity. Mineral dissolution in acidic solutions (pH2) resulted in a rapid (<10 h) increase in aqueous carbonate (with Ca(2+), Mg(2+)) and phosphate and a slow (100 s of hours) increase in silica, Al(3+), and K(+), likely from 2:1 clay dissolution. Infiltration of uranium with a strong acid resulted in significant shallow uranium mineral dissolution and deeper uranium precipitation (likely as phosphates and carbonates) with downward uranium migration of three times greater mass at a faster velocity relative to uranium infiltration in pH neutral groundwater. In contrast, mineral dissolution in an alkaline environment (pH13) resulted in a rapid (<10h) increase in carbonate, followed by a slow (10 s to 100 s of hours) increase in silica concentration, likely from montmorillonite, muscovite, and kaolinite dissolution. Infiltration of uranium with a strong base resulted in not only uranium-silicate precipitation (presumed Na-boltwoodite) but also desorption of natural uranium on the sediment due to the high ionic strength solution, or 60% greater mass with greater retardation compared with groundwater. Overall, these results show that acidic or alkaline co-contaminant disposal with uranium can result in complex depth- and time-dependent changes in uranium dissolution/precipitation reactions and uranium sorption, which alter the uranium migration mass, concentration, and velocity. Copyright © 2013 Elsevier B.V. All rights reserved.

The Numerical Simulation of a Tracer-Release Field Project to Study Motion within the Nocturnal Boundary Layer

NASA Astrophysics Data System (ADS)

Werth, D. W.; Leclerc, M. Y.; Buckley, R.; Parker, M.; Kurzeja, R.; Duarte, H. F.; Zhang, G.; Durden, D.

2009-12-01

The Savannah River National Laboratory (SRNL), Brookhaven National Laboratory (BNL), the University of Georgia (UGA), and the National Oceanic and Atmospheric Administration (NOAA) conducted a regional tracer experiment to study the nocturnal behavior of CO2 in the vicinity of an instrumented tall tower during two nights on May 11th and 12th, 2009. The experiment consisted of a release of five perfluorocarbon tracer (PFTs) compounds in twelve unique locations in Aiken County, South Carolina. Intensive meteorological measurements including in-situ turbulence were made in conjunction with the release and sampling of the PFTs. A 300m tower was also used to collect data from higher levels, allowing us to determine the extent to which the tracer was mixed vertically. Lagrangian plume simulations performed during the experiment demonstrated transport over distances of >8 km, and correlated well with in situ sampling. The area was characterized by heavy vegetation cover, and carbon dioxide concentrations were also monitored in an effort to determine how respiration and advection affect CO2 levels in the stable layer. Tracer release locations were carefully selected via a fine-scale mesoscale modeling study of similar nights. The purpose of these experiments was to provide data that will be used to increase the understanding of the terrestrial carbon budget, especially with respect to nocturnal boundary layer (NBL) phenomena such as low level jets and breaking gravity waves. Using these data, a simulation of the motion of the tracer within the boundary layer was developed using the Regional Atmospheric Modeling System (RAMS) mesoscale model coupled to a tracer model. The RAMS model was also coupled to the Simple Biosphere (SiB) vegetation model, which allowed for the simulation of the release of carbon dioxide into the NBL. The simulation results are used to validate the NBL hypothesis of CO2 monitoring, by which the release of CO2 can be correlated with the accumulation of CO2 in the boundary layer beneath a stable ‘lid’, which impedes vertical mixing. This is done with both the tracer, in which the release rate is known and no advection occurs, and for CO2, in which the release rate is not known and for which advection of CO2 must be accounted. The high resolution of the simulation allows us to resolve the small-scale motions within the NBL, which are important to nocturnal transport. Flux data from the tall tower were studied to learn more about the eddy transport, and also to detect the occurrence of transport ‘events’ in which the CO2 and H2O values experience a sudden increase. A wavelet analysis is also applied, and reveals the existence of eddy activity dominated by eddies of diameter 90-240m.

Characterizing Microbial Diversity and Function in Natural Subsurface CO2 Reservoir Systems for Applied Use in Geologic Carbon Sequestration Environments

NASA Astrophysics Data System (ADS)

Freedman, A.; Thompson, J. R.

2013-12-01

The injection of CO2 into geological formations at quantities necessary to significantly reduce CO2 emissions will represent an environmental perturbation on a continental scale. The extent to which biological processes may play a role in the fate and transport of CO2 injected into geological formations has remained an open question due to the fact that at temperatures and pressures associated with reservoirs targeted for sequestration CO2 exists as a supercritical fluid (scCO2), which has generally been regarded as a sterilizing agent. Natural subsurface accumulations of CO2 serve as an excellent analogue for studying the long-term effects, implications and benefits of CO2 capture and storage (CCS). While several geologic formations bearing significant volumes of nearly pure scCO2 phases have been identified in the western United States, no study has attempted to characterize the microbial community present in these systems. Because the CO2 in the region is thought to have first accumulated millions of years ago, it is reasonable to assume that native microbial populations have undergone extensive and unique physiological and behavioral adaptations to adjust to the exceedingly high scCO2 content. Our study focuses on the microbial communities associated with the dolomite limestone McElmo Dome scCO2 Field in the Colorado Plateau region, approximately 1,000 m below the surface. Fluid samples were collected from 10 wells at an industrial CO2 production facility outside Cortez, CO. Subsamples preserved on site in 3.7% formaldehyde were treated in the lab with Syto 9 green-fluorescent nucleic acid stain, revealing 3.2E6 to 1.4E8 microbial cells per liter of produced fluid and 8.0E9 cells per liter of local pond water used in well drilling fluids. Extracted DNAs from sterivex 0.22 um filters containing 20 L of sample biomass were used as templates for PCR targeting the 16S rRNA gene. 16S rRNA amplicons from these samples were cloned, sequenced and subjected to microbial community analysis to test the hypothesis that a low but non-zero diversity that includes taxa from other subsurface environments will be present, reflecting the extreme ecological selective pressures of scCO2. A wide range of phylogenies have been identified, including genera that fall within the Proteobacteria, Bacilli, and Clostridial classes. Several species identified by 16S BLAST best hits are also known to inhabit deep subsurface environments, preliminarily confirming that a non-zero diversity has been able to survive, and possibly thrive, in the extreme scCO2-exposed deep subsurface environment at McElmo Dome. It thus appears that at least a subsection of native subsurface community biota may withstand the severe stresses associated with the injection of scCO2 for long-term geologic carbon sequestration efforts.

Amidine-Functionalized Poly(2-vinyl-4,4-dimethylazlactone) for Selective and Efficient CO 2 Fixing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barkakaty, Balaka; Browning, Katie L.; Sumpter, Bobby

Development of novel polymeric materials capable of efficient CO 2 capture and separation under ambient conditions is crucial for cost-effective and practical industrial applications. Here we report the facile synthesis of a new CO 2-responsive polymer through post-polymerization modification of poly(2 vinyl-4,4-dimethylazlactone) (PVDMA). The reactive pendant azlactone groups of PVDMA are easily modified with 4-(N-methyltetrahydropyrimidine) benzyl alcohol (PBA) without any by-product formation. FTIR and TGA experiments show the new PBA functionalized polymer powder can reversibly capture CO 2 at room temperature and under atmospheric pressure. CO2 capture was selective, showing a high fixing efficiency even with a mixed gas systemmore » (20% CO 2, 80% N 2) similar to flue gas. CO 2 release occurred at room temperature and release profiles were investigated as a function of temperature. Density Functional Theory (DFT) calculations coupled with modeling and simulation reveal the presence of two CO 2 binding sites in the PBA functionalized polymer resulting in a two-step CO 2 release at room temperature. Finally, we find that the ease of material preparation, high fixing efficiency, and robust release characteristics suggest that post-polymerization modification may be a useful route to designing new materials for CO 2 capture.« less

Amidine-Functionalized Poly(2-vinyl-4,4-dimethylazlactone) for Selective and Efficient CO 2 Fixing

DOE PAGES

Barkakaty, Balaka; Browning, Katie L.; Sumpter, Bobby; ...

2016-02-12

Development of novel polymeric materials capable of efficient CO 2 capture and separation under ambient conditions is crucial for cost-effective and practical industrial applications. Here we report the facile synthesis of a new CO 2-responsive polymer through post-polymerization modification of poly(2 vinyl-4,4-dimethylazlactone) (PVDMA). The reactive pendant azlactone groups of PVDMA are easily modified with 4-(N-methyltetrahydropyrimidine) benzyl alcohol (PBA) without any by-product formation. FTIR and TGA experiments show the new PBA functionalized polymer powder can reversibly capture CO 2 at room temperature and under atmospheric pressure. CO2 capture was selective, showing a high fixing efficiency even with a mixed gas systemmore » (20% CO 2, 80% N 2) similar to flue gas. CO 2 release occurred at room temperature and release profiles were investigated as a function of temperature. Density Functional Theory (DFT) calculations coupled with modeling and simulation reveal the presence of two CO 2 binding sites in the PBA functionalized polymer resulting in a two-step CO 2 release at room temperature. Finally, we find that the ease of material preparation, high fixing efficiency, and robust release characteristics suggest that post-polymerization modification may be a useful route to designing new materials for CO 2 capture.« less

In Situ Oxalic Acid Injection to Accelerate Arsenic Remediation at a Superfund Site in New Jersey.

PubMed

Wovkulich, Karen; Stute, Martin; Mailloux, Brian J; Keimowitz, Alison R; Ross, James; Bostick, Benjamin; Sun, Jing; Chillrud, Steven N

2014-09-25

Arsenic is a prevalent contaminant at a large number of US Superfund sites; establishing techniques that accelerate As remediation could benefit many sites. Hundreds of tons of As were released into the environment by the Vineland Chemical Co. in southern New Jersey during its manufacturing lifetime (1949-1994), resulting in extensive contamination of surface and subsurface soils and sediments, groundwater, and the downstream watershed. Despite substantial intervention at this Superfund site, sufficient aquifer cleanup could require many decades if based on traditional pump and treat technologies only. Laboratory column experiments have suggested that oxalic acid addition to contaminated aquifer solids could promote significant As release from the solid phase. To evaluate the potential of chemical additions to increase As release in situ and boost treatment efficiency, a forced gradient pilot scale study was conducted on the Vineland site. During spring/summer 2009, oxalic acid and bromide tracer were injected into a small portion (~50 m 2 ) of the site for 3 months. Groundwater samples indicate that introduction of oxalic acid led to increased As release. Between 2.9 and 3.6 kg of As were removed from the sampled wells as a result of the oxalic acid treatment during the 3-month injection. A comparison of As concentrations on sediment cores collected before and after treatment and analyzed using X-ray fluorescence spectroscopy suggested reduction in As concentrations of ~36% (median difference) to 48% (mean difference). While further study is necessary, the addition of oxalic acid shows potential for accelerating treatment of a highly contaminated site and decreasing the As remediation time-scale.

Integrated Monitoring and Modeling of Carbon Dioxide Leakage Risk Using Remote Sensing, Ground-Based Monitoring, Atmospheric Models and Risk-Indexing Tools

NASA Astrophysics Data System (ADS)

Burton, E. A.; Pickles, W. L.; Gouveia, F. J.; Bogen, K. T.; Rau, G. H.; Friedmann, J.

2006-12-01

Correct assessment of the potential for CO2 leakage to the atmosphere or near surface is key to managing the risk associated with CO2 storage. Catastrophic, point-source leaks, diffuse seepage, and low leakage rates all merit assessment. Smaller leaks may be early warnings of catastrophic failures, and may be sufficient to damage natural vegetation or crops. Small leaks also may lead to cumulative build-up of lethal levels of CO2 in enclosed spaces, such as basements, groundwater-well head spaces, and caverns. Working with our ZERT partners, we are integrating a variety of monitoring and modeling approaches to understand how to assess potential health, property and environmental risks across this spectrum of leakage types. Remote sensing offers a rapid technique to monitor large areas for adverse environmental effects. If it can be deployed prior to the onset of storage operations, remote sensing also can document baseline conditions against which future claims of environmental damage can be compared. LLNL has been using hyperspectral imaging to detect plant stress associated with CO2 gas leakage, and has begun investigating use of NASA's new satellite or airborne instrumentation that directly measures gas compositions in the atmosphere. While remote sensing techniques have been criticized as lacking the necessary resolution to address environmental problems, new instruments and data processing techniques are demonstrated to resolve environmental changes at the scale associated with gas-leakage scenarios. During the shallow low-flow- CO2 release field experiments planned by ZERT, for the first time, we will have the opportunity to ground- truth hyperspectral data by simultaneous measurement of changes in hyperspectral readings, soil and root zone microbiology, ambient air, soil and aquifer CO2 concentrations. When monitoring data appear to indicate a CO2 leakage event, risk assessment and mitigation of that event requires a robust and nearly real-time method for estimating its associated risk, spatially and temporally. This requires integration of subsurface, surface and atmospheric data and models. To date, we have developed techniques to map risk based on predicted atmospheric plumes and GIS/MT (meteorologic- topographic) risk-indexing tools. This methodology was derived from study of large CO2 releases from an abandoned well penetrating a natural CO2 reservoir at Crystal Geyser, Utah. This integrated approach will provide a powerful tool to screen for high-risk zones at proposed sequestration sites, to design and optimize surface networks for site monitoring and/or to guide setting science-based regulatory compliance requirements for monitoring sequestration sites, as well as to target critical areas for first responders should a catastrophic-release event occur. This work was performed under the auspices of the U.S. Dept. of Energy by University of California, Lawrence Livermore National Laboratory under Contract W-7405-Eng-48.

CO2-Water-Rock Wettability: Variability, Influencing Factors, and Implications for CO2 Geostorage.

PubMed

Iglauer, Stefan

2017-05-16

Carbon geosequestration (CGS) has been identified as a key technology to reduce anthropogenic greenhouse gas emissions and thus significantly mitigate climate change. In CGS, CO 2 is captured from large point-source emitters (e.g., coal fired power stations), purified, and injected deep underground into geological formations for disposal. However, the CO 2 has a lower density than the resident formation brine and thus migrates upward due to buoyancy forces. To prevent the CO 2 from leaking back to the surface, four trapping mechanisms are used: (1) structural trapping (where a tight caprock acts as a seal barrier through which the CO 2 cannot percolate), (2) residual trapping (where the CO 2 plume is split into many micrometer-sized bubbles, which are immobilized by capillary forces in the pore network of the rock), (3) dissolution trapping (where CO 2 dissolves in the formation brine and sinks deep into the reservoir due to a slight increase in brine density), and (4) mineral trapping (where the CO 2 introduced into the subsurface chemically reacts with the formation brine or reservoir rock or both to form solid precipitates). The efficiency of these trapping mechanisms and the movement of CO 2 through the rock are strongly influenced by the CO 2 -brine-rock wettability (mainly due to the small capillary-like pores in the rock which form a complex network), and it is thus of key importance to rigorously understand CO 2 -wettability. In this context, a substantial number of experiments have been conducted from which several conclusions can be drawn: of prime importance is the rock surface chemistry, and hydrophilic surfaces are water-wet while hydrophobic surfaces are CO 2 -wet. Note that CO 2 -wet surfaces dramatically reduce CO 2 storage capacities. Furthermore, increasing pressure, salinity, or dissolved ion valency increases CO 2 -wettability, while the effect of temperature is not well understood. Indeed theoretical understanding of CO 2 -wettability and the ability to quantitatively predict it are currently limited although recent advances have been made. Moreover, data for real storage rock and real injection gas (which contains impurities) is scarce and it is an open question how realistic subsurface conditions can be reproduced in laboratory experiments. In conclusion, however, it is clear that in principal CO 2 -wettability can vary drastically from completely water-wet to almost completely CO 2 -wet, and this possible variation introduces a large uncertainty into trapping capacity and containment security predictions.

Large temporal scale and capacity subsurface bulk energy storage with CO2

NASA Astrophysics Data System (ADS)

Saar, M. O.; Fleming, M. R.; Adams, B. M.; Ogland-Hand, J.; Nelson, E. S.; Randolph, J.; Sioshansi, R.; Kuehn, T. H.; Buscheck, T. A.; Bielicki, J. M.

2017-12-01

Decarbonizing energy systems by increasing the penetration of variable renewable energy (VRE) technologies requires efficient and short- to long-term energy storage. Very large amounts of energy can be stored in the subsurface as heat and/or pressure energy in order to provide both short- and long-term (seasonal) storage, depending on the implementation. This energy storage approach can be quite efficient, especially where geothermal energy is naturally added to the system. Here, we present subsurface heat and/or pressure energy storage with supercritical carbon dioxide (CO2) and discuss the system's efficiency, deployment options, as well as its advantages and disadvantages, compared to several other energy storage options. CO2-based subsurface bulk energy storage has the potential to be particularly efficient and large-scale, both temporally (i.e., seasonal) and spatially. The latter refers to the amount of energy that can be stored underground, using CO2, at a geologically conducive location, potentially enabling storing excess power from a substantial portion of the power grid. The implication is that it would be possible to employ centralized energy storage for (a substantial part of) the power grid, where the geology enables CO2-based bulk subsurface energy storage, whereas the VRE technologies (solar, wind) are located on that same power grid, where (solar, wind) conditions are ideal. However, this may require reinforcing the power grid's transmission lines in certain parts of the grid to enable high-load power transmission from/to a few locations.

3-D loaded scaffolds obtained by supercritical CO2 assisted process

NASA Astrophysics Data System (ADS)

Cardea, S.; Reverchon, E.

2014-08-01

In this work, a supercritical CO2 (SC-CO2) drying process for the formation of 3-D PVDF-HFP loaded scaffolds was tested. Experiments at pressures ranging between 150 and 250 bar and at temperatures ranging between 35 and 55°C were performed. The PVDF-HFP- acetone-ethanol solution at 15% w/w polymer was selected as the base case. The drug (amoxicillin) concentration was varied from 20 to 30% w/w with respect to PVDF-HFP. SC- CO2 drying process was confirmed to be a valid alternative to generate loaded structures; indeed, scaffolds characterized by nanometric networks (with mean pore diameter of about 300 nm) with a homogeneous drug distribution were obtained. Drug controlled release experiments were also performed and a quasi-zero order release kinetic was observed.

Multi-Spectral imaging of vegetation for detecting CO2 leaking from underground

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rouse, J.H.; Shaw, J.A.; Lawrence, R.L.

2010-06-01

Practical geologic CO{sub 2} sequestration will require long-term monitoring for detection of possible leakage back into the atmosphere. One potential monitoring method is multi-spectral imaging of vegetation reflectance to detect leakage through CO{sub 2}-induced plant stress. A multi-spectral imaging system was used to simultaneously record green, red, and near-infrared (NIR) images with a real-time reflectance calibration from a 3-m tall platform, viewing vegetation near shallow subsurface CO{sub 2} releases during summers 2007 and 2008 at the Zero Emissions Research and Technology field site in Bozeman, Montana. Regression analysis of the band reflectances and the Normalized Difference Vegetation Index with timemore » shows significant correlation with distance from the CO{sub 2} well, indicating the viability of this method to monitor for CO{sub 2} leakage. The 2007 data show rapid plant vigor degradation at high CO{sub 2} levels next to the well and slight nourishment at lower, but above-background CO{sub 2} concentrations. Results from the second year also show that the stress response of vegetation is strongly linked to the CO{sub 2} sink-source relationship and vegetation density. The data also show short-term effects of rain and hail. The real-time calibrated imaging system successfully obtained data in an autonomous mode during all sky and daytime illumination conditions.« less

A new tracer experiment to estimate the methane emissions from a dairy cow shed using sulfur hexafluoride (SF6)

NASA Astrophysics Data System (ADS)

Marik, Thomas; Levin, Ingeborg

1996-09-01

Methane emission from livestock and agricultural wastes contribute globally more than 30% to the anthropogenic atmospheric methane source. Estimates of this number have been derived from respiration chamber experiments. We determined methane emission rates from a tracer experiment in a modern cow shed hosting 43 dairy cows in their accustomed environment. During a 24-hour period the concentrations of CH4, CO2, and SF6, a trace gas which has been released at a constant rate into the stable air, have been measured. The ratio between SF6 release rate and measured SF6 concentration was then used to estimate the ventilation rate of the stable air during the course of the experiment. The respective ratio between CH4 or CO2 and SF6 concentration together with the known SF6 release rate allows us to calculate the CH4 (and CO2) emissions in the stable. From our experiment we derive a total daily mean CH4 emission of 441 LSTP per cow (9 cows nonlactating), which is about 15% higher than previous estimates for German cows with comparable milk production obtained during respiration chamber experiments. The higher emission in our stable experiment is attributed to the contribution of CH4 release from about 50 m3 of liquid manure present in the cow shed in underground channels. Also, considering measurements we made directly on a liquid manure tank, we obtained an estimate of the total CH4 production from manure: The normalized contribution of methane from manure amounts to 12-30% of the direct methane release of a dairy cow during rumination. The total CH4 release per dairy cow, including manure, is 521-530 LSTP CH4 per day.

Detectability of Wellbore CO2 Leakage using the Magnetotelluric Method

NASA Astrophysics Data System (ADS)

Yang, X.; Buscheck, T. A.; Mansoor, K.; Carroll, S.

2016-12-01

We assessed the effectiveness of the magnetotelluric (MT) method in detecting CO2 and brine leakage through a wellbore, which penetrates a CO2 storage reservoir, into overlying aquifers, 0 to 1720 m in depth, in support of the USDOE National Risk Assessment Partnership (NRAP) monitoring program. Synthetic datasets based on the Kimberlina site in the southern San Joaquin Basin, California were created using CO2 storage reservoir models, wellbore leakage models, and groundwater/geochemical models of the overlying aquifers. The species concentrations simulated with the groundwater/geochemical models were converted into bulk electrical conductivity (EC) distributions as the MT model input. Brine and CO2 leakage into the overlying aquifers increases ion concentrations, and thus results in an EC increase, which may be detected by the MT method. Our objective was to estimate and maximize the probability of leakage detection using the MT method. The MT method is an electromagnetic geophysical technique that images the subsurface EC distribution by measuring natural electric and magnetic fields in the frequency range from 0.01 Hz to 1 kHz with sensors on the ground surface. The ModEM software was used to predict electromagnetic responses from brine and CO2 leakage and to invert synthetic MT data for recovery of subsurface conductivity distribution. We are in the process of building 1000 simulations for ranges of permeability, leakage flux, and hydraulic gradient to study leakage detectability and to develop an optimization method to answer when, where and how an MT monitoring system should be deployed to maximize the probability of leakage detection. This work was sponsored by the USDOE Fossil Energy, National Energy Technology Laboratory, managed by Traci Rodosta and Andrea McNemar. This work was performed under the auspices of the USDOE by LLNL under contract DE-AC52-07NA27344. LLNL IM release number is LLNL-ABS-699276.

Kinetic Release of Alkalinity from Particle-Containing Oil-in-Water Emulsions

NASA Astrophysics Data System (ADS)

Muller, K.; Chapra, S. C.; Ramsburg, A.

2014-12-01

Oil-in-water emulsions are typically employed during remediation to promote biotic reduction of contaminants. Emulsions, however, hold promise for encapsulated delivery of many types of active ingredients required for successful site remediation or long-term site stewardship. Our research is currently focused on using alkalinity-containing particles held within oil-in-water emulsions to sustain control of subsurface pH. Here we describe results from laboratory experiments and mathematical modeling conducted to quantify the kinetics associated with the emulsion delivery and alkalinity release process. Kinetically stable oil-in-water emulsions containing (~60 nmCaCO3 or ~100 nm MgO particles) were previously developed using soybean oil and Gum Arabic as a stabilizing agent. Batch and column experiments were employed to assess the accessibility and release of the alkalinity from the emulsion. Successive additions of HCl were used in batch systems to produce several pH responses (pH rebounds) that were subsequently modeled to elucidate release mechanisms and rates for varying emulsion compositions and particle types. Initial results suggest that a linear-driving-force model is generally able to capture the release behavior in the batch system when the temporally-constant, lumped mass-transfer coefficient is scaled by the fraction of particle mass remaining within the droplets. This result suggests that the rate limiting step in the release process may be the interphase transfer of reactive species at the oil-water interface. 1-d column experiments were also completed in order to quantify the extent and rate of alkalinity release from emulsion droplets retained in a sandy medium. Alkalinity release from the retained droplets treated a pH 4 influent water for 25-60 pore volumes (the duration depended on particle type and mass loading), and the cessation in treatment corresponded to exhaustion of the particle mass held within the oil. Column experiments were simulated using a transport code containing the linear-driving-force expression evaluated in the batch experiments. In these simulations the lumped mass transfer coefficient was fit and compared with values predicted using existing correlations for liquid-liquid and solid-liquid interfaces in porous media.

Biological instrumentation for the Viking 1975 mission to Mars.

PubMed

Klein, H P; Vishniac, W

1972-01-01

A brief introduction is given on why Mars is of interest from a biological point of view, along with an overview of the Viking 1975 mission. Details are given about the four biology instruments aboard the spacecraft and the experiments for which they are to be used. These are: the carbon assimilation experiment to determine whether the soil is biologically active, by incubation in presence of 14C-labelled CO and CO2 (known to be present in the Martian atmosphere); the label release experiment to detect metabolic activity by the release of radioactive CO2, from 14C-labelled simple organic substrates; the gas exchange experiment to detect biological activity by repeated gas chromatography analysis of soil samples; the light scattering experiment, where increase of scattering and decrease of light transmission would indicate the growth of organisms. Examples are given of data obtained with terrestrial soils in these experiments.

Muon borehole detector development for use in four-dimensional tomographic density monitoring

NASA Astrophysics Data System (ADS)

Flygare, Joshua

The increase of CO2 concentrations in the atmosphere and the correlated temperature rise has initiated research into methods of carbon sequestration. One promising possibility is to store CO2 in subsurface reservoirs of porous rock. After injection, the monitoring of the injected CO2 is of paramount importance because the CO2 plume, if escaped, poses health and environmental risks. Traditionally, seismic reflection methods are the chosen method of determining changes in the reservoir density due to CO2 injection, but this is expensive and not continuous. A potential and promising alternative is to use cosmic muon tomography to determine density changes in the reservoir over a period of time. The work I have completed was the development of a muon detector that will be capable of being deployed in boreholes and perform long-term tomography of the reservoir of interest. The detector has the required dimensions, an angular resolution of approximately 2 degrees, and is robust enough to survive the caustic nature of the fluids in boreholes, as well as temperature and pressure fluctuations. The detector design is based on polystyrene scintillating rods arrayed in alternating layers. The layers, as arranged, can provide four-dimensional (4D) tomographic data to detect small changes in density at depths up to approximately 2 kilometers. Geant4, a Monte Carlo simulation code, was used to develop and optimize the detector design. Additionally, I developed a method of determining the muon flux at depth, including CO2 saturation changes in subsurface reservoirs. Preliminary experiments were performed at Pacific Northwest National Laboratory. This thesis will show the simulations I performed to determine the angular resolution and background discrimination required of the detector, the experiments to determine light transport through the polystyrene scintillating rods and fibers, and the method developed to predict muon flux changes at depth expected after injection.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Friedmann, S J

Carbon capture and sequestration (CCS) has emerged as a key technology for dramatic short-term reduction in greenhouse gas emissions in particular from large stationary. A key challenge in this arena is the monitoring and verification (M&V) of CO2 plumes in the deep subsurface. Towards that end, we have developed a tool that can simultaneously invert multiple sub-surface data sets to constrain the location, geometry, and saturation of subsurface CO2 plumes. We have focused on a suite of unconventional geophysical approaches that measure changes in electrical properties (electrical resistance tomography, electromagnetic induction tomography) and bulk crustal deformation (til-meters). We had alsomore » used constraints of the geology as rendered in a shared earth model (ShEM) and of the injection (e.g., total injected CO{sub 2}). We describe a stochastic inversion method for mapping subsurface regions where CO{sub 2} saturation is changing. The technique combines prior information with measurements of injected CO{sub 2} volume, reservoir deformation and electrical resistivity. Bayesian inference and a Metropolis simulation algorithm form the basis for this approach. The method can (a) jointly reconstruct disparate data types such as surface or subsurface tilt, electrical resistivity, and injected CO{sub 2} volume measurements, (b) provide quantitative measures of the result uncertainty, (c) identify competing models when the available data are insufficient to definitively identify a single optimal model and (d) rank the alternative models based on how well they fit available data. We present results from general simulations of a hypothetical case derived from a real site. We also apply the technique to a field in Wyoming, where measurements collected during CO{sub 2} injection for enhanced oil recovery serve to illustrate the method's performance. The stochastic inversions provide estimates of the most probable location, shape, volume of the plume and most likely CO{sub 2} saturation. The results suggest that the method can reconstruct data with poor signal to noise ratio and use hard constraints available from many sites and applications. External interest in the approach and method is high, and already commercial and DOE entities have requested technical work using the newly developed methodology for CO{sub 2} monitoring.« less

Sampling Soil CO2 for Isotopic Flux Partitioning: Non Steady State Effects and Methodological Biases

NASA Astrophysics Data System (ADS)

Snell, H. S. K.; Robinson, D.; Midwood, A. J.

2014-12-01

Measurements of δ13C of soil CO2 are used to partition the surface flux into autotrophic and heterotrophic components. Models predict that the δ13CO2 of the soil efflux is perturbed by non-steady state (NSS) diffusive conditions. These could be large enough to render δ13CO2 unsuitable for accurate flux partitioning. Field studies sometimes find correlations between efflux δ13CO2 and flux or temperature, or that efflux δ13CO2 is not correlated as expected with biological drivers. We tested whether NSS effects in semi-natural soil were comparable with those predicted. We compared chamber designs and their sensitivity to changes in efflux δ13CO2. In a natural soil mesocosm, we controlled temperature to generate NSS conditions of CO2 production. We measured the δ13C of soil CO2 using in situ probes to sample the subsurface, and dynamic and forced-diffusion chambers to sample the surface efflux. Over eight hours we raised soil temperature by 4.5 OC to increase microbial respiration. Subsurface CO2 concentration doubled, surface efflux became 13C-depleted by 1 ‰ and subsurface CO2 became 13C-enriched by around 2 ‰. Opposite changes occurred when temperature was lowered and CO2 production was decreasing. Different chamber designs had inherent biases but all detected similar changes in efflux δ13CO2, which were comparable to those predicted. Measurements using dynamic chambers were more 13C-enriched than expected, probably due to advection of CO2 into the chamber. In the mesocosm soil, δ13CO2 of both efflux and subsurface was determined by physical processes of CO2 production and diffusion. Steady state conditions are unlikely to prevail in the field, so spot measurements of δ13CO2 and assumptions based on the theoretical 4.4 ‰ diffusive fractionation will not be accurate for estimating source δ13CO2. Continuous measurements could be integrated over a period suitable to reduce the influence of transient NSS conditions. It will be difficult to disentangle biologically driven changes in soil δ13CO2 from physical controls, particularly as they occur on similar timescales and are driven by the same environmental variables, such as temperature, moisture and daylight.

Detecting potential impacts of deep subsurface CO2 injection on shallow drinking water

NASA Astrophysics Data System (ADS)

Smyth, R. C.; Yang, C.; Romanak, K.; Mickler, P. J.; Lu, J.; Hovorka, S. D.

2012-12-01

Presented here are results from one aspect of collective research conducted at Gulf Coast Carbon Center, BEG, Jackson School at UT Austin. The biggest hurdle to public acceptance of CCS is to show that drinking water resources will not be impacted. Since late 1990s our group has been supported by US DOE NETL and private industry to research how best to detect potential impacts to shallow (0 to ~0.25 km) subsurface drinking water from deep (~1 to 3.5 km) injection of CO2. Work has and continues to include (1) field sampling and testing, (2) laboratory batch experiments, (3) geochemical modeling. The objective has been to identify the most sensitive geochemical indicators using data from research-level investigations, which can be economically applied on an industrial-scale. The worst-case scenario would be introduction of CO2 directly into drinking water from a leaking wellbore at a brownfield site. This is unlikely for a properly screened and/or maintained site, but needs to be considered. Our results show aquifer matrix (carbonate vs. clastic) to be critical to interpretation of pH and carbonate (DIC, Alkalinity, and δ13C of DIC) parameters because of the influence of water-rock reaction (buffering vs. non-buffering) on aqueous geochemistry. Field groundwater sampling sites to date are Cranfield, MS and SACROC, TX CO2-EOR oilfields. Two major aquifer types are represented, one dominated by silicate (Cranfield) and the other by carbonate (SACROC) water-rock reactions. We tested sensitivity of geochemical indicators (pH, DIC, Alkalinity, and δ13C of DIC) by modeling the effects of increasing pCO2 on aqueous geochemistry, and laboratory batch experiments, both with partial pressure of CO2 gas (pCO2) at 1x105 Pa (1 atm). Aquifer matrix and groundwater data provided constraints for the geochemical models. We used results from modeling and batch experiments to rank geochemical parameter sensitivity to increased pCO2 into weakly, mildly and strongly sensitive categories for both aquifer systems. DIC concentration is strongly sensitive to increased pCO2 for both aquifers; however, CO2 outgassing during sampling complicates direct field measurement of DIC. Interpretation of data from in-situ push-pull aquifer tests is ongoing and will be used to augment results summarized here. We are currently designing groundwater monitoring plans for two additional industrial-scale sites where we will further test the sensitivity and utility of our sampling approach.

Simple dielectric mixing model in the monitoring of CO2 leakage from geological storage aquifer

NASA Astrophysics Data System (ADS)

Abidoye, L. K.; Bello, A. A.

2017-03-01

The principle of the dielectric mixing for multiphase systems in porous media has been employed to investigate CO2-water-porous media system and monitor the leakage of CO2, in analogy to scenarios that can be encountered in geological carbon sequestration. A dielectric mixing model was used to relate the relative permittivity for different subsurface materials connected with the geological carbon sequestration. The model was used to assess CO2 leakage and its upward migration, under the influences of the depth-dependent characteristics of the subsurface media as well as the fault-connected aquifers. The results showed that for the upward migration of CO2 in the subsurface, the change in the bulk relative permittivity (εb) of the CO2-water-porous media system clearly depicts the leakage and movement of CO2, especially at depth shallower than 800 m. At higher depth, with higher pressure and temperature, the relative permittivity of CO2 increases with pressure, while that of water decreases with temperature. These characteristics of water and supercritical CO2, combine to limit the change in the εb, at higher depth. Furthermore, it was noted that if the pore water was not displaced by the migrating CO2, the presence of CO2 in the system increases the εb. But, with the displacement of pore water by the migrating CO2, it was shown how the εb profile decreases with time. Owing to its relative simplicity, composite dielectric behaviour of multiphase materials can be effectively deployed for monitoring and enhancement of control of CO2 movement in the geological carbon sequestration.

High CO2 subsurface environment enriches for novel microbial lineages capable of autotrophic carbon fixation

NASA Astrophysics Data System (ADS)

Probst, A. J.; Jerett, J.; Castelle, C. J.; Thomas, B. C.; Sharon, I.; Brown, C. T.; Anantharaman, K.; Emerson, J. B.; Hernsdorf, A. W.; Amano, Y.; Suzuki, Y.; Tringe, S. G.; Woyke, T.; Banfield, J. F.

2015-12-01

Subsurface environments span the planet but remain little understood from the perspective of the capacity of the resident organisms to fix CO2. Here we investigated the autotrophic capacity of microbial communities in range of a high-CO2 subsurface environments via analysis of 250 near-complete microbial genomes (151 of them from distinct species) that represent the most abundant organisms over a subsurface depth transect. More than one third of the genomes belonged to the so-called candidate phyla radiation (CPR), which have limited metabolic capabilities. Approximately 30% of the community members are autotrophs that comprise 70% of the microbiome with metabolism likely supported by sulfur and nitrogen respiration. Of the carbon fixation pathways, the Calvin Benson Basham Cycle was most common, but the Wood-Ljungdhal pathway was present in the greatest phylogenetic diversity of organisms. Unexpectedly, one organism from a novel phylum sibling to the CPR is predicted to fix carbon by the reverse TCA cycle. The genome of the most abundant organism, an archaeon designated "Candidatus Altiarchaeum hamiconexum", was also found in subsurface samples from other continents including Europe and Asia. The archaeon was proven to be a carbon fixer using a novel reductive acetyl-CoA pathway. These results provide evidence that carbon dioxide is the major carbon source in these environments and suggest that autotrophy in the subsurface represents a substantial carbon dioxide sink affecting the global carbon cycle.

Multispectral imaging of plant stress for detection of CO2 leaking from underground

NASA Astrophysics Data System (ADS)

Rouse, J.; Shaw, J. A.; Repasky, K. S.; Lawrence, R. L.

2008-12-01

Multispectral imaging of plant stress is a potentially useful method of detecting CO2 leaking from underground. During the summers of 2007 and 2008, we deployed a multispectral imager for vegetation sensing as part of an underground CO2 release experiment conducted at the Zero Emission Research and Technology (ZERT) field site near the Montana State University campus in Bozeman, Montana. The imager was mounted on a low tower and observed the vegetation in a region near an underground pipe during a multi-week CO2 release. The imager was calibrated to measure absolute reflectance, from which vegetation indices were calculated as a measure of vegetation health. The temporal evolution of these indices over the course of the experiment show that the vegetation nearest the pipe exhibited more stress than the vegetation located further from the pipe. The imager observed notably increased stress in vegetation at locations exhibiting particularly high flux of CO2 from the ground into the atmosphere. These data from the 2007 and 2008 experiments will be used to demonstrate the utility of a tower-mounted multispectral imaging system for detecting CO2 leakage from below ground with the ability to operate continuously during clear and cloudy conditions.

Mineral storage of CO2/H2S gas mixture injection in basaltic rocks

NASA Astrophysics Data System (ADS)

Clark, D. E.; Gunnarsson, I.; Aradottir, E. S.; Oelkers, E. H.; Sigfússon, B.; Snæbjörnsdottír, S. Ó.; Matter, J. M.; Stute, M.; Júlíusson, B. M.; Gíslason, S. R.

2017-12-01

Carbon capture and storage is one solution to reducing CO2 emissions in the atmosphere. The long-term geological storage of buoyant supercritical CO2 requires high integrity cap rock. Some of the risk associated with CO2 buoyancy can be overcome by dissolving CO2 into water during its injection, thus eliminating its buoyancy. This enables injection into fractured rocks, such as basaltic rocks along oceanic ridges and on continents. Basaltic rocks are rich in divalent cations, Ca2+, Mg2+ and Fe2+, which react with CO2 dissolved in water to form stable carbonate minerals. This possibility has been successfully tested as a part of the CarbFix CO2storage pilot project at the Hellisheiði geothermal power plant in Iceland, where they have shown mineralization occurs in less than two years [1, 2]. Reykjavik Energy and the CarbFix group has been injecting a mixture of CO2 and H2S at 750 m depth and 240-250°C since June 2014; by 1 January 2016, 6290 tons of CO2 and 3530 tons of H2S had been injected. Once in the geothermal reservoir, the heat exchange and sufficient dissolution of the host rock neutralizes the gas-charged water and saturates the formation water respecting carbonate and sulfur minerals. A thermally stable inert tracer was also mixed into the stream to monitor the subsurface transport and to assess the degree of subsurface carbonation and sulfide precipitation [3]. Water and gas samples have been continuously collected from three monitoring wells and geochemically analyzed. Based on the results, mineral saturation stages have been defined. These results and tracer mass balance calculations are used to evaluate the rate and magnitude of CO2 and H2S mineralization in the subsurface, with indications that mineralization of carbon and sulfur occurs within months. [1] Gunnsarsson, I., et al. (2017). Rapid and cost-effective capture and subsurface mineral storage of carbon and sulfur. Manuscript submitted for publication. [2] Matter, J., et al. (2016). Rapid carbon mineralization for permanent disposal of anthropogenic carbon dioxide emissions. Science 352 (6291), 1312-1314. [3] Snæbjörnsdottír, S.O., et al. (2017). The chemistry and saturation states of subsurface fluids during the in-situ mineralisation of CO2 and H2S at the CarbFix site in SW-Iceland. International Journal of Greenhouse Gas Control 58, 87-102.

Bursts of CO2 released during freezing offer a new perspective on avoidance of winter embolism in trees.

PubMed

Lintunen, A; Lindfors, L; Kolari, P; Juurola, E; Nikinmaa, E; Hölttä, T

2014-12-01

Woody plants can suffer from winter embolism as gas bubbles are formed in the water-conducting conduits when freezing occurs: gases are not soluble in ice, and the bubbles may expand and fill the conduits with air during thawing. A major assumption usually made in studies of winter embolism formation is that all of the gas dissolved in the xylem sap is trapped within the conduits and forms bubbles during freezing. The current study tested whether this assumption is actually valid, or whether efflux of gases from the stem during freezing reduces the occurrence of embolism. CO2 efflux measurements were conducted during freezing experiments for saplings of three Scots pine (Pinus sylvestris) and three Norway spruce (Picea abies) trees under laboratory conditions, and the magnitudes of the freezing-related bursts of CO2 released from the stems were analysed using a previously published mechanistic model of CO2 production, storage, diffusion and efflux from a tree stem. The freezing-related bursts of CO2 released from a mature Scots pine tree growing in field conditions were also measured and analysed. Substantial freezing-related bursts of CO2 released from the stem were found to occur during both the laboratory experiments and under field conditions. In the laboratory, the fraction of CO2 released from the stem ranged between 27 and 96 % of the total CO2 content within the stem. All gases dissolved in the xylem sap are not trapped within the ice in the stem during freezing, as has previously been assumed, thus adding a new dimension to the understanding of winter embolism formation. The conduit water volume not only determines the volume of bubbles formed during freezing, but also the efficiency of gas efflux out of the conduit during the freezing process. © The Author 2014. Published by Oxford University Press on behalf of the Annals of Botany Company.

CO2 Storage related Groundwater Impacts and Protection

NASA Astrophysics Data System (ADS)

Fischer, Sebastian; Knopf, Stefan; May, Franz; Rebscher, Dorothee

2016-03-01

Injection of CO2 into the deep subsurface will affect physical and chemical conditions in the storage environment. Hence, geological CO2 storage can have potential impacts on groundwater resources. Shallow freshwater can only be affected if leakage pathways facilitate the ascent of CO2 or saline formation water. Leakage associated with CO2 storage cannot be excluded, but potential environmental impacts could be reduced by selecting suitable storage locations. In the framework of risk assessment, testing of models and scenarios against operational data has to be performed repeatedly in order to predict the long-term fate of CO2. Monitoring of a storage site should reveal any deviations from expected storage performance, so that corrective measures can be taken. Comprehensive R & D activities and experience from several storage projects will enhance the state of knowledge on geological CO2 storage, thus enabling safe storage operations at well-characterised and carefully selected storage sites while meeting the requirements of groundwater protection.

Examination of oxygen release from plants in constructed wetlands in different stages of wetland plant life cycle.

PubMed

Zhang, Jian; Wu, Haiming; Hu, Zhen; Liang, Shuang; Fan, Jinlin

2014-01-01

The quantification of oxygen release by plants in different stages of wetland plant life cycle was made in this study. Results obtained from 1 year measurement in subsurface wetland microcosms demonstrated that oxygen release from Phragmites australis varied from 108.89 to 404.44 mg O₂/m(2)/d during the different periods from budding to dormancy. Plant species, substrate types, and culture solutions had a significant effect on the capacity of oxygen release of wetland plants. Oxygen supply by wetland plants was estimated to potentially support a removal of 300.37 mg COD/m(2)/d or 55.87 mg NH₄-N/m(2)/d. According to oxygen balance analysis, oxygen release by plants could provide 0.43-1.12% of biochemical oxygen demand in typical subsurface-flow constructed wetlands (CWs). This demonstrates that oxygen release of plants may be a potential source for pollutants removal especially in low-loaded CWs. The results make it possible to quantify the role of plants in wastewater purification.

Your View or Mine: Spatially Quantifying CO2 Storage Risk from Various Stakeholder Perspectives

NASA Astrophysics Data System (ADS)

Bielicki, J. M.; Pollak, M.; Wilson, E.; Elliot, T. R.; Guo, B.; Nogues, J. P.; Peters, C. A.

2011-12-01

CO2 capture and storage involves injecting captured CO2 into geologic formations, such as deep saline aquifers. This injected CO2 is to be "stored" within the rock matrix for hundreds to thousands of years, but injected CO2, or the brine it displaces, may leak from the target reservoir. Such leakage could interfere with other subsurface activities-water production, energy production, energy storage, and waste disposal-or migrate to the surface. Each of these interferences will incur multiple costs to a variety of stakeholders. Even if injected or displaced fluids do not interfere with other subsurface activities or make their way to the surface, costs will be incurred to find and fix the leak. Consequently, the suitability of a site for CO2 storage must therefore include an assessment of the risk of leakage and interference with various other activities within a three-dimensional proximity of where CO2 is being injected. We present a spatial analysis of leakage and interference risk associated with injecting CO2 into a portion of the Mount Simon sandstone in the Michigan Basin. Risk is the probability of an outcome multiplied by the impact of that outcome (Ro=po*Io). An outcome is the result of the leakage (e.g., interference with oil production), and the impact is the cost associated with the outcome. Each outcome has costs that will vary by stakeholder. Our analysis presents CO2 storage risk for multiple outcomes in a spatially explicit manner that varies by stakeholder. We use the ELSA semi-analytical model for estimating CO2 and brine leakage from aquifers to determine plume and pressure front radii, and CO2 and brine leakage probabilities for the Mount Simon sandstone and multiple units above it. Results of ELSA simulations are incorporated into RISCS: the Risk Interference Subsurface CO2 Storage model. RISCS uses three-dimensional data on subsurface geology and the locations of wells and boreholes to spatially estimate risks associated with CO2 leakage from injection reservoirs. Where plumes probabilistically intersect subsurface activities, reach groundwater, or reach the surface, RISCS uses cost estimates from the Leakage Impact Valuation framework to estimate CO2 storage leakage and interference risk in monetary terms. This framework estimates costs that might be incurred if CO2 leaks from an injection reservoir. Such leakage could beget a variety of costs, depending on the nature and extent of the impacts. The framework identifies multiple costs under headings of: (a) finding and fixing the leak, (b) business disruption, and (c) cleaning up and paying for damages. The framework also enumerates the distribution of costs between ten different stakeholders, and allocates these costs along four leakage scenarios: 1) No interference, 2) interference with a subsurface activity, 3) interference with groundwater, and 4) migration to the surface. Our methodology facilitates research along two lines. First, it allows a probabilistic assessment of leakage costs to an injection operator, and thus what the effect of leakage might be on CCS market effectiveness. Second, it allows a broader inquiry about injection site prioritization from the point of view of various stakeholders.

Influence of Common Bean (Phaseolus vulgaris) Grown in Elevated CO2 on Apatite Dissolution

NASA Astrophysics Data System (ADS)

Olsen, A. A.; Morra, B.

2016-12-01

We ran a series of experiments to test the hypothesis that release of plant nutrients contained in apatite will be accelerated by the growth of Langstrath Stringless green bean in the presence of atmospheric CO2 meant to simulate possible future atmospheric conditions due a higher demand of nutrients and growth rate caused by elevated CO2. We hypothesize that elevated atmospheric CO2 will lead to both increased root growth and organic acid exudation. These two traits will lead to improved acquisition of P derived from apatite. Experiments were designed to investigate the effect of these changes on soil mineral weathering using plants grown under two conditions, ambient CO2 (400ppm) and elevated CO2 (1000ppm). Plants were grown in flow-through microcosms consisting of a mixture of quartz and apatite sands. Mini-greenhouses were utilized to control CO2 levels. Plant growth was sustained by a nutrient solution lacking in Ca and P. Calcium and P content of the leachate and plant tissue served as a proxy for apatite dissolution. Plants were harvested biweekly during the eight-week experiment and analyzed for Ca and P to calculate apatite dissolution kinetics. Preliminary results suggest that approximately four times more P and Ca are present in the leachate from experiments containing plants under both ambient and elevated CO2 levels than in abiotic experiments; however, the amounts of both P and Ca released in experiments conducted under both ambient and elevated CO2 levels are similar. Additionally, the amount of P in plant tissue grown under ambient and elevated CO2 conditions is similar. Plants grown in elevated CO2 had a greater root to shoot ratio. The planted microcosms were found to have a lower pH than abiotic controls most likely due to root respiration and exudation of organic acids.

Natural analogues for CO2 storage sites - analysis of a global dataset

NASA Astrophysics Data System (ADS)

Miocic, Johannes; Gilfillan, Stuart; McDermott, Christopher; Haszeldine, R. Stuart

2013-04-01

Carbon Capture and Storage is the only industrial scale technology currently available to reduce CO2 emissions from fossil-fuelled power plants and large industrial source to the atmosphere and thus mitigate climate change. CO2 is captured at the source and transported to subsurface storage sites, such as depleted oil and gas fields or saline aquifers. In order to have an effect on emissions and to be considered safe it is crucial that the amount of CO2 leaking from storage sites to shallow aquifers or the surface remains very low (<1% over 1000 years). Some process that influence the safety of a reservoir, such as CO2-rock-brine interactions, can be studied using experiments on both laboratory and field-scale. However, long-term processes such as the development of leakage pathways can only be understood by either predictive modelling or by studying natural CO2 reservoirs as analogues for long term CO2 storage sites. Natural CO2 reservoirs have similar geological trapping mechanisms as anticipated for CO2 storage sites and often have held CO2 for a geological period of time (millions of years) without any indication for leakage. Yet, migration of CO2 from reservoirs to the surface is also common and evidenced by gas seeps such as springs and soil degassing. We have compiled and analysed a dataset comprising of more than 50 natural CO2 reservoirs from different settings all around the globe to provide an overview of the factors that are important for the retention of CO2 in the subsurface and what processes lead to leakage of CO2 from the reservoir. Initial results indicate that if the reservoir is found to be leaking, CO2 migration is along faults and not through caprock layers. This indicates that faults act as fluid pathways and play an important role when characterizing a storage site. Additionally, it appears that overpressure of the overburden and the state of CO2 in the reservoir influence the likelihood of migration and hence the safety of a reservoir.

Microbial potential for carbon and nutrient cycling in a geogenic supercritical carbon dioxide reservoir

PubMed Central

Freedman, Adam J.E.; Tan, BoonFei

2017-01-01

Summary Microorganisms catalyze carbon cycling and biogeochemical reactions in the deep subsurface and thus may be expected to influence the fate of injected supercritical (sc) CO2 following geological carbon sequestration (GCS). We hypothesized that natural subsurface scCO2 reservoirs, which serve as analogs for the long‐term fate of sequestered scCO2, harbor a ‘deep carbonated biosphere’ with carbon cycling potential. We sampled subsurface fluids from scCO2‐water separators at a natural scCO2 reservoir at McElmo Dome, Colorado for analysis of 16S rRNA gene diversity and metagenome content. Sequence annotations indicated dominance of Sulfurospirillum, Rhizobium, Desulfovibrio and four members of the Clostridiales family. Genomes extracted from metagenomes using homology and compositional approaches revealed diverse mechanisms for growth and nutrient cycling, including pathways for CO2 and N2 fixation, anaerobic respiration, sulfur oxidation, fermentation and potential for metabolic syntrophy. Differences in biogeochemical potential between two production well communities were consistent with differences in fluid chemical profiles, suggesting a potential link between microbial activity and geochemistry. The existence of a microbial ecosystem associated with the McElmo Dome scCO2 reservoir indicates that potential impacts of the deep biosphere on CO2 fate and transport should be taken into consideration as a component of GCS planning and modelling. PMID:28229521

Microbial potential for carbon and nutrient cycling in a geogenic supercritical carbon dioxide reservoir: Microbial life in the deep carbonated biosphere

DOE Office of Scientific and Technical Information (OSTI.GOV)

Freedman, Adam J. E.; Tan, BoonFei; Thompson, Janelle R.

Microorganisms catalyze carbon cycling and biogeochemical reactions in the deep subsurface and thus may be expected to influence the fate of injected super-critical (sc) CO 2 following geological carbon sequestration (GCS). We hypothesized that natural subsurface scCO 2 reservoirs, which serve as analogs for the long-term fate of sequestered scCO 2 harbor a ‘deep carbonated biosphere’ with carbon cycling potential. We sampled subsurface fluids from scCO 2- water separators at a natural scCO 2 reservoir at McElmo Dome, Colorado for analysis of 16S rRNA gene diversity and metagenome content. Sequence annotations indicated dominance of Sulfurospirillum, Rhizobium, Desulfovibrio and four membersmore » of the Clostridiales family. Genomes extracted from metagenomes using homology and compositional approaches revealed diverse mechanisms for growth and nutrient cycling, including pathways for CO 2 and N 2 fixation, anaerobic respiration, sulfur oxidation, fermentation and potential for metabolic syntrophy. Differences in biogeochemical potential between two production well communities were consistent with differences in fluid chemical profiles, suggesting a potential link between microbial activity and geochemistry. In conclusion, the existence of a microbial ecosystem associated with the McElmo Dome scCO 2 reservoir indicates that potential impacts of the deep biosphere on CO 2 fate and transport should be taken into consideration as a component of GCS planning and modelling.« less

Microbial potential for carbon and nutrient cycling in a geogenic supercritical carbon dioxide reservoir: Microbial life in the deep carbonated biosphere

DOE PAGES

Freedman, Adam J. E.; Tan, BoonFei; Thompson, Janelle R.

2017-05-02

Microorganisms catalyze carbon cycling and biogeochemical reactions in the deep subsurface and thus may be expected to influence the fate of injected super-critical (sc) CO 2 following geological carbon sequestration (GCS). We hypothesized that natural subsurface scCO 2 reservoirs, which serve as analogs for the long-term fate of sequestered scCO 2 harbor a ‘deep carbonated biosphere’ with carbon cycling potential. We sampled subsurface fluids from scCO 2- water separators at a natural scCO 2 reservoir at McElmo Dome, Colorado for analysis of 16S rRNA gene diversity and metagenome content. Sequence annotations indicated dominance of Sulfurospirillum, Rhizobium, Desulfovibrio and four membersmore » of the Clostridiales family. Genomes extracted from metagenomes using homology and compositional approaches revealed diverse mechanisms for growth and nutrient cycling, including pathways for CO 2 and N 2 fixation, anaerobic respiration, sulfur oxidation, fermentation and potential for metabolic syntrophy. Differences in biogeochemical potential between two production well communities were consistent with differences in fluid chemical profiles, suggesting a potential link between microbial activity and geochemistry. In conclusion, the existence of a microbial ecosystem associated with the McElmo Dome scCO 2 reservoir indicates that potential impacts of the deep biosphere on CO 2 fate and transport should be taken into consideration as a component of GCS planning and modelling.« less

Immobilization of cobalt by sulfate-reducing bacteria in subsurface sediments

USGS Publications Warehouse

Krumholz, Lee R.; Elias, Dwayne A.; Suflita, Joseph M.

2003-01-01

We investigated the impact of sulfate-reduction on immobilization of metals in subsurface aquifers. Co 2+ was used as a model for heavy metals. Factors limiting sulfate-reduction dependent Co 2+ immobilization were tested on pure cultures of sulfate-reducing bacteria, and in sediment columns from a landfill leachate contaminated aquifer. In the presence of 1 mM Co 2+ , the growth of pure cultures of sulfate-reducing bacteria was not impacted. Cultures of Desulfovibrio desulfuricans, Desulfotomaculum gibsoniae , and Desulfomicrobium hypogeia removed greater than 99.99% of the soluble Co 2+ when CoCl 2 was used with no chelators. The above cultures and Desulfoarcula baarsi removed 98-99.94% of the soluble Co(II) when the metal was complexed with the model ligand nitrilotriacetate (Co-NTA). Factors controlling the rate of sulfate-reduction based Co 2+ precipitation were investigated in sediment-cobalt mixtures. Several electron donors were tested and all but toluene accelerated soluble Co 2+ loss. Ethanol and formate showed the greatest stimulation. All complex nitrogen sources tested slowed and decreased the extent of Co 2+ removal from solution relative to formate-amended sediment incubations. A range of pH values were tested (6.35-7.81), with the more alkaline incubations exhibiting the largest precipitation of Co 2+ . The immobilization of Co 2+ in sediments was also investigated with cores to monitor the flow of Co 2+ through undisturbed sediments. An increase in the amount of Co 2+ immobilized as CoS was observed as sulfate reduction activity was stimulated in flow through columns. Both pure culture and sediment incubation data indicate that stimulation of sulfate reduction is a viable strategy in the immobilization of contaminating metals in subsurface systems.

TOUGHREACT Version 2.0: A simulator for subsurface reactive transport under non-isothermal multiphase flow conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, T.; Spycher, N.; Sonnenthal, E.

2010-08-01

TOUGHREACT is a numerical simulation program for chemically reactive non-isothermal flows of multiphase fluids in porous and fractured media, and was developed by introducing reactive chemistry into the multiphase fluid and heat flow simulator TOUGH2 V2. The first version of TOUGHREACT was released to the public through the U.S. Department of Energy's Energy Science and Technology Software Center (ESTSC) in August 2004. It is among the most frequently requested of ESTSC's codes. The code has been widely used for studies in CO{sub 2} geological sequestration, nuclear waste isolation, geothermal energy development, environmental remediation, and increasingly for petroleum applications. Over themore » past several years, many new capabilities have been developed, which were incorporated into Version 2 of TOUGHREACT. Major additions and improvements in Version 2 are discussed here, and two application examples are presented: (1) long-term fate of injected CO{sub 2} in a storage reservoir and (2) biogeochemical cycling of metals in mining-impacted lake sediments.« less

Bioremediation of uranium-contaminated groundwater: a systems approach to subsurface biogeochemistry.

PubMed

Williams, Kenneth H; Bargar, John R; Lloyd, Jonathan R; Lovley, Derek R

2013-06-01

Adding organic electron donors to stimulate microbial reduction of highly soluble U(VI) to less soluble U(IV) is a promising strategy for immobilizing uranium in contaminated subsurface environments. Studies suggest that diagnosing the in situ physiological status of the subsurface community during uranium bioremediation with environmental transcriptomic and proteomic techniques can identify factors potentially limiting U(VI) reduction activity. Models which couple genome-scale in silico representations of the metabolism of key microbial populations with geochemical and hydrological models may be able to predict the outcome of bioremediation strategies and aid in the development of new approaches. Concerns remain about the long-term stability of sequestered U(IV) minerals and the release of co-contaminants associated with Fe(III) oxides, which might be overcome through targeted delivery of electrons to select microorganisms using in situ electrodes. Copyright © 2012 Elsevier Ltd. All rights reserved.

Modeling and Evaluation of Geophysical Methods for Monitoring and Tracking CO2 Migration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Daniels, Jeff

2012-11-30

Geological sequestration has been proposed as a viable option for mitigating the vast amount of CO{sub 2} being released into the atmosphere daily. Test sites for CO{sub 2} injection have been appearing across the world to ascertain the feasibility of capturing and sequestering carbon dioxide. A major concern with full scale implementation is monitoring and verifying the permanence of injected CO{sub 2}. Geophysical methods, an exploration industry standard, are non-invasive imaging techniques that can be implemented to address that concern. Geophysical methods, seismic and electromagnetic, play a crucial role in monitoring the subsurface pre- and post-injection. Seismic techniques have beenmore » the most popular but electromagnetic methods are gaining interest. The primary goal of this project was to develop a new geophysical tool, a software program called GphyzCO2, to investigate the implementation of geophysical monitoring for detecting injected CO{sub 2} at test sites. The GphyzCO2 software consists of interconnected programs that encompass well logging, seismic, and electromagnetic methods. The software enables users to design and execute 3D surface-to-surface (conventional surface seismic) and borehole-to-borehole (cross-hole seismic and electromagnetic methods) numerical modeling surveys. The generalized flow of the program begins with building a complex 3D subsurface geological model, assigning properties to the models that mimic a potential CO{sub 2} injection site, numerically forward model a geophysical survey, and analyze the results. A test site located in Warren County, Ohio was selected as the test site for the full implementation of GphyzCO2. Specific interest was placed on a potential reservoir target, the Mount Simon Sandstone, and cap rock, the Eau Claire Formation. Analysis of the test site included well log data, physical property measurements (porosity), core sample resistivity measurements, calculating electrical permittivity values, seismic data collection, and seismic interpretation. The data was input into GphyzCO2 to demonstrate a full implementation of the software capabilities. Part of the implementation investigated the limits of using geophysical methods to monitor CO{sub 2} injection sites. The results show that cross-hole EM numerical surveys are limited to under 100 meter borehole separation. Those results were utilized in executing numerical EM surveys that contain hypothetical CO{sub 2} injections. The outcome of the forward modeling shows that EM methods can detect the presence of CO{sub 2}.« less

Biofilm-induced calcium carbonate precipitation: application in the subsurface

NASA Astrophysics Data System (ADS)

Phillips, A. J.; Eldring, J.; Lauchnor, E.; Hiebert, R.; Gerlach, R.; Mitchell, A. C.; Esposito, R.; Cunningham, A. B.; Spangler, L.

2012-12-01

We have investigated mitigation strategies for sealing high permeability regions, like fractures, in the subsurface. This technology has the potential to, for example, improve the long-term security of geologically-stored carbon dioxide (CO2) by sealing fractures in cap rocks or to mitigate leakage pathways to prevent contamination of overlying aquifers from hydraulic fracturing fluids. Sealing technologies using low-viscosity fluids are advantageous since they potentially reduce the necessary injection pressures and increase the radius of influence around injection wells. In this technology, aqueous solutions and suspensions are used to promote microbially-induced mineral precipitation which can be applied in subsurface environments. To this end, a strategy was developed to twice seal a hydraulically fractured, 74 cm (2.4') diameter Boyles Sandstone core, collected in North-Central Alabama, with biofilm-induced calcium carbonate (CaCO3) precipitates under ambient pressures. Sporosarcina pasteurii biofilms were established and calcium and urea containing reagents were injected to promote saturation conditions favorable for CaCO3 precipitation followed by growth reagents to resuscitate the biofilm's ureolytic activity. Then, in order to evaluate this process at relevant deep subsurface pressures, a novel high pressure test vessel was developed to house the 74 cm diameter core under pressures as high as 96 bar (1,400 psi). After determining that no impact to the fracture permeability occurred due to increasing overburden pressure, the fractured core was sealed under subsurface relevant pressures relating to 457 meters (1,500 feet) below ground surface (44 bar (650 psi) overburden pressure). After fracture sealing under both ambient and subsurface relevant pressure conditions, the sandstone core withstood three times higher well bore pressure than during the initial fracturing event, which occurred prior to biofilm-induced CaCO3 mineralization. These studies suggest biofilm-induced CaCO3 precipitation technologies may potentially seal and strengthen high permeability regions or fractures (either natural or induced) in the subsurface. Novel high pressure test vessel to investigate biogeochemical processes under relevant subsurface scales and pressures.

Investigation of Reactions between Glauconite and Carbon Dioxide, with Implications for Carbon Sequestration

NASA Astrophysics Data System (ADS)

Nguyen, A. V.; Gabitov, R. I.; Beckingham, L. E.; Toghiani, H.; Fei, Y.; Kirkland, B. L.

2017-12-01

Mineral trapping is one potentially effective technology for long-term storage of carbon dioxide in a subsurface environment that has high temperature and pressure. Conceptually, upon injection of CO2 as a supercritical fluid into geological formations, the CO2 will react with the host rock to form a secondary carbonate mineral that is stable, thus creating a long-term carbon sink under thermodynamic condition of the reaction. Previous studies have demonstrated crystallization of magnesite by reactivity of CO2 and olivine-bearing basalt. Glauconite, a Fe/Ca/Mg bearing aluminosilicate mineral, a potential candidate for reaction with CO2 is common in sedimentary rock formations. The objectives of this study are to 1) develop a protocol for testing mineral trapping in the subsurface and 2) use that protocol to test the reactivity and effectiveness of the mineral glauconite in carbon sequestration. A sample from the Cambrian Riley Formation of Central Texas was selected for this study because it is extremely rich in glauconite. Mineral composition of the powdered sample was investigated by X-ray diffraction (XRD), which revealed that the glauconitic sandstone contains glauconite 20.4%, quartz 71%, and celadonite 8.6%. In the first experiment, 1.5 g of 0.01- 0.5 cm diameter grains reacted with a supercritical CO2 fluid in 30 g of sea water. The laboratory experiment was conducted in a stainless steel vessel in situ reservoir conditions at 120 degrees Celsius and 100 bars. After CO2 injection, pH of the brine decreased from 8.23 to 7. Scanning electron microscopy (SEM) and X-ray diffraction method showed no carbonate formed after 10 days of reaction. However, further experimental modifications facilitated formation of calcite at higher pH. In the second experiment, 0.7 g of 10-75 μm grains presumably reacted with CO2 formed by ammonium carbonate decomposition in a brine of NaCl 0.5 and CaCl2 0.25M; pH after the end of experiment was 7.74. The autoclave was set at 120 degrees Celsius and pressure of saturated water vapour for 14 days. XRD and EDS confirmed the presence of calcite in the sample after the treatment. This material is based upon work supported by the Department of Energy National Energy Technology Laboratory under the Southern States Energy Board's Cooperative Agreement Award Number DE-FE0029465.

In Situ Oxalic Acid Injection to Accelerate Arsenic Remediation at a Superfund Site in New Jersey

PubMed Central

Wovkulich, Karen; Stute, Martin; Mailloux, Brian J.; Keimowitz, Alison R.; Ross, James; Bostick, Benjamin; Sun, Jing; Chillrud, Steven N.

2015-01-01

Arsenic is a prevalent contaminant at a large number of US Superfund sites; establishing techniques that accelerate As remediation could benefit many sites. Hundreds of tons of As were released into the environment by the Vineland Chemical Co. in southern New Jersey during its manufacturing lifetime (1949–1994), resulting in extensive contamination of surface and subsurface soils and sediments, groundwater, and the downstream watershed. Despite substantial intervention at this Superfund site, sufficient aquifer cleanup could require many decades if based on traditional pump and treat technologies only. Laboratory column experiments have suggested that oxalic acid addition to contaminated aquifer solids could promote significant As release from the solid phase. To evaluate the potential of chemical additions to increase As release in situ and boost treatment efficiency, a forced gradient pilot scale study was conducted on the Vineland site. During spring/summer 2009, oxalic acid and bromide tracer were injected into a small portion (~50 m2) of the site for 3 months. Groundwater samples indicate that introduction of oxalic acid led to increased As release. Between 2.9 and 3.6 kg of As were removed from the sampled wells as a result of the oxalic acid treatment during the 3-month injection. A comparison of As concentrations on sediment cores collected before and after treatment and analyzed using X-ray fluorescence spectroscopy suggested reduction in As concentrations of ~36% (median difference) to 48% (mean difference). While further study is necessary, the addition of oxalic acid shows potential for accelerating treatment of a highly contaminated site and decreasing the As remediation time-scale. PMID:25598701

Biogeochemical Cycle of Methanol in Anoxic Deep-Sea Sediments

PubMed Central

Yanagawa, Katsunori; Tani, Atsushi; Yamamoto, Naoya; Hachikubo, Akihiro; Kano, Akihiro; Matsumoto, Ryo; Suzuki, Yohey

2016-01-01

The biological flux and lifetime of methanol in anoxic marine sediments are largely unknown. We herein reported, for the first time, quantitative methanol removal rates in subsurface sediments. Anaerobic incubation experiments with radiotracers showed high rates of microbial methanol consumption. Notably, methanol oxidation to CO2 surpassed methanol assimilation and methanogenesis from CO2/H2 and methanol. Nevertheless, a significant decrease in methanol was not observed after the incubation, and this was attributed to the microbial production of methanol in parallel with its consumption. These results suggest that microbial reactions play an important role in the sources and sinks of methanol in subseafloor sediments. PMID:27301420

Interfacial stability of CoSi2/Si structures grown by molecular beam epitaxy

NASA Technical Reports Server (NTRS)

George, T.; Fathauer, R. W.

1992-01-01

The stability of CoSi2/Si interfaces was examined in this study using columnar silicide structures grown on (111) Si substrates. In the first set of experiments, Co and Si were codeposited using MBE at 800 C and the resulting columnar silicide layer was capped by epitaxial Si. Deposition of Co on the surface of the Si capping layer at 800 C results in the growth of the buried silicide columns. The buried columns grow by subsurface diffusion of the deposited Co, suppressing the formation of surface islands of CoSi2. The column sidewalls appear to be less stable than the top and bottom interfaces, resulting in preferential lateral growth and ultimately in the coalescence of the columns to form a continuous buried CoSi2 layer. In the second set of experiments, annealing of a 250 nm-thick buried columnar layer at 1000 C under a 100 nm-thick Si capping layer results in the formation of a surface layer of CoSi2 with a reduction in the sizes of the CoSi2 columns. For a sample having a thicker Si capping layer the annealing leads to Ostwald ripening producing buried equiaxed columns. The high CoSi2/Si interfacial strain could provide the driving force for the observed behavior of the buried columns under high-temperature annealing.

Potential for the Use of Wireless Sensor Networks for Monitoring of CO2 Leakage Risks

NASA Astrophysics Data System (ADS)

Pawar, R.; Illangasekare, T. H.; Han, Q.; Jayasumana, A.

2015-12-01

Storage of supercritical CO2 in deep saline geologic formation is under study as a means to mitigate potential global climate change from green house gas loading to the atmosphere. Leakage of CO2 from these formations poses risk to the storage permanence goal of 99% of injected CO2 remaining sequestered from the atmosphere,. Leaked CO2 that migrates into overlying groundwater aquifers may cause changes in groundwater quality that pose risks to environmental and human health. For these reasons, technologies for monitoring, measuring and accounting of injected CO2 are necessary for permitting of CO2 sequestration projects under EPA's class VI CO2 injection well regulations. While the probability of leakage related to CO2 injection is thought to be small at characterized and permitted sites, it is still very important to protect the groundwater resources and develop methods that can efficiently and accurately detect CO2 leakage. Methods that have been proposed for leakage detection include remote sensing, soil gas monitoring, geophysical techniques, pressure monitoring, vegetation stress and eddy covariance measurements. We have demonstrated the use of wireless sensor networks (WSN) for monitoring of subsurface contaminant plumes. The adaptability of this technology for leakage monitoring of CO2 through geochemical changes in the shallow subsurface is explored. For this technology to be viable, it is necessary to identify geochemical indicators such as pH or electrical conductivity that have high potential for significant change in groundwater in the event of CO2 leakage. This talk presents a conceptual approach to use WSNs for CO2 leakage monitoring. Based on our past work on the use of WSN for subsurface monitoring, some of the challenges that need to be over come for this technology to be viable for leakage detection will be discussed.

Investigations of potential microbial methanogenic and carbon monoxide utilization pathways in ultra-basic reducing springs associated with present-day continental serpentinization: the Tablelands, NL, CAN

PubMed Central

Morrill, Penny L.; Brazelton, William J.; Kohl, Lukas; Rietze, Amanda; Miles, Sarah M.; Kavanagh, Heidi; Schrenk, Matthew O.; Ziegler, Susan E.; Lang, Susan Q.

2014-01-01

Ultra-basic reducing springs at continental sites of serpentinization act as portals into the biogeochemistry of a subsurface environment with H2 and CH4 present. Very little, however, is known about the carbon substrate utilization, energy sources, and metabolic pathways of the microorganisms that live in this ultra-basic environment. The potential for microbial methanogenesis with bicarbonate, formate, acetate, and propionate precursors and carbon monoxide (CO) utilization pathways were tested in laboratory experiments by adding substrates to water and sediment from the Tablelands, NL, CAD, a site of present-day continental serpentinization. Microbial methanogenesis was not observed after bicarbonate, formate, acetate, or propionate addition. CO was consumed in the live experiments but not in the killed controls and the residual CO in the live experiments became enriched in 13C. The average isotopic enrichment factor resulting from this microbial utilization of CO was estimated to be 11.2 ± 0.2‰. Phospholipid fatty acid concentrations and δ13C values suggest limited incorporation of carbon from CO into microbial lipids. This indicates that in our experiments, CO was used primarily as an energy source, but not for biomass growth. Environmental DNA sequencing of spring fluids collected at the same time as the addition experiments yielded a large proportion of Hydrogenophaga-related sequences, which is consistent with previous metagenomic data indicating the potential for these taxa to utilize CO. PMID:25431571

Investigations of potential microbial methanogenic and carbon monoxide utilization pathways in ultra-basic reducing springs associated with present-day continental serpentinization: the Tablelands, NL, CAN.

PubMed

Morrill, Penny L; Brazelton, William J; Kohl, Lukas; Rietze, Amanda; Miles, Sarah M; Kavanagh, Heidi; Schrenk, Matthew O; Ziegler, Susan E; Lang, Susan Q

2014-01-01

Ultra-basic reducing springs at continental sites of serpentinization act as portals into the biogeochemistry of a subsurface environment with H2 and CH4 present. Very little, however, is known about the carbon substrate utilization, energy sources, and metabolic pathways of the microorganisms that live in this ultra-basic environment. The potential for microbial methanogenesis with bicarbonate, formate, acetate, and propionate precursors and carbon monoxide (CO) utilization pathways were tested in laboratory experiments by adding substrates to water and sediment from the Tablelands, NL, CAD, a site of present-day continental serpentinization. Microbial methanogenesis was not observed after bicarbonate, formate, acetate, or propionate addition. CO was consumed in the live experiments but not in the killed controls and the residual CO in the live experiments became enriched in (13)C. The average isotopic enrichment factor resulting from this microbial utilization of CO was estimated to be 11.2 ± 0.2‰. Phospholipid fatty acid concentrations and δ(13)C values suggest limited incorporation of carbon from CO into microbial lipids. This indicates that in our experiments, CO was used primarily as an energy source, but not for biomass growth. Environmental DNA sequencing of spring fluids collected at the same time as the addition experiments yielded a large proportion of Hydrogenophaga-related sequences, which is consistent with previous metagenomic data indicating the potential for these taxa to utilize CO.

Substrate lability and plant activity controls greenhouse gas release from Neotropical peatland

NASA Astrophysics Data System (ADS)

Sjogersten, Sofie; Hoyos, Jorge; Lomax, Barry; Turner, Ben; Wright, Emma

2014-05-01

Almost one third of global CO2 emissions resulting from land use change and substantial CH4 emissions originate from tropical peatlands. However, our understanding of the controls of CO2 and CH4 release from tropical peatlands are limited. The aim of this study was to investigate the role of peat lability and the activity of the vegetation on gas release using a combination of field and laboratory experiments. We demonstrated that peat lability constrained CH4 production to the surface peat under anaerobic conditions. The presence of plants shifted the C balance from a C source to a C sink with respect to CO2 while the activity of the root system strongly influenced CH4 emissions through its impact on soil O2 inputs. Both field and laboratory data suggest a coupling between the photosynthetic activity of the vegetation and the release of both CO2 and CH4 following the circadian rhythm of the dominant plant functional types. Forest clearance for agriculture resulted in elevated CH4 release, which we attribute in part to the cessation of root O2 inputs to the peat. We conclude that high emissions of CO2 and CH4 from forested tropical peatlands are likely driven by labile C inputs from the vegetation but that root O2 release may limit CH4 emissions.

Mathematical models as tools for probing long-term safety of CO2 storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pruess, Karsten; Birkholzer, Jens; Zhou, Quanlin

Subsurface reservoirs being considered for storing CO{sub 2} include saline aquifers, oil and gas reservoirs, and unmineable coal seams (Baines and Worden, 2004; IPCC, 2005). By far the greatest storage capacity is in saline aquifers (Dooley et al., 2004), and our discussion will focus primarily on CO{sub 2} storage in saline formations. Most issues for safety and security of CO{sub 2} storage arise from the fact that, at typical temperature and pressure conditions encountered in terrestrial crust, CO{sub 2} is less dense than aqueous fluids. Accordingly, CO{sub 2} will experience an upward buoyancy force in most subsurface environments, and willmore » tend to migrate upwards whenever (sub-)vertical permeable pathways are available, such as fracture zones, faults, or improperly abandoned wells (Bachu, 2008; Pruess, 2008a, b; Tsang et al., 2008). CO{sub 2} injection will increase fluid pressures in the target formation, thereby altering effective stress distributions, and potentially triggering movement along fractures and faults that could increase their permeability and reduce the effectiveness of a caprock in containing CO{sub 2} (Rutqvist et al., 2008; Chiaramonte et al., 2008). Induced seismicity as a consequence of fluid injection is also a concern (Healy et al., 1968; Raleigh et al., 1976; Majer et al., 2007). Dissolution of CO{sub 2} in the aqueous phase generates carbonic acid, which may induce chemical corrosion (dissolution) of minerals with associated increase in formation porosity and permeability, and may also mediate sequestration of CO{sub 2} as solid carbonate (Gaus et al., 2008). Chemical dissolution of caprock minerals could promote leakage of CO{sub 2} from a storage reservoir (Gherardi et al., 2007). Chemical dissolution and geomechanical effects could reinforce one another in compromising CO{sub 2} containment. Additional issues arise from the potential of CO{sub 2} to mobilize hazardous chemical species (Kharaka et al., 2006), and from migration of the large amounts of brine that would be mobilized by industrial-scale CO{sub 2} injection (Nicot et al., 2008; Birkholzer et al., 2008a, b).« less

Underground Habitats in the Río Tinto Basin: A Model for Subsurface Life Habitats on Mars

NASA Astrophysics Data System (ADS)

Fernández-Remolar, David C.; Prieto-Ballesteros, Olga; Rodríguez, Nuria; Gómez, Felipe; Amils, Ricardo; Gómez-Elvira, Javier; Stoker, Carol R.

2008-10-01

A search for evidence of cryptic life in the subsurface region of a fractured Paleozoic volcanosedimentary deposit near the source waters of the Río Tinto River (Iberian pyrite belt, southwest Spain) was carried out by Mars Astrobiology Research and Technology Experiment (MARTE) project investigators in 2003 and 2004. This conventional deep-drilling experiment is referred to as the MARTE ground truth drilling project. Boreholes were drilled at three sites, and samples from extracted cores were analyzed with light microscopy, scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy. Core leachates were analyzed with ion chromatography, and borehole fluids were analyzed with ion and gas chromatography. Key variables of the groundwater system (e.g. , pO2, pH, and salinity) exhibit huge ranges probably due to surficial oxygenation of overall reducing waters, physical mixing of waters, and biologically mediated water-rock interactions. Mineral distribution is mainly driven by the pH of subsurface solutions, which range from highly acidic to neutral. Borehole fluids contain dissolved gases such as CO2, CH4, and H2. SEM-EDS analyses of core samples revealed evidence of microbes attacking pyrite. The Río Tinto alteration mechanisms may be similar to subsurface weathering of the martian crust and provide insights into the possible (bio)geochemical cycles that may have accompanied underground habitats in extensive early Mars volcanic regions and associated sulfide ores.

Underground habitats in the Río Tinto basin: a model for subsurface life habitats on Mars.

PubMed

Fernández-Remolar, David C; Prieto-Ballesteros, Olga; Rodríguez, Nuria; Gómez, Felipe; Amils, Ricardo; Gómez-Elvira, Javier; Stoker, Carol R

2008-10-01

A search for evidence of cryptic life in the subsurface region of a fractured Paleozoic volcanosedimentary deposit near the source waters of the Río Tinto River (Iberian pyrite belt, southwest Spain) was carried out by Mars Astrobiology Research and Technology Experiment (MARTE) project investigators in 2003 and 2004. This conventional deep-drilling experiment is referred to as the MARTE ground truth drilling project. Boreholes were drilled at three sites, and samples from extracted cores were analyzed with light microscopy, scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy. Core leachates were analyzed with ion chromatography, and borehole fluids were analyzed with ion and gas chromatography. Key variables of the groundwater system (e.g., pO(2), pH, and salinity) exhibit huge ranges probably due to surficial oxygenation of overall reducing waters, physical mixing of waters, and biologically mediated water-rock interactions. Mineral distribution is mainly driven by the pH of subsurface solutions, which range from highly acidic to neutral. Borehole fluids contain dissolved gases such as CO(2), CH(4), and H(2). SEM-EDS analyses of core samples revealed evidence of microbes attacking pyrite. The Río Tinto alteration mechanisms may be similar to subsurface weathering of the martian crust and provide insights into the possible (bio)geochemical cycles that may have accompanied underground habitats in extensive early Mars volcanic regions and associated sulfide ores.

Greenhouse gas emissions from oilfield-produced water in Shengli Oilfield, Eastern China.

PubMed

Yang, Shuang; Yang, Wei; Chen, Guojun; Fang, Xuan; Lv, Chengfu; Zhong, Jiaai; Xue, Lianhua

2016-08-01

Greenhouse gas (GHG) emissions from oil and gas systems are an important component of the GHG emission inventory. To assess the carbon emissions from oilfield-produced water under atmospheric conditions correctly, in situ detection and simulation experiments were developed to study the natural release of GHG into the atmosphere in the Shengli Oilfield, the second largest oilfield in China. The results showed that methane (CH4) and carbon dioxide (CO2) were the primary gases released naturally from the oilfield-produced water. The atmospheric temperature and release time played important roles in determining the CH4 and CO2 emissions under atmospheric conditions. Higher temperatures enhanced the carbon emissions. The emissions of both CH4 and CO2 from oilfield-produced water were highest at 27°C and lowest at 3°C. The bulk of CH4 and CO2 was released from the oilfield-produced water during the first release period, 0-2hr, for each temperature, with a maximum average emission rate of 0.415gCH4/(m(3)·hr) and 3.934gCO2/(m(3)·hr), respectively. Then the carbon emissions at other time periods gradually decreased with the extension of time. The higher solubility of CO2 in water than CH4 results in a higher emission rate of CH4 than CO2 over the same release duration. The simulation proved that oilfield-produced water is one of the potential emission sources that should be given great attention in oil and gas systems. Copyright © 2016. Published by Elsevier B.V.

Geologic Storage of CO2: Leakage Pathways and Environmental Risks

NASA Astrophysics Data System (ADS)

Celia, M. A.; Peters, C. A.; Bachu, S.

2002-05-01

Geologic storage of CO2 appears to be an attractive option for carbon mitigation because it offers sufficient capacity to solve the problem, and it can be implemented with existing technology. Among the list of options for storage sites, depleted hydrocarbon reservoirs and deep saline aquifers are two major categories. While injection into hydrocarbon reservoirs offers immediate possibilities, especially in the context of enhanced oil recovery, it appears that deep saline aquifers provide the extensive capacity necessary to solve the problem over the decade to century time scale. Capacity and technology argue favorably for this option, but remaining obstacles to implementation include capture technologies, overall economic considerations, and potential environmental consequences of the injection. Of these, the environmental questions may be most difficult to solve. Experience from CO2 floods for enhanced oil recovery and from CO2 and acid gas disposal operations indicates that geological storage of CO2 is safe over the short term for comparatively small amounts of CO2. However, there is no experience to date regarding the long-term fate and safety of the large volumes of CO2 that must be injected to significantly reduce atmospheric emissions. In order to make proper evaluation of environmental risks, the full range of possible environmental consequences must be considered. Most of these environmental concerns involve migration and leakage of CO2 into shallow portions of the subsurface and eventually into the atmosphere. In shallow subsurface zones, elevated levels of carbon dioxide can cause pH changes, leading to possible mobilization of ground-water contaminants including metals. In the unsaturated zone, vegetation can be adversely affected, as can other ecosystem components. At the land surface, elevated levels of CO2 can lead to asphyxiation in humans and other animals. And finally, in the atmosphere, CO2 that leaks from underground diminishes the effectiveness of the overall storage scheme and contributes to possible climate change. To characterize these environmental consequences, reliable models of leakage characteristics and rates are needed. While leakage through natural flowpaths in the subsurface may occur, a more likely pathway is leakage through abandoned wells. This may be especially troublesome in mature sedimentary basins, which are often "punctured" by a very large number of exploration and production wells. For example, in the Alberta Basin there are more than 100,000 abandoned wells, the oldest from 1883. The cement used in the completion and abandonment of these wells, historically of variable quality and quantity, most probably has degraded with age and under the effect of formation brines. The cement may degrade even more rapidly when contacted by CO2 and possibly other components in the injection mixture (such as H2S). Cement properties and their modification through time must be understood in order to provide reliable estimates of leakage rates. Those leakage rates must then be linked to models of environmental consequences, and ultimately the entire analysis must be embedded in a probabilistic framework. Such an approach will allow leakage to be addressed rationally in terms of safety and long-term environmental impacts.

Liberation of microbial substrates from macromolecular organic matter by non-supercritical CO2

NASA Astrophysics Data System (ADS)

Sauer, P.; Glombitza, C.; Kallmeyer, J.

2012-12-01

The worldwide search for suitable underground storage formations for CO2 also considers coal-bearing strata. CO2 is already injected into coal seams for enhanced recovery of coal bed methane. However, the geochemical and microbiological effects of increased CO2 concentrations on organic matter rich formations are rarely investigated. The injected CO2 will dissolve in the pore water, causing a decrease in pH and resulting in acidic formation waters. Low molecular weight organic acids (LMWOAs) are chemically bound to the macromolecular matrix of sedimentary organic matter and may be liberated by hydrolysis, which is enhanced under acidic conditions. Recent investigations outlined the importance of LMWOAs as a feedstock for subsurface microbial life [1]. Therefore, injection of CO2 into coal formations may result in enhanced nutrient supply for subsurface microbes. To investigate the effects of highly CO2-saturated waters on the release of LMWOAs from coal, we developed an inexpensive high-pressure-high-temperature system that allows manipulating the concentration of dissolved gases up to 60 MPa and 120°C, respectively. The sample is placed in a flexible, gas-tight and inert PVDF sleeve, separating it from the pressure fluid and allowing for subsampling without loss of pressure. Lignite samples from the DEBITS-1 well, Waikato Basin, NZ and the Welzow-Süd open-cast mine, Niederlausitz, Germany, were extracted at 90° C and 5 MPa, with either pure water, CO2-saturated water, CO2/NO2 or CO2/SO2-saturated water. Subsamples were taken at different time points during the 72 hrs. long extraction. Extraction of LMWOAs from coal samples with our pressurised system resulted in yields that were up to four times higher than those reported for Soxhlet extraction [2]. These higher yields may be explained by the fact that during Soxhlet extraction the sample only gets into contact with freshly distilled water, whereas in our system the extraction fluid is circulated, resulting in more acidic extraction conditions. In comparison to pure water extractions, CO2-saturated water affected the extraction yield in both directions by up to 40 percent. For the lignite from DEBITS-1 well, CO2-saturated water resulted in a permanently lower yield, whereas the lignites from the Lausitz showed an increase in formate and a decrease in oxalate. LMWOAs found in the extraction fluid may not just result from hydrolysis but also from different secondary reactions. It was suggested that oxalate in aqueous extracts of coals is a result of the decomposition of 1,2-dihydroxy-carboxylic acids [3]. We assume that for oxalate (and maybe for other LMWOAs as well) the extraction yield is not only affected by hydrolysis but also by secondary reactions, which may be suppressed in the presence of CO2 and other gasses dissolved in the extraction medium. These results show the importance of performing laboratory simulations of subsurface processes under conditions that resemble the true in-situ conditions as closely as possible. References [1] Glombitza et al., 2009, Org. Geochem. 40, 175-183 [2] Vieth et al., 2008, Org. Geochem. 39, 985-991 [3] Bou-Raad et al., 2000, Fuel 79, 1185-1193

DUSEL and the future of deep terrestrial microbiology (Invited)

NASA Astrophysics Data System (ADS)

Onstott, T. C.; Peters, C. A.; Murdoch, L. C.; Elsworth, D.; Sonnenthal, E. L.; Kieft, T.; Boutt, D. F.; Germanovich, L.; Glaser, S. D.; Wang, H. F.; Roggenthen, B.; Lesko, K.; Cushman, P.; Stetler, L. D.; Bang, S.; Anderson, C.

2009-12-01

DUSEL will take advantage of the existing subsurface architecture of the deepest mine in the U.S. to provide a platform for launching new exploration into the deep terrestrial biosphere. Multi-year experiments are currently being designed to delineate the relationships between microbial diversity and activity and hydraulic connectivity, temperature, pressure, strain rate and multiphase fluids. Unlike the physics experiments, which will be located close to the center of the mine, most of these experiments will be located at the periphery in existing tunnels at 100 to 2400 m depth in order to access fluid fill fractures with boreholes. Hydrological models suggest that DUSEL could sample ~100 km3 volume for microbial biogeographic and transport studies. The high-capacity underground water filtration plant used to generate ultrapure water for neutrino detectors will readily supply water for microbiology coring projects reducing microbial contamination. This will be essential for the drilling platform located at 2400 m depth that will drill down to 7+ km and 120oC in search of the upper temperature limit for life. Another advantage of underground coring is that the drilling fluid pressure will be much less than that of the fracture water, which means that when the coring bit intersects a water-filled fracture, the fracture water will flow into the core barrel reducing the contamination of fracture surfaces in the cores. The ultra-low radiation background counting facility to be located at 1475 m depth will potentially enable 106 times improvement in the detection limit for subsurface microbial respiration rates using radioactive tracers. The Coupled Thermal-Hydrological-Mechanical-Chemical-Biological, block-heating experiment will examine how the microbial communities within fractures respond to the increased thermal and fluid flux. The Fracture Processes Facility is not only designed to determine what controls rock strength, but could also determine to what extent subsurface chemoautotrophic activity is regulated by tectonic episodicity. The DUSEL CO2 Facility will investigate how microbial activity is impacted by CO2 injection and whether microbial activity has a significant impact upon long-term sequestration of CO2. These three experiments represent a subset of the integrated suite of experiments planned for the first 5 years, but many more microbial experiments can be accommodated within DUSEL. With its unique experimental assets, km-scale spatial access and multi-decade observational lifetime, DUSEL will usher in the next generation of exploration into the deep terrestrial biosphere and not only reveal the answers to many of its well-hidden secrets, but perhaps to the origin of life itself.

Laboratory investigations of stable carbon and oxygen isotope ratio data enhance monitoring of CO2 underground

NASA Astrophysics Data System (ADS)

Barth, Johannes A. C.; Myrttinen, Anssi; Becker, Veith; Nowak, Martin; Mayer, Bernhard

2014-05-01

Stable carbon and oxygen isotope data play an important role in monitoring CO2 in the subsurface, for instance during carbon capture and storage (CCS). This includes monitoring of supercritical and gaseous CO2 movement and reactions under reservoir conditions and detection of potential CO2 leakage scenarios. However, in many cases isotope data from field campaigns are either limited due to complex sample retrieval or require verification under controlled boundary conditions. Moreover, experimentally verified isotope fractionation factors are also accurately known only for temperatures and pressures lower than commonly found in CO2 reservoirs (Myrttinen et al., 2012). For this reason, several experimental series were conducted in order to investigate effects of elevated pressures, temperatures and salinities on stable carbon and oxygen isotope changes of CO2 and water. These tests were conducted with a heateable pressure device and with glass or metal gas containers in which CO2 reacted with fluids for time periods of hours to several weeks. The obtained results revealed systematic differences in 13C/12C-distributions between CO2 and the most important dissolved inorganic carbon (DIC) species under reservoir conditions (CO2(aq), H2CO3 and HCO3-). Since direct measurements of the pH, even immediately after sampling, were unreliable due to rapid CO2 de-gassing, one of the key results of this work is that carbon isotope fractionation data between DIC and CO2 may serve to reconstruct in situ pH values. pH values reconstructed with this approach ranged between 5.5 and 7.4 for experiments with 60 bars and up to 120 °C and were on average 1.4 pH units lower than those measured with standard pH electrodes directly after sampling. In addition, pressure and temperature experiments with H2O and CO2 revealed that differences between the oxygen isotope ratios of both phases depended on temperature, water-gas ratios as well as salt contents of the solutions involved. Such systematic knowledge of the extent of oxygen isotope fractionation between H2O and CO2 can help to reconstruct equilibration times, fluid-CO2 ratios as well as temperature and salinity conditions. Isotope results from systematic laboratory studies and the information they provide for assessing in situ reservoir conditions can be transferred to field applications concerning integrity of CO2 reservoirs. They can also apply to natural systems and other industrial uses that involve monitoring of gases in the subsurface under similar pressure and temperature conditions. Reference: Myrttinen, A., Becker, V., Barth, J.A.C., 2012. A review of methods used for equilibrium isotope fractionation investigations between dissolved inorganic carbon and CO2. Earth-Science Reviews, 115(3): 192-199.

The Impact of Mineralogy on the Geochemical Alteration of Shales During Hydraulic Fracturing Operations

NASA Astrophysics Data System (ADS)

Maher, K.; Harrison, A. L.; Jew, A. D.; Dustin, M. K.; Kiss, A. M.; Kohli, A. H.; Thomas, D.; Joe-Wong, C. M.; Brown, G. E.; Bargar, J.

2016-12-01

The extraction of oil and gas resources from low permeability shale reservoirs using hydraulic fracturing techniques has increased significantly in recent years. During hydraulic fracturing, large volumes of fluid are injected into subsurface shale formations, which drives substantial fluid-rock interaction that can release contaminants and alter rock permeability. Here, a combined experimental, imaging, and modeling approach was employed to systematically evaluate the impact of shale mineralogy on its physical and chemical alteration when exposed to fracturing fluids of different composition. Batch reactor experiments contained different shales with unique mineralogical compositions that were exposed to simulated hydraulic fracturing fluid. Experiments revealed that the balance between fluid acidity and acid neutralizing capacity of the rock was the strongest control on the evolution of fluid and rock chemistry. Carbonate mineral-rich shales rapidly recovered solution pH to circum-neutral conditions, whereas fluids in contact with carbonate mineral-poor shales remained acidic. The dissolution of shale minerals released metal contaminants, yet the precipitation of Fe(III)-bearing secondary phases helped to attenuate their release via co-precipitation or sorption. Post-reaction imaging illustrated that selective dissolution of carbonate minerals generated secondary porosity, the connectivity of which was dictated by initial carbonate distribution. Conversely, the precipitation of secondary Al- and Fe-bearing phases may occlude porosity, potentially inhibiting transport of water, contaminants, and hydrocarbons. The maturation of secondary Fe-bearing phases from amorphous to crystalline over time suggests that porosity will continue to evolve even after oxidation reactions have effectively ceased. These experiments reveal that the relative abundance and distribution of carbonate minerals is the master variable dictating both porosity alteration and contaminant release from shale formations, implying that the response of a reservoir to hydraulic fracturing can be better assessed using robust mineralogical data.

Effect of Co-Contaminants Uranium and Nitrate on Iodine Remediation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szecsody, James E.; Lee, Brady D.; Lawter, Amanda R.

The objective of this study is to evaluate the significance of co-contaminants on the migration and transformation of iodine species in the Hanford subsurface environment. These impacts are relevant because remedies that target individual contaminants like iodine, may not only impact the fate and transport of other contaminants in the subsurface, but also inhibit the effectiveness of a targeted remedy. For example, iodine (as iodate) co-precipitates with calcite, and has been identified as a potential remedy because it immobilizes iodine. Since uranium also co-precipitates with calcite in field sediments, the presence of uranium may also inhibit iodine co-precipitation. Another potentiallymore » significant impact from co-existing contaminants is iodine and nitrate. The presence of nitrate has been shown to promote biogeochemical reduction of iodate to iodide, thereby increasing iodine species subsurface mobility (as iodide exhibits less sorption). Hence, this study reports on both laboratory batch and column experiments that investigated a) the change in iodate uptake mass and rate of uptake into precipitating calcite due to the presence of differing amounts of uranium, b) the amount of change of the iodate bio-reduction rate due to the presence of differing nitrate concentrations, and c) whether nitrite can reduce iodate in the presence of microbes and/or minerals acting as catalysts.« less

Hydrological and Climate Controls on Hyporheic Contributions to River Net Ecosystem Productivity

NASA Astrophysics Data System (ADS)

Newcomer, M. E.; Hubbard, S. S.; Fleckenstein, J. H.; Maier, U.; Schmidt, C.; Laube, G.; Chen, N.; Ulrich, C.; Dwivedi, D.; Steefel, C. I.; Rubin, Y.

2016-12-01

Hyporheic zone contributions to river net ecosystem productivity (NEP) can represent a substantial source or sink for organic and inorganic carbon (C). Hyporheic zone processes are estimated to vary with network location as a function of river-aquifer interactions as well as with climatic factors supporting riverbed gross primary productivity (GPP) and ecosystem respiration. Even though hyporheic zone NEP is hypothesized to be a significant budgetary component to river-aquifer biogeochemical cycling, models of river NEP often parameterize hyporheic zone contributions as a space-time constant input of CO2 to rivers, leading to overestimation of hyporheic zone NEP and underestimation of C storage. This assumption is problematic during the summer growing season, when GPP is largest and C is stored in surface and subsurface biomass. We investigated the dynamic role of hyporheic zone NEP using the MIN3P flow and reactive transport model with surface water GPP and ecosystem respiration simulated as a function of light, depth, temperature, pH, and atmospheric CO2. We simulated hyporheic zone NEP for low-order and high-order streams, which collectively represent a range of characteristic flow paths and subsurface residence times. Downscaled climate predictions of temperature and atmospheric CO2 representing carbon emission futures were used to force the models and to compare future and current hyporheic zone NEP. Our results show that river-aquifer flow conditions determine the relative role of the river as either a store or sink of C through direct contributions of O2 and dissolved organic content from river GPP. Modeled results show that high discharge, high order rivers are net stores of CO2 from the atmosphere; however this is dependent on perturbation events that allow stored C from summer GPP to be released (i.e. rising water tables during winter storms). Lacking a perturbation event, C remains in pore-water storage as dissolved CO2 and biomass. Conversely, low-discharge mountainous streams with continuous hyporheic zone flow represent a net source of CO2, with future temperature rises stimulating additional heterotrophic activity. Our work contributes to a better understanding of how river and hyporheic zone processes significantly influence biogeochemical cycling under changing climate conditions.

Microbial potential for carbon and nutrient cycling in a geogenic supercritical carbon dioxide reservoir.

PubMed

Freedman, Adam J E; Tan, BoonFei; Thompson, Janelle R

2017-06-01

Microorganisms catalyze carbon cycling and biogeochemical reactions in the deep subsurface and thus may be expected to influence the fate of injected supercritical (sc) CO 2 following geological carbon sequestration (GCS). We hypothesized that natural subsurface scCO 2 reservoirs, which serve as analogs for the long-term fate of sequestered scCO 2 , harbor a 'deep carbonated biosphere' with carbon cycling potential. We sampled subsurface fluids from scCO 2 -water separators at a natural scCO 2 reservoir at McElmo Dome, Colorado for analysis of 16S rRNA gene diversity and metagenome content. Sequence annotations indicated dominance of Sulfurospirillum, Rhizobium, Desulfovibrio and four members of the Clostridiales family. Genomes extracted from metagenomes using homology and compositional approaches revealed diverse mechanisms for growth and nutrient cycling, including pathways for CO 2 and N 2 fixation, anaerobic respiration, sulfur oxidation, fermentation and potential for metabolic syntrophy. Differences in biogeochemical potential between two production well communities were consistent with differences in fluid chemical profiles, suggesting a potential link between microbial activity and geochemistry. The existence of a microbial ecosystem associated with the McElmo Dome scCO 2 reservoir indicates that potential impacts of the deep biosphere on CO 2 fate and transport should be taken into consideration as a component of GCS planning and modelling. © 2017 The Authors. Environmental Microbiology published by Society for Applied Microbiology and John Wiley & Sons Ltd.

Geochemical Impacts of Leaking CO2 from Subsurface Storage Reservoirs on the Fate of Metal Contaminants in an Overlaying Groundwater Aquifer

NASA Astrophysics Data System (ADS)

Shao, H.; Qafoku, N. P.; Lawter, A.; Bowden, M. E.; Brown, C. F.

2014-12-01

The leakage of CO2 and the concomitant upward transport of brine solutions and contaminants from deep storage reservoirs to overlaying groundwater aquifers is considered one of the major risks associated with geologic carbon sequestration (GCS). A systematic understanding of how such leakage would impact the geochemistry of potable aquifers is crucial to the maintenance of environmental quality and the widespread acceptance of GCS. A series of batch and column experiments studies were conducted to understand the fate (mobilization and immobilization) of trace metals, such as Cd and As in the groundwater aquifer after the intrusion of CO2 gas and CO2-saturated fluids containing leached metals from deep subsurface storage reservoirs. Sediments from the High Plains aquifer in Kansas, United States, were used in this investigation, which is part of the National Risk Assessment Partnership Program sponsored by the US DOE. This aquifer was selected to be representative of consolidated sand and gravel/sandstone aquifers overlying potential CO2 sequestration repositories within the continental US. The experiments were conducted at room temperature and atmospheric pressure. The results demonstrated that Cd and As that intrude into groundwater aquifers with the leaking CO2 at initial concentrations of 40 and 114 mg/L, respectively, will be adsorbed on the sediments, in spite of the acidic pH (between 5 and 6) due to CO2 dissolution in the groundwater. Cd concentrations were well below its MCL in both the aqueous solution of the batch study and the effluent of the column study, even for one of the sediment samples which had undetectable amount of carbonate minerals to buffer the pH. Arsenic concentrations were also significantly lower than that in the influent, suggesting that natural sediments have the capacity to mitigate the adverse effects of the CO2 leakage. However, the mitigation capacity of sediments is influenced by its geochemical properties. When there are anions such as phosphate in the sediment, competitive adsorption may occur and result in higher concentrations of toxic metals in the aqueous phase. Results from these investigations will provide useful information to support site selection, risk assessment, and public education efforts associated with geological CO2 storage and sequestration.

Influence of Hydrological Perturbations and Riverbed Sediment Characteristics on Hyporheic Zone Respiration of CO2 and N2

NASA Astrophysics Data System (ADS)

Newcomer, Michelle E.; Hubbard, Susan S.; Fleckenstein, Jan H.; Maier, Ulrich; Schmidt, Christian; Thullner, Martin; Ulrich, Craig; Flipo, Nicolas; Rubin, Yoram

2018-03-01

Rivers in climatic zones characterized by dry and wet seasons often experience periodic transitions between losing and gaining conditions across the river-aquifer continuum. Infiltration shifts can stimulate hyporheic microbial biomass growth and cycling of riverine carbon and nitrogen leading to major exports of biogenic CO2 and N2 to rivers. In this study, we develop and test a numerical model that simulates biological-physical feedback in the hyporheic zone. We used the model to explore different initial conditions in terms of dissolved organic carbon availability, sediment characteristics, and stochastic variability in aerobic and anaerobic conditions from water table fluctuations. Our results show that while highly losing rivers have greater hyporheic CO2 and N2 production, gaining rivers allowed the greatest fraction of CO2 and N2 production to return to the river. Hyporheic aerobic respiration and denitrification contributed 0.1-2 g/m2/d of CO2 and 0.01-0.2 g/m2/d of N2; however, the suite of potential microbial behaviors varied greatly among sediment characteristics. We found that losing rivers that consistently lacked an exit pathway can store up to 100% of the entering C/N as subsurface biomass and dissolved gas. Our results demonstrate the importance of subsurface feedbacks whereby microbes and hydrology jointly control fate of C and N and are strongly linked to wet-season control of initial sediment conditions and hydrologic control of seepage direction. These results provide a new understanding of hydrobiological and sediment-based controls on hyporheic zone respiration, including a new explanation for the occurrence of anoxic microzones and large denitrification rates in gravelly riverbeds.

Characterization of the CO2 fluid adsorption in coal as a function of pressure using neutron scattering techniques (SANS and USANS)

USGS Publications Warehouse

Melnichenko, Y.B.; Radlinski, A.P.; Mastalerz, Maria; Cheng, G.; Rupp, J.

2009-01-01

Small angle neutron scattering techniques have been applied to investigate the phase behavior of CO2 injected into coal and possible changes in the coal pore structure that may result from this injection. Three coals were selected for this study: the Seelyville coal from the Illinois Basin (Ro = 0.53%), Baralaba coal from the Bowen Basin (Ro = 0.67%), and Bulli 4 coal from the Sydney Basin (Ro = 1.42%). The coals were selected from different depths to represent the range of the underground CO2 conditions (from subcritical to supercritical) which may be realized in the deep subsurface environment. The experiments were conducted in a high pressure cell and CO2 was injected under a range of pressure conditions, including those corresponding to in-situ hydrostatic subsurface conditions for each coal. Our experiments indicate that the porous matrix of all coals remains essentially unchanged after exposure to CO2 at pressures up to 200??bar (1??bar = 105??Pa). Each coal responds differently to the CO2 exposure and this response appears to be different in pores of various sizes within the same coal. For the Seelyville coal at reservoir conditions (16????C, 50??bar), CO2 condenses from a gas into liquid, which leads to increased average fluid density in the pores (??pore) with sizes (r) 1 ?? 105 ??? r ??? 1 ?? 104???? (??pore ??? 0.489??g/cm3) as well as in small pores with size between 30 and 300???? (??pore ??? 0.671??g/cm3). These values are by a factor of three to four higher than the density of bulk CO2 (??CO2) under similar thermodynamic conditions (??CO2 ??? 0.15??g/cm3). At the same time, in the intermediate size pores with r ??? 1000???? the average fluid density is similar to the density of bulk fluid, which indicates that adsorption does not occur in these pores. At in situ conditions for the Baralaba coal (35 OC, 100??bar), the average fluid density of CO2 in all pores is lower than that of the bulk fluid (??pore / ??CO2 ??? 0.6). Neutron scattering from the Bulli 4 coal did not show any significant variation with pressure, a phenomenon which we assign to the extremely small amount of porosity of this coal in the pore size range between 35 and 100,000????. ?? 2008 Elsevier B.V.

Sorption of Pseudomonas putida onto differently structured kaolinite minerals

NASA Astrophysics Data System (ADS)

Vasiliadou, I. A.; Papoulis, D.; Chrysikopoulos, C.; Panagiotaras, D.; Karakosta, E.; Fardis, M.; Papavassiliou, G.

2010-12-01

The presence of bio-colloids (e.g. bacteria and viruses) in the subsurface could be attributed to the release of particles from septic tanks, broken sewer lines or from artificial recharge with treated municipal wastewater. Bio-colloid transport in the subsurface is significantly affected by sorption onto the solid matrix. Bio-colloid attachment onto mobile or suspended in the aqueous phase soil particles (e.g. clay or other minerals) also may influence their fate and transport in the subsurface. The present study focuses on the investigation of Pseudomonas (Ps.) putida sorption onto well (KGa-1) and poorly (KGa-2) crystallized kaolinite minerals. Batch experiments were carried out to determine the sorption isotherms of Ps. putida onto both types of kaolinite particles. The sorption process of Ps. putida onto KGa-1 and KGa-2 is adequately described by a Langmuir isotherm. Attenuated Total Reflection Fourier Transform Infrared Spectroscopy as well as Nuclear Magnetic Resonance were employed to study the sorption mechanisms of Ps. putida. Experimental results indicated that KGa-2 presented higher affinity and sorption capacity than KGa-1. It was shown that electrostatic interactions and structural disorders can influence the sorption capacity of clay particles.

Thermal release of D2 from new Be-D co-deposits on previously baked co-deposits

NASA Astrophysics Data System (ADS)

Baldwin, M. J.; Doerner, R. P.

2015-12-01

Past experiments and modeling with the TMAP code in [1, 2] indicated that Be-D co-deposited layers are less (time-wise) efficiently desorbed of retained D in a fixed low-temperature bake, as the layer grows in thickness. In ITER, beryllium rich co-deposited layers will grow in thickness over the life of the machine. Although, compared with the analyses in [1, 2], ITER presents a slightly different bake efficiency problem because of instances of prior tritium recover/control baking. More relevant to ITER, is the thermal release from a new and saturated co-deposit layer in contact with a thickness of previously-baked, less-saturated, co-deposit. Experiments that examine the desorption of saturated co-deposited over-layers in contact with previously baked under-layers are reported and comparison is made to layers of the same combined thickness. Deposition temperatures of ∼323 K and ∼373 K are explored. It is found that an instance of prior bake leads to a subtle effect on the under-layer. The effect causes the thermal desorption of the new saturated over-layer to deviate from the prediction of the validated TMAP model in [2]. Instead of the D thermal release reflecting the combined thickness and levels of D saturation in the over and under layer, experiment differs in that, i) the desorption is a fractional superposition of desorption from the saturated over-layer, with ii) that of the combined over and under -layer thickness. The result is not easily modeled by TMAP without the incorporation of a thin BeO inter-layer which is confirmed experimentally on baked Be-D co-deposits using X-ray micro-analysis.

Stabilization of carbon dioxide and chromium slag via carbonation.

PubMed

Wu, Xingxing; Yu, Binbin; Xu, Wei; Fan, Zheng; Wu, Zucheng; Zhang, Huimin

2017-08-01

As the main greenhouse gas, CO 2 is considered as a threat in the context of global warming. Many available technologies to reduce CO 2 emission was about CO 2 separation from coal combustion and geological sequestration. However, how to deal with the cost-effective storage of CO 2 has become a new challenge. Moreover, chromium pollution, the treatment of which requires huge energy consumption, has attracted people's widespread attention. This study is aimed to develop the sequestration of CO 2 via chromium slag. A dynamic leaching experiment of chromium slag was designed to testify the ability of CO 2 adsorption onto chromium slag and to release Cr(VI) for stabilization. The results showed that the accumulative amounts of Cr(VI) were ca. 2.6 mg/g released from the chromium slag after 24 h of leaching. In addition, ca. 89 mg/g CO 2 was adsorbed by using pure CO 2 in the experiment at 12 h. Calcite is the only carbonate species in the post-carbonated slag analyzed by powder X-ray diffraction and thermal analysis. The approach provides the feasibility of the utilization of chromium slag and sequestration of the carbon dioxide at the same time at ordinary temperatures and pressures.

Mineral changes in cement-sandstone matrices induced by biocementation

DOE PAGES

Verba, C.; Thurber, A. R.; Alleau, Y.; ...

2016-04-01

Prevention of wellbore CO 2 leakage is a critical component of any successful carbon capture, utilization, and storage program. Sporosarcina pasteurii is a bacterium that has demonstrated the potential ability to seal a compromised wellbore through the enzymatic precipitation of CaCO 3. In this paper, we investigate the growth of S. pasteurii in a synthetic brine that mimics the Illinois Basin and on Mt. Simon sandstone encased in Class H Portland cement under high pressure and supercritical CO 2 (P CO2) conditions. The bacterium grew optimum at 30 °C compared to 40 °C under ambient and high pressure (10 MPa)more » conditions; and growth was comparable in experiments at high P CO2. Sporosarcina pasteurii actively induced the biomineralization of CaCO 3 polymorphs and MgCa(CO 3) 2 in both ambient and high pressure conditions as observed in electron microscopy. In contrast, abiotic (non-biological) samples exposed to CO 2 resulted in the formation of surficial vaterite and calcite. Finally, the ability of S. pasteurii to grow under subsurface conditions may be a promising mechanism to enhance wellbore integrity.« less

Fundamental Understanding of Methane-Carbon Dioxide-Water (CH4-CO2-H2O) Interactions in Shale Nanopores under Reservoir Conditions: Quarterly Report.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yifeng

Shale is characterized by the predominant presence of nanometer-scale (1-100 nm) pores. The behavior of fluids in those pores directly controls shale gas storage and release in shale matrix and ultimately the wellbore production in unconventional reservoirs. Recently, it has been recognized that a fluid confined in nanopores can behave dramatically differently from the corresponding bulk phase due to nanopore confinement (Wang, 2014). CO 2 and H 2O, either preexisting or introduced, are two major components that coexist with shale gas (predominately CH 4) during hydrofracturing and gas extraction. Note that liquid or supercritical CO 2 has been suggested asmore » an alternative fluid for subsurface fracturing such that CO 2 enhanced gas recovery can also serve as a CO 2 sequestration process. Limited data indicate that CO 2 may preferentially adsorb in nanopores (particularly those in kerogen) and therefore displace CH 4 in shale. Similarly, the presence of water moisture seems able to displace or trap CH 4 in shale matrix. Therefore, fundamental understanding of CH 4-CO 2-H 2O behavior and their interactions in shale nanopores is of great importance for gas production and the related CO 2 sequestration. This project focuses on the systematic study of CH 4-CO 2-H 2O interactions in shale nanopores under high-pressure and high temperature reservoir conditions. The proposed work will help to develop new stimulation strategies to enable efficient resource recovery from fewer and less environmentally impactful wells.« less

Fundamental Understanding of Methane-Carbon Dioxide-Water (CH 4-CO 2-H 2O) Interactions in Shale Nanopores under Reservoir Conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yifeng

2016-04-29

Shale is characterized by the predominant presence of nanometer-scale (1-100 nm) pores. The behavior of fluids in those pores directly controls shale gas storage and release in shale matrix and ultimately the wellbore production in unconventional reservoirs. Recently, it has been recognized that a fluid confined in nanopores can behave dramatically differently from the corresponding bulk phase due to nanopore confinement (Wang, 2014). CO 2 and H 2O, either preexisting or introduced, are two major components that coexist with shale gas (predominately CH 4) during hydrofracturing and gas extraction. Note that liquid or supercritical CO 2 has been suggested asmore » an alternative fluid for subsurface fracturing such that CO 2 enhanced gas recovery can also serve as a CO 2 sequestration process. Limited data indicate that CO 2 may preferentially adsorb in nanopores (particularly those in kerogen) and therefore displace CH 4 in shale. Similarly, the presence of water moisture seems able to displace or trap CH 4 in shale matrix. Therefore, fundamental understanding of CH 4-CO 2-H 2O behavior and their interactions in shale nanopores is of great importance for gas production and the related CO 2 sequestration. This project focuses on the systematic study of CH 4-CO 2-H 2O interactions in shale nanopores under high-pressure and high temperature reservoir conditions. The proposed work will help to develop new stimulation strategies to enable efficient resource recovery from fewer and less environmentally impactful wells.« less

Fundamental Understanding of Methane-Carbon Dioxide-Water (CH4-CO2-H2O) Interactions in Shale Nanopores under Reservoir Conditions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yifeng

Shale is characterized by the predominant presence of nanometer-scale (1-100 nm) pores. The behavior of fluids in those pores directly controls shale gas storage and release in shale matrix and ultimately the wellbore production in unconventional reservoirs. Recently, it has been recognized that a fluid confined in nanopores can behave dramatically differently from the corresponding bulk phase due to nanopore confinement (Wang, 2014). CO 2 and H 2O, either preexisting or introduced, are two major components that coexist with shale gas (predominately CH 4) during hydrofracturing and gas extraction. Note that liquid or supercritical CO 2 has been suggested asmore » an alternative fluid for subsurface fracturing such that CO 2 enhanced gas recovery can also serve as a CO 2 sequestration process. Limited data indicate that CO 2 may preferentially adsorb in nanopores (particularly those in kerogen) and therefore displace CH4 in shale. Similarly, the presence of water moisture seems able to displace or trap CH 4 in shale matrix. Therefore, fundamental understanding of CH 4-CO 2-H 2O behavior and their interactions in shale nanopores is of great importance for gas production and the related CO 2 sequestration. This project focuses on the systematic study of CH 4-CO 2-H 2O interactions in shale nanopores under high-pressure and high temperature reservoir conditions. The proposed work will help to develop new stimulation strategies to enable efficient resource recovery from fewer and less environmentally impactful wells.« less

Conceptual Model of Iodine Behavior in the Subsurface at the Hanford Site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Truex, Michael J.; Lee, Brady D.; Johnson, Christian D.

Isotopes of iodine were generated during plutonium production within the nine production reactors at the U.S. Department of Energy Hanford Site. The short half-life 131I that was released from the fuel into the atmosphere during the dissolution process (when the fuel was dissolved) in the Hanford Site 200 Area is no longer present at concentrations of concern in the environment. The long half-life 129I generated at the Hanford Site during reactor operations was (1) stored in single-shell and double-shell tanks, (2) discharged to liquid disposal sites (e.g., cribs and trenches), (3) released to the atmosphere during fuel reprocessing operations, ormore » (4) captured by off-gas absorbent devices (silver reactors) at chemical separations plants (PUREX, B-Plant, T-Plant, and REDOX). Releases of 129I to the subsurface have resulted in several large, though dilute, plumes in the groundwater. There is also 129I remaining in the vadose zone beneath disposal or leak locations. The fate and transport of 129I in the environment and potential remediation technologies are currently being studied as part of environmental remediation activities at the Hanford Site. A conceptual model describing the nature and extent of subsurface contamination, factors that control plume behavior, and factors relevant to potential remediation processes is needed to support environmental remedy decisions. Because 129I is an uncommon contaminant, relevant remediation experience and scientific literature are limited. In addition, its behavior in subsurface is different from that of other more common and important contaminants (e.g., U, Cr and Tc) in terms of sorption (adsorption and precipitation), and aqueous phase species transformation via redox reactions. Thus, the conceptual model also needs to both describe known contaminant and biogeochemical process information and identify aspects about which additional information is needed to effectively support remedy decisions.« less

Large-scale CO2 storage — Is it feasible?

NASA Astrophysics Data System (ADS)

Johansen, H.

2013-06-01

CCS is generally estimated to have to account for about 20% of the reduction of CO2 emissions to the atmosphere. This paper focuses on the technical aspects of CO2 storage, even if the CCS challenge is equally dependent upon finding viable international solutions to a wide range of economic, political and cultural issues. It has already been demonstrated that it is technically possible to store adequate amounts of CO2 in the subsurface (Sleipner, InSalah, Snøhvit). The large-scale storage challenge (several Gigatons of CO2 per year) is more an issue of minimizing cost without compromising safety, and of making international regulations.The storage challenge may be split into 4 main parts: 1) finding reservoirs with adequate storage capacity, 2) make sure that the sealing capacity above the reservoir is sufficient, 3) build the infrastructure for transport, drilling and injection, and 4) set up and perform the necessary monitoring activities. More than 150 years of worldwide experience from the production of oil and gas is an important source of competence for CO2 storage. The storage challenge is however different in three important aspects: 1) the storage activity results in pressure increase in the subsurface, 2) there is no production of fluids that give important feedback on reservoir performance, and 3) the monitoring requirement will have to extend for a much longer time into the future than what is needed during oil and gas production. An important property of CO2 is that its behaviour in the subsurface is significantly different from that of oil and gas. CO2 in contact with water is reactive and corrosive, and may impose great damage on both man-made and natural materials, if proper precautions are not executed. On the other hand, the long-term effect of most of these reactions is that a large amount of CO2 will become immobilized and permanently stored as solid carbonate minerals. The reduced opportunity for direct monitoring of fluid samples close to the reservoir, the general pressure build up, and the reactive nature of CO2, have created a need for new research and knowledge, to be used in conjunction with operating competence from the oil and gas industry. Experimental work on fluid flow, deformation and reaction, as well as simulations to predict the future performance of the injected CO2, are much more important in connection with CO2 storage, as compared with conventional oil and gas production. To conclude this overview of the CO2 storage challenge, the technical feasibility of large-scale CO2 storage has been demonstrated. The cost is however going to be significant, especially in the initial phase. The public acceptance of CCS, and the willingness to pay the bill, will depend on several important factors: a serious acceptance of the climate problem, economic and political regulations that are globally fair, and the willingness of each and one of us to accept a higher price for energy.

An Advanced Reservoir Simulator for Tracer Transport in Multicomponent Multiphase Compositional Flow and Applications to the Cranfield CO2 Sequestration Site

NASA Astrophysics Data System (ADS)

Moortgat, J.

2015-12-01

Reservoir simulators are widely used to constrain uncertainty in the petrophysical properties of subsurface formations by matching the history of injection and production data. However, such measurements may be insufficient to uniquely characterize a reservoir's properties. Monitoring of natural (isotopic) and introduced tracers is a developing technology to further interrogate the subsurface for applications such as enhanced oil recovery from conventional and unconventional resources, and CO2 sequestration. Oak Ridge National Laboratory has been piloting this tracer technology during and following CO2 injection at the Cranfield, Mississippi, CO2 sequestration test site. Two campaigns of multiple perfluorocarbon tracers were injected together with CO2 and monitored at two wells at 68 m and 112 m from the injection site. The tracer data suggest that multiple CO2 flow paths developed towards the monitoring wells, indicative of either channeling through high permeability pathways or of fingering. The results demonstrate that tracers provide an important complement to transient pressure data. Numerical modeling is essential to further explain and interpret the observations. To aid the development of tracer technology, we enhanced a compositional multiphase reservoir simulator to account for tracer transport. Our research simulator uses higher-order finite element (FE) methods that can capture the small-scale onset of fingering on the coarse grids required for field-scale modeling, and allows for unstructured grids and anisotropic heterogeneous permeability fields. Mass transfer between fluid phases and phase behavior are modeled with rigorous equation-of-state based phase-split calculations. We present our tracer simulator and preliminary results related to the Cranfield experiments. Applications to noble gas tracers in unconventional resources are presented by Darrah et al.

CO2 enrichment and N addition increase nutrient loss from decomposing leaf litter in subtropical model forest ecosystems

PubMed Central

Liu, Juxiu; Fang, Xiong; Deng, Qi; Han, Tianfeng; Huang, Wenjuan; Li, Yiyong

2015-01-01

As atmospheric CO2 concentration increases, many experiments have been carried out to study effects of CO2 enrichment on litter decomposition and nutrient release. However, the result is still uncertain. Meanwhile, the impact of CO2 enrichment on nutrients other than N and P are far less studied. Using open-top chambers, we examined effects of elevated CO2 and N addition on leaf litter decomposition and nutrient release in subtropical model forest ecosystems. We found that both elevated CO2 and N addition increased nutrient (C, N, P, K, Ca, Mg and Zn) loss from the decomposing litter. The N, P, Ca and Zn loss was more than tripled in the chambers exposed to both elevated CO2 and N addition than those in the control chambers after 21 months of treatment. The stimulation of nutrient loss under elevated CO2 was associated with the increased soil moisture, the higher leaf litter quality and the greater soil acidity. Accelerated nutrient release under N addition was related to the higher leaf litter quality, the increased soil microbial biomass and the greater soil acidity. Our results imply that elevated CO2 and N addition will increase nutrient cycling in subtropical China under the future global change. PMID:25608664

Variation in Biofilm Stability with Decreasing pH Affects Porous Medium Hydraulic Properties

NASA Astrophysics Data System (ADS)

Kirk, M. F.; Santillan, E. F.; McGrath, L. K.; Altman, S. J.

2010-12-01

Changes to microbial communities caused by subsurface CO2 injection may have many consequences, including possible impacts to CO2 transport. We used column experiments to examine how decreasing pH, a geochemical change associated with CO2 injection, will affect biofilm stability and ultimately the hydraulic properties of porous media. Columns consisted of 1 mm2 square capillary tubes filled with 105-150 µm diameter glass beads. Artificial groundwater medium containing 1 mM glucose was pumped through the columns at a rate of 0.01 mL/min (q = 14.4 m/day; Re = 0.03). Columns were inoculated with 3 × 10^8 CFU (avg.) of Pseudomonas fluorescens, a model biofilm former, transformed with a green fluorescent protein. Biomass distribution and transport was examined using scanning laser confocal microscopy and effluent plating. Variation in the bulk hydraulic properties of the columns was measured using manometers. In an initial experiment, biofilm growth was allowed to occur for seven days in medium with pH 7.3. Within this period, cells uniformly coated bead surfaces, effluent cell numbers stabilized at 1 × 10^9 CFU/mL, and hydraulic conductivity (K) decreased 77%. Next, medium with pH 4 was introduced. As a result, biomass within the reactor redistributed from bead surfaces to pores, effluent cell numbers decreased to 3 × 10^5 CFU/mL, and K decreased even further (>94% reduction). This decreased K was maintained until the experiment was terminated, seven days after introducing low pH medium. These results suggest that changes in biomass distribution as a result of decreased pH may initially limit transport of solubility-trapped CO2 following CO2 injection. Experiments in progress and planned will test this result in more detail and over longer periods of time. This material is based upon work supported as part of the Center for Frontiers of Subsurface Energy Security, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001114. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-AC04-94AL85000.

Burrows of the semi-terrestrial crab Ucides cordatus enhance CO2 release in a North Brazilian mangrove forest.

PubMed

Pülmanns, Nathalie; Diele, Karen; Mehlig, Ulf; Nordhaus, Inga

2014-01-01

Ucides cordatus is an abundant mangrove crab in Brazil constructing burrows of up to 2 m depth. Sediment around burrows may oxidize during low tides. This increase in sediment-air contact area may enhance carbon degradation processes. We hypothesized that 1) the sediment CO2 efflux rate is greater with burrows than without and 2) the reduction potential in radial profiles in the sediment surrounding the burrows decreases gradually, until approximating non-bioturbated conditions. Sampling was conducted during the North Brazilian wet season at neap tides. CO2 efflux rates of inhabited burrows and plain sediment were measured with a CO2/H2O gas analyzer connected to a respiration chamber. Sediment redox potential, pH and temperature were measured in the sediment surrounding the burrows at horizontal distances of 2, 5, 8 and 15 cm at four sediment depths (1, 10, 30 and 50 cm) and rH values were calculated. Sediment cores (50 cm length) were taken to measure the same parameters for plain sediment. CO2 efflux rates of plain sediment and individual crab burrows with entrance diameters of 7 cm were 0.7-1.3 µmol m(-2) s(-1) and 0.2-0.4 µmol burrows(-1) s(-1), respectively. CO2 released from a Rhizophora mangle dominated forest with an average of 1.7 U. cordatus burrows(-1) m(-2) yielded 1.0-1.7 µmol m(-2) s(-1), depending on the month and burrow entrance diameter. Laboratory experiments revealed that 20-60% of the CO2 released by burrows originated from crab respiration. Temporal changes in the reduction potential in the sediment surrounding the burrows did not influence the CO2 release from burrows. More oxidized conditions of plain sediment over time may explain the increase in CO2 release until the end of the wet season. CO2 released by U. cordatus and their burrows may be a significant pathway of CO2 export from mangrove sediments and should be considered in mangrove carbon budget estimates.

Burrows of the Semi-Terrestrial Crab Ucides cordatus Enhance CO2 Release in a North Brazilian Mangrove Forest

PubMed Central

Pülmanns, Nathalie; Diele, Karen; Mehlig, Ulf; Nordhaus, Inga

2014-01-01

Ucides cordatus is an abundant mangrove crab in Brazil constructing burrows of up to 2 m depth. Sediment around burrows may oxidize during low tides. This increase in sediment-air contact area may enhance carbon degradation processes. We hypothesized that 1) the sediment CO2 efflux rate is greater with burrows than without and 2) the reduction potential in radial profiles in the sediment surrounding the burrows decreases gradually, until approximating non-bioturbated conditions. Sampling was conducted during the North Brazilian wet season at neap tides. CO2 efflux rates of inhabited burrows and plain sediment were measured with a CO2/H2O gas analyzer connected to a respiration chamber. Sediment redox potential, pH and temperature were measured in the sediment surrounding the burrows at horizontal distances of 2, 5, 8 and 15 cm at four sediment depths (1, 10, 30 and 50 cm) and rH values were calculated. Sediment cores (50 cm length) were taken to measure the same parameters for plain sediment. CO2 efflux rates of plain sediment and individual crab burrows with entrance diameters of 7 cm were 0.7–1.3 µmol m−2 s−1 and 0.2–0.4 µmol burrows−1 s−1, respectively. CO2 released from a Rhizophora mangle dominated forest with an average of 1.7 U. cordatus burrows−1 m−2 yielded 1.0–1.7 µmol m−2 s−1, depending on the month and burrow entrance diameter. Laboratory experiments revealed that 20–60% of the CO2 released by burrows originated from crab respiration. Temporal changes in the reduction potential in the sediment surrounding the burrows did not influence the CO2 release from burrows. More oxidized conditions of plain sediment over time may explain the increase in CO2 release until the end of the wet season. CO2 released by U. cordatus and their burrows may be a significant pathway of CO2 export from mangrove sediments and should be considered in mangrove carbon budget estimates. PMID:25313661

CO2 cycle

USGS Publications Warehouse

Titus, Timothy N.; Byrne, Shane; Colaprete, Anthony; Forget, Francois; Michaels, Timothy I.; Prettyman, Thomas H.

2017-01-01

This chapter discusses the use of models, observations, and laboratory experiments to understand the cycling of CO2 between the atmosphere and seasonal Martian polar caps. This cycle is primarily controlled by the polar heat budget, and thus the emphasis here is on its components, including solar and infrared radiation, the effect of clouds (water- and CO2-ice), atmospheric transport, and subsurface heat conduction. There is a discussion about cap properties including growth and regression rates, albedos and emissivities, grain sizes and dust and/or water-ice contamination, and curious features like cold gas jets and araneiform (spider-shaped) terrain. The nature of the residual south polar cap is discussed as well as its long-term stability and ability to buffer atmospheric pressures. There is also a discussion of the consequences of the CO2 cycle as revealed by the non-condensable gas enrichment observed by Odyssey and modeled by various groups.

Electrospray ionization study of tricarbonyl fac-[Re(CO)3 (PO)(X)]-type complexes: influence of ancillary co-ligands in the release of carbon monoxide.

PubMed

Tisato, Francesco; Porchia, Marina; Shegani, Antoni; Maina, Theodosia; Papadopoulos, Minas S; Seraglia, Roberta; Traldi, Pietro

2018-05-08

fac-[Re(CO) 3 (PO)(X)]-type complexes (PO = chelated bidentate tertiary phosphine(1-), X = various neutral, mono-dentate ligands) represent a class of compounds that meets the synthetic criteria for the preparation of potential carbon monoxide (CO) release molecules (CORMs) for medicinal application. The aim of our investigation was to achieve qualitative information whether the nature of the ancillary X ligand might influence the release of CO. The release of CO has been investigated by means of product ion spectrometry of electrospray ionization-generated [M + H] + species, produced by multiple collisional experiments, using an ion trap mass spectrometer. Tandem mass spectrometry applied to the protonated species [Re(CO) 3 (PO)(X) + H] + of seven complexes (those including X = OH 2 (1), isonitrile (2, 3), imidazole (4), pyridine (5) and phosphine (6, 7) show initial loss of coordinated water (1) or pyridine (5), whereas the majority of investigated entries display initial, sequential release of CO groups. The energetics of CO release have been investigated by breakdown curves for selected collisionally-activated decomposition processes involving CO, and compared with those involving X groups. The nature of the co-ligand X drives the primary loss in the MS n processes of [Re(CO) 3 (PO)(X) + H] + compounds. When X = solvent, the energetics of these decompositions follow the trend H 2 O < MeOH < CO. In each case, loss of CO is a favored fragmentation route with associated energies following the trend: N-py ≤ P-phosphine < C-isonitrile. Overall, MS n pathways indicate that [Re(PO)] (Re with chelated PO phosphine) constitutes the residual moiety. This behavior indicates that the presence of a functionalized phosphine is essential for a sequential, controlled release of CO. This article is protected by copyright. All rights reserved.

Detection of CO2 leaks from carbon capture and storage sites to the atmosphere with combined CO2 and O2 measurements

NASA Astrophysics Data System (ADS)

van Leeuwen, Charlotte; Meijer, Harro A. J.

2015-04-01

One of the main issues in carbon capture and storage (CCS) is the possibility of leakage of CO2 from the storage reservoir to the atmosphere, both from a public health and a climate change combat perspective. Detecting these leaks in the atmosphere is difficult due to the rapid mixing of the emitted CO2 with the surrounding air masses and the high natural variability of the atmospheric CO2 concentration. Instead of measuring only the CO2 concentration of the atmosphere, its isotopes or chemical tracers that are released together with the CO2, our method uses O2 measurements in addition to CO2 measurements to detect a leak from a CCS site. CO2 and O2 are coupled in most processes on earth. In photosynthesis, plants take up CO2 and release O2 at the same time. In respiration and fossil fuel burning, O2 is consumed while CO2 is released. In case of a leak from a CCS site, however, there is no relationship between CO2 and O2. A CO2 leak can therefore be distinguished from other sources of CO2 by looking at the atmospheric CO2-O2 ratio. A natural increase of the CO2 concentration is accompanied by a drop in the O2 concentration, while an increase in the CO2 concentration caused by a leak from a CCS site does not have any effect on the O2 concentration. To demonstrate this leak detection strategy we designed and built a transportable CO2 and O2 measurement system, that is capable of measuring the relatively minute (ppm's variations on a 21% concentration) changes in the O2 concentration. The system comprises of three cases that contain the instrumentation and gas handling equipment, the gas cylinders used as reference and calibration gases and a drying system, respectively. Air is pumped to the system from an air inlet that is placed in a small tower in the field. At the conference, we will demonstrate the success of leak detection with our system by showing measurements of several CO2 release experiments, where CO2 was released at a small distance from the air inlet of our instrument.

Surface Meteorology at Kougarok Site Station, Seward Peninsula, Alaska, Ongoing from 2017

DOE Data Explorer

Bob Busey; Bob Bolton; Cathy Wilson; Lily Cohen

2017-12-04

Meteorological data are currently being collected at one location at the top of the Kougarok hill, Seward Peninsula. This December 18, 2017 release includes data for: Teller Creek Station near TL_BSV (TELLER BOTTOM METEOROLOGICAL STATION) Station is located in the lower watershed in a tussock / willow transition zone and co-located with continuous snow depth measurements and subsurface measurements. Teller Creek Station near TL_IS_5 (TELLER TOP METEOROLOGICAL STATION) Station is located in the upper watershed and co-located with continuous snow depth measurements and subsurface measurements. Two types of data products are provided for these stations: First, meteorological and site characterization data grouped by sensor/measurement type (e.g., radiation or soil pit temperature and moisture). These are *.csv files. Second, a Data Visualization tool is provided for quick visualization of measurements over time at a station. Download the *_Visualizer.zip file, extract, and click on the 'index.html' file. Data values are the same in both products.

Geological Sequestration of CO2 A Brief Overview and Potential for Application for Oklahoma

EPA Science Inventory

Geologic sequestration of CO2 is a component of C capture and storage (CCS), an emerging technology for reducing CO2 emissions to the atmosphere, and involves injection of captured CO2 into deep subsurface formations. Similar to the injection of hazardous wastes, before injection...

Mathematical model of CO2 release during milk fermentation using natural kefir grains.

PubMed

Goršek, Andreja; Ritonja, Jožef; Pečar, Darja

2018-03-12

Milk fermentation takes place in the presence of various micro-organisms, producing a variety of dairy products. The oldest of them is kefir, which is usually produced by the fermentation of milk with kefir grains. Carbon dioxide (CO 2 ), as one of the process products, also contributes to the characteristic flavor of kefir. The amount of CO 2 generated during fermentation depends on bioprocessing conditions and may change, which is not desirable at the industrial level. In this study we developed a simplified mathematical model of CO 2 release in the milk-fermentation process. An intuitive approach based on superposition and experimental analysis was used for the modeling. The chemical system studied was considered as a two-input (temperature, rotational frequency of the stirrer) one-output (CO 2 concentration) dynamic system. Based on an analysis of CO 2 release transients in the case of non-simultaneous stepwise changed input quantities, two differential equations were defined that describe the influence of the two input quantities on the output quantity. The simulation results were verified by experiments. The proposed model can be used for a comprehensive analysis of the process that is being studied and for the design and synthesis of advanced control systems, which will ensure a controlled CO 2 release at the industrial level. © 2018 Society of Chemical Industry. © 2018 Society of Chemical Industry.

Automated life-detection experiments for the Viking mission to Mars

NASA Technical Reports Server (NTRS)

Klein, H. P.

1974-01-01

As part of the Viking mission to Mars in 1975, an automated set of instruments is being built to test for the presence of metabolizing organisms on that planet. Three separate modules are combined in this instrument so that samples of the Martian surface can be subjected to a broad array of experimental conditions so as to measure biological activity. The first, the Pyrolytic Release Module, will expose surface samples to a mixture of C-14O and C-14O2 in the presence of Martian atmosphere and a light source that simulates the Martian visible spectrum. The assay system is designed to determine the extent of assimilation of CO or CO2 into organic compounds. The Gas Exchange Module will incubate surface samples in a humidified CO2 atmosphere. At specified times, portions of the incubation atmosphere will be analyzed by gas chromatography to detect the release or uptake of CO2 and several additional gases. The Label Release Module will incubate surface samples with a dilute aqueous solution of simple radioactive organic substrates in Martian atmosphere, and the gas phase will be monitored continuously for the release of labeled CO2.

Microbial Stimulation and Succession following a Test Well Injection Simulating CO₂ Leakage into a Shallow Newark Basin Aquifer

PubMed Central

O’Mullan, Gregory; Dueker, M. Elias; Clauson, Kale; Yang, Qiang; Umemoto, Kelsey; Zakharova, Natalia; Matter, Juerg; Stute, Martin; Takahashi, Taro; Goldberg, David

2015-01-01

In addition to efforts aimed at reducing anthropogenic production of greenhouse gases, geological storage of CO2 is being explored as a strategy to reduce atmospheric greenhouse gas emission and mitigate climate change. Previous studies of the deep subsurface in North America have not fully considered the potential negative effects of CO2 leakage into shallow drinking water aquifers, especially from a microbiological perspective. A test well in the Newark Rift Basin was utilized in two field experiments to investigate patterns of microbial succession following injection of CO2-saturated water into an isolated aquifer interval, simulating a CO2 leakage scenario. A decrease in pH following injection of CO2 saturated aquifer water was accompanied by mobilization of trace elements (e.g. Fe and Mn), and increased bacterial cell concentrations in the recovered water. 16S ribosomal RNA gene sequence libraries from samples collected before and after the test well injection were compared to link variability in geochemistry to changes in aquifer microbiology. Significant changes in microbial composition, compared to background conditions, were found following the test well injections, including a decrease in Proteobacteria, and an increased presence of Firmicutes, Verrucomicrobia and microbial taxa often noted to be associated with iron and sulfate reduction. The concurrence of increased microbial cell concentrations and rapid microbial community succession indicate significant changes in aquifer microbial communities immediately following the experimental CO2 leakage event. Samples collected one year post-injection were similar in cell number to the original background condition and community composition, although not identical, began to revert toward the pre-injection condition, indicating microbial resilience following a leakage disturbance. This study provides a first glimpse into the in situ successional response of microbial communities to CO2 leakage after subsurface injection in the Newark Basin and the potential microbiological impact of CO2 leakage on drinking water resources. PMID:25635675

Targeted Control of Permeability Using Carbonate Dissolution/Precipitation Reactions

NASA Astrophysics Data System (ADS)

Clarens, A. F.; Tao, Z.; Plattenberger, D.

2016-12-01

Targeted mineral precipitation reactions are a promising approach for controlling fluid flow in the deep subsurface. Here we studied the potential to use calcium and magnesium bearing silicates as cation donors that would react with aqueous phase CO2 under reservoir conditions to form solid carbonate precipitates. Preliminary experiments in high pressure and temperature columns suggest that these reactions can effectively lower the permeability of a porous media. Wollastonite (CaSiO3) was used as the model silicate, injected as solid particles into the pore space of a packed column, which was then subsequently flooded with CO2(aq). The reactions occur spontaneously, leveraging the favorable kinetics that occur at the high temperature and pressure conditions characteristic of the deep subsurface, to form solid phase calcium carbonate (CaCO3) and amorphous silica (SiO2) within the pore space. Both x-ray tomography imaging of reacted columns and electron microscopy imaging of thin sections were used to characterize where dissolution/precipitation occurred within the porous media. The spatial distribution of the products was closely tied to the flow rate and the duration of the experiment. The SiO2 product precipitated in close spatial proximity to the CaSiO3 reactant. The CaCO3 product, which is sensitive to the low pH and high pCO2 brine, precipitated out of solution further down the column as Ca2+ ions moved with the brine. The permeability of the columns decreased by several orders of magnitude after injecting the CaSiO3 particles. Following carbonation, the permeability decreased even further as precipitates filled flow paths within the pore network. A pore network model was developed to help understand the interplay between precipitation kinetics and flow in altering the permeability of the porous media. The effect of particle concentration and size, pore size, reaction time, and pCO2, are explored on pore/fracture aperture and reaction extent. To provide better control of these dynamics and ultimately devise a mechanism to deliver carbonation seed particles into leakage pathways, we are exploring the potential to functionalize the silicate particles using temperature sensitive polymer coatings.

The viking biological investigation: preliminary results.

PubMed

Klein, H P; Horowitz, N H; Levin, G V; Oyama, V I; Lederberg, J; Rich, A; Hubbard, J S; Hobby, G L; Straat, P A; Berdahl, B J; Carle, G C; Brown, F S; Johnson, R D

1976-10-01

Three different types of biological experiments on samples of martian surface material ("soil") were conducted inside the Viking lander. In the carbon assimilation or pyrolytic release experiment, (14)CO(2) and (14)CO were exposed to soil in the presence of light. A small amount of gas was found to be converted into organic material. Heat treatment of a duplicate sample prevented such conversion. In the gas exchange experiment, soil was first humidified (exposed to water vapor) for 6 sols and then wet with a complex aqueous solution of metabolites. The gas above the soil was monitored by gas chromatography. A substantial amount of O(2) was detected in the first chromatogram taken 2.8 hours after humidification. Subsequent analyses revealed that significant increases in CO(2) and only small changes in N(2) had also occurred. In the labeled release experiment, soil was moistened with a solution containing several (14)C-labeled organic compounds. A substantial evolution of radioactive gas was registered but did not occur with a duplicate heat-treated sample. Alternative chemical and biological interpretations are possible for these preliminary data. The experiments are still in process, and these results so far do not allow a decision regarding the existence of life on the plonet Mars.

Evaluation of the effect of sulfate, alkalinity and disinfector on iron release of iron pipe and iron corrosion scale characteristics under water quality changing condition using response surface methodology

NASA Astrophysics Data System (ADS)

Yang, Fan; Shi, Baoyou; Zhang, Weiyu; Guo, Jianbo; Wu, Nana; Liu, Xinyuan

2018-02-01

The response surface methodology (RSM), particularly Box-Behnken design model, was used in this study to evaluate the sulfate, alkalinity and free chlorine on iron release of pipe with groundwater supply history and its iron corrosion scale characteristics under water quality changing experiment. The RSM results together with response surface contour plots indicated that the iron release of pipe section reactors was positively related with Larson Ratio and free chlorine. The thin Corrosion scales with groundwater supply history upon collection site contained Fe3O4 (18%), α-FeOOH (64%), FeCO3 (9%), β-FeOOH (8%) and γ-FeOOH (5%), besides their averaged amorphous iron oxide content was 13.6%. After the RSM water quality changing experiment, Fe3O4, amorphous iron oxide and intermediate iron products (FeCO3, Green Rust (GR)) content on scale of Cl2Rs increased, while their α-FeOOH contents decreased and β-FeOOH disappeared. The high iron released Cl2Rs receiving higher LR water (1.40-2.04) contained highest FeCO3 (20%) and amorphous iron oxide (42%), while the low iron release Cl2Rs receiving lower LR water (0.52-0.73) had higher GR(6.5%) and the amorphous iron oxide (23.7%). In high LR water (>0.73), the thin and non-protective corrosion scale containing higher amorphous iron oxide, Fe(II) derived from new produced Fe3O4 or FeCO3 or GR was easy for oxidants and sulfate ions penetration, and had higher iron release. However the same unstable corrosion scale didn’t have much iron release in low LR water (≤0.73). RSM experiment indicated that iron release of these unstable corrosion scales had close relationship with water quality (Larson Ratio and disinfectant). Optimizing the water quality of new source water and using reasonable water purification measures can help to eliminate the red water case.

Insights into Silicate Carbonation Processes in Water-Bearing Supercritical CO2 Fluids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, Quin RS; Thompson, Christopher J.; Loring, John S.

2013-07-01

Long-term geologic storage of carbon dioxide (CO2) is considered an integral part to moderating CO2 concentrations in the atmosphere and subsequently minimizing effects of global climate change. Although subsurface injection of CO2 is common place in certain industries, deployment at the scale required for emission reduction is unprecedented and therefore requires a high degree of predictability. Accurately modeling geochemical processes in the subsurface requires experimental derived data for mineral reactions occurring between the CO2, water, and rocks. Most work in this area has focused on aqueous-dominated systems in which dissolved CO2 reacts to form crystalline carbonate minerals. Comparatively little laboratorymore » research has been conducted on reactions occurring between minerals in the host rock and the wet supercritical fluid phase. In this work, we studied the carbonation of wollastonite [CaSiO3] exposed to variably hydrated supercritical CO2 (scCO2) at a range of temperatures (50, 55 and 70 °C) and pressures (90,120 and 160 bar) that simulate conditions in geologic repositories. Mineral transformation reactions were followed by three novel in situ high pressure techniques, including x-ray diffraction that tracked the rate and extents of wollastonite conversion to calcite. Increased dissolved water concentrations in the supercritical CO2 resulted in increased silicate carbonation approaching ~50 wt. %. Development of thin water films on the mineral surface were directly observed with infrared spectroscopy and determined to be critical for facilitating carbonation processes. Even in extreme low water conditions, magic angle spinning nuclear magnetic resonance detected formation of Q3 [Si(OSi)3OH] and Q4 [Si(OSi)4] amorphous silica species. Unlike the thick (<10 μm) passivating silica layers observed in the fully water saturated scCO2 experiments, images obtained from a focused ion beam sectioned sample indicted these coatings were chemically wollastonite but structurally amorphous. In addition, evidence of an intermediate hydrated amorphous calcium carbonate forming under these conditions further emphasize the importance of understanding geochemical processes occurring in water bearing scCO2 fluids.« less

On the Role of Multi-Scale Processes in CO2 Storage Security and Integrity

NASA Astrophysics Data System (ADS)

Pruess, K.; Kneafsey, T. J.

2008-12-01

Consideration of multiple scales in subsurface processes is usually referred to the spatial domain, where we may attempt to relate process descriptions and parameters from pore and bench (Darcy) scale to much larger field and regional scales. However, multiple scales occur also in the time domain, and processes extending over a broad range of time scales may be very relevant to CO2 storage and containment. In some cases, such as in the convective instability induced by CO2 dissolution in saline waters, space and time scales are coupled in the sense that perturbations induced by CO2 injection will grow concurrently over many orders of magnitude in both space and time. In other cases, CO2 injection may induce processes that occur on short time scales, yet may affect large regions. Possible examples include seismicity that may be triggered by CO2 injection, or hypothetical release events such as "pneumatic eruptions" that may discharge substantial amounts of CO2 over a short time period. This paper will present recent advances in our experimental and modeling studies of multi-scale processes. Specific examples that will be discussed include (1) the process of CO2 dissolution-diffusion-convection (DDC), that can greatly accelerate the rate at which free-phase CO2 is stored as aqueous solute; (2) self- enhancing and self-limiting processes during CO2 leakage through faults, fractures, or improperly abandoned wells; and (3) porosity and permeability reduction from salt precipitation near CO2 injection wells, and mitigation of corresponding injectivity loss. This work was supported by the Office of Basic Energy Sciences and by the Zero Emission Research and Technology project (ZERT) under Contract No. DE-AC02-05CH11231 with the U.S. Department of Energy.

The impacts of permafrost thaw on land-atmosphere greenhouse gas exchange

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hayes, Daniel J; Kicklighter, David W.; McGuire, A. David

2014-01-01

Permafrost thaw and the subsequent mobilization of carbon stored in previously frozen soil organic matter (SOM) would be a strong positive feedback to climate1. As the northern permafrost region experiences double the rate of warming as the rest of the Earth2, the vast amount of carbon in permafrost soils3 is vulnerable to thaw, decomposition and release as atmospheric greenhouse gases (GHG). Here, we employ a process-based model simulation experiment to assess the net effect of this so-called permafrost carbon feedback (PCF) in recent decades. Results show a wide-spread increase in the depth to permafrost between 1990 and 2006, with simulatedmore » active layer thickness (ALT) capturing the mean and spatial variability of the observational data. Analysis of the simulation experiment provides an estimate of a 2.8 mm/yr increase in permafrost depth, which translates to 281 TgC/yr thawed from previously frozen SOM. Overall, we estimate a net GHG forcing of 534 MtCO2eq/yr directly tied to ALT dynamics, while accounting for CO2 (562 MtCO2eq/yr) and CH4 (52 MtCO2eq/yr) release as well as CO2 uptake by vegetation (-80 MtCO2eq/yr). This net forcing represents a significant factor in the estimated 640 MtCO2eq/yr pan-arctic GHG source4, and an additional 6.9% contribution on top of the combined 7792 MtCO2eq/yr fossil fuel emissions from the eight Arctic nations over this time period5.« less

Geochemical Impacts of Leaking CO2 from Subsurface Storage Reservoirs to Unconfined and Confined Aquifers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qafoku, Nikolla; Brown, Christopher F.; Wang, Guohui

2013-04-15

Experimental research work has been conducted and is undergoing at Pacific Northwest National Laboratory (PNNL) to address a variety of scientific issues related with the potential leaks of the carbon dioxide (CO2) gas from deep storage reservoirs. The main objectives of this work are as follows: • Develop a systematic understanding of how CO2 leakage is likely to influence pertinent geochemical processes (e.g., dissolution/precipitation, sorption/desorption and redox reactions) in the aquifer sediments. • Identify prevailing environmental conditions that would dictate one geochemical outcome over another. • Gather useful information to support site selection, risk assessment, policy-making, and public education effortsmore » associated with geological carbon sequestration. In this report, we present results from experiments conducted at PNNL to address research issues related to the main objectives of this effort. A series of batch and column experiments and solid phase characterization studies (quantitative x-ray diffraction and wet chemical extractions with a concentrated acid) were conducted with representative rocks and sediments from an unconfined, oxidizing carbonate aquifer, i.e., Edwards aquifer in Texas, and a confined aquifer, i.e., the High Plains aquifer in Kansas. These materials were exposed to a CO2 gas stream simulating CO2 gas leaking scenarios, and changes in aqueous phase pH and chemical composition were measured in liquid and effluent samples collected at pre-determined experimental times. Additional research to be conducted during the current fiscal year will further validate these results and will address other important remaining issues. Results from these experimental efforts will provide valuable insights for the development of site-specific, generation III reduced order models. In addition, results will initially serve as input parameters during model calibration runs and, ultimately, will be used to test model predictive capability and competency. The results from these investigations will provide useful information to support site selection, risk assessment, and public education efforts associated with geological, deep subsurface CO2 storage and sequestration.« less

Electrical Resistance Tomography Field Trials to Image CO2 Sequestration

NASA Astrophysics Data System (ADS)

Newmark, R.

2003-12-01

If geologic formations are used to sequester or store carbon dioxide (CO2) for long periods of time, it will be necessary to verify the containment of injected CO2 by assessing leaks and flow paths, and by understanding the geophysical and geochemical interactions between the CO2 and the geologic minerals and fluids. Remote monitoring methods are preferred, to minimize cost and impact to the integrity of the disposal reservoir. Electrical methods are especially well suited for monitoring processes involving fluids, as electrical properties are most sensitive to the presence and nature of the fluids contained in the medium. High resolution tomographs of electrical properties have been used with success for site characterization, monitoring subsurface migration of fluids in instances of leaking underground tanks, water infiltration events, subsurface steam floods, contaminant movement, and assessing the integrity of subsurface barriers. These surveys are commonly conducted utilizing vertical arrays of point electrodes in a crosswell configuration. Alternative ways of monitoring the reservoir are desirable due to the high costs of drilling the required monitoring boreholes Recent field results obtained using steel well casings as long electrodes are also promising. We have conducted field trials to evaluate the effectiveness of long electrode ERT as a potential monitoring approach for CO2 sequestration. In these trials, CO2 is not being sequestered but rather is being used as a solvent for enhanced oil recovery. This setting offers the same conditions expected during sequestration so monitoring secondary oil recovery allows a test of the method under realistic physical conditions and operational constraints. Field experience has confirmed the challenges identified during model studies. The principal difficulty are the very small signals due to the fact that formation changes occur only over a small segment of the 5000 foot length of the electrodes. In addition, telluric noise can be comparable to the signal levels during periods of geomagnetic activity. Finally, instrumentation stability over long periods is necessary to follow trends in reservoir behavior for several years. Solutions to these and other problems will be presented along with results from the first two years of work at a producing field undergoing CO2 flood. If electrical resistance tomography (ERT) imaging can be performed using existing well casings as long electrodes, it will substantially reduce the cost to monitor CO2 sequestration. This work was performed under the auspices of the U.S. Department of Energy by University of California Lawrence Livermore National Laboratory under contract No. W-7405-Eng-48.

Injectable Silica–Permanganate Gel as a Slow-Release MnO 4 - Source for Groundwater Remediation. Rheological Properties and Release Dynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Shuo; Oostrom, Martinus; Truex, Michael J.

2016-01-12

Injectable slow-release permanganate gel (ISRPG), formed by mixing KMnO 4 solution with fumed silica powder, may have a potential application in remediating chlorinated solvent plumes in groundwater. A series of batch, column, and flow cell experiments has been completed to test the gel behavior under a variety of conditions. The experiments have provided information on ISRPG rheology, permanganate (MnO 4 - ) release dynamics and distribution, and trichloroethene (TCE) degradation by ISRPG-released oxidant. The gel possesses remarkable shear thinning characteristics, resulting in a relative low viscosity during mixing, and facilitating its subsurface injection and distribution. Batch tests revealed that MnOmore » 4 - was diffused out from ISRPG into water while the gel did not dissolve or disperse into water but maintained its initial shape. Column experiments showed that MnO 4 - release from ISRPG lasted considerably longer than the release from aqueous solution. TCE degradation by ISRPG-released MnO 4 - was much more effective than that when MnO 4 - was delivered using aqueous solution injection. In two-dimensional flow cell experiments, it was demonstrated that ISRPG slowly released a long-lasting low concentration MnO 4 - plume sufficient for remediation and sustainable in an aquifer for a long period of time.« less

THE HYDROCARBON SPILL SCREENING MODEL (HSSM), VOLUME 2: THEORETICAL BACKGROUND AND SOURCE CODES

EPA Science Inventory

A screening model for subsurface release of a nonaqueous phase liquid which is less dense than water (LNAPL) is presented. The model conceptualizes the release as consisting of 1) vertical transport from near the surface to the capillary fringe, 2) radial spreading of an LNAPL l...

Multifluid geo-energy systems: Using geologic CO 2 storage for geothermal energy production and grid-scale energy storage in sedimentary basins

DOE PAGES

Buscheck, Thomas A.; Bielicki, Jeffrey M.; Edmunds, Thomas A.; ...

2016-05-05

We present an approach that uses the huge fluid and thermal storage capacity of the subsurface, together with geologic carbon dioxide (CO 2) storage, to harvest, store, and dispatch energy from subsurface (geothermal) and surface (solar, nuclear, fossil) thermal resources, as well as excess energy on electric grids. Captured CO 2 is injected into saline aquifers to store pressure, generate artesian flow of brine, and provide a supplemental working fluid for efficient heat extraction and power conversion. Concentric rings of injection and production wells create a hydraulic mound to store pressure, CO 2, and thermal energy. This energy storage canmore » take excess power from the grid and excess/waste thermal energy, and dispatch that energy when it is demanded and thus enable higher penetration of variable renewable energy technologies (e.g., wind, solar). CO 2 stored in the subsurface functions as a cushion gas to provide enormous pressure-storage capacity and displace large quantities of brine, some of which can be treated for a variety of beneficial uses. Geothermal power and energy-storage applications may generate enough revenues to compensate for CO 2 capture costs. While our approach can use nitrogen (N 2), in addition to CO 2, as a supplemental fluid, and store thermal energy, this study focuses using CO 2 for geothermal energy production and grid-scale energy storage. We conduct a techno-economic assessment to determine the levelized cost of electricity of using this approach to generate geothermal power. We present a reservoir pressure-management strategy that diverts a small portion of the produced brine for beneficial consumptive use to reduce the pumping cost of fluid recirculation, while reducing the risk of seismicity, caprock fracture, and CO 2 leakage.« less

Imaging and quantification of spreading and trapping of carbon dioxide in saline aquifers using meter-scale laboratory experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Trevisan, Luca; Pini, Ronny; Cihan, Abdullah

The role of capillary forces during buoyant migration of CO 2 is critical toward plume immobilization within the postinjection phase of a geological carbon sequestration operation. However, the inherent heterogeneity of the subsurface makes it very challenging to evaluate the effects of capillary forces on the storage capacity of these formations and to assess in situ plume evolution. To overcome the lack of accurate and continuous observations at the field scale and to mimic vertical migration and entrapment of realistic CO 2 plumes in the presence of a background hydraulic gradient, we conducted two unique long-term experiments in a 2.44more » m × 0.5 m tank. X-ray attenuation allowed measuring the evolution of a CO 2 -surrogate fluid saturation, thus providing direct insight into capillarity-dominated and buoyancy-dominated flow processes occurring under successive drainage and imbibition conditions. The comparison of saturation distributions between two experimental campaigns suggests that layered-type heterogeneity plays an important role on nonwetting phase (NWP) migration and trapping, because it leads to (i) longer displacement times (3.6 months versus 24 days) to reach stable trapping conditions, (ii) limited vertical migration of the plume (with center of mass at 39% versus 55% of aquifer thickness), and (iii) immobilization of a larger fraction of injected NWP mass (67.2% versus 51.5% of injected volume) as compared to the homogenous scenario. Finally, while these observations confirm once more the role of geological heterogeneity in controlling buoyant flows in the subsurface, they also highlight the importance of characterizing it at scales that are below seismic resolution (1–10 m).« less

Imaging and quantification of spreading and trapping of carbon dioxide in saline aquifers using meter-scale laboratory experiments

DOE PAGES

Trevisan, Luca; Pini, Ronny; Cihan, Abdullah; ...

2016-12-27

The role of capillary forces during buoyant migration of CO 2 is critical toward plume immobilization within the postinjection phase of a geological carbon sequestration operation. However, the inherent heterogeneity of the subsurface makes it very challenging to evaluate the effects of capillary forces on the storage capacity of these formations and to assess in situ plume evolution. To overcome the lack of accurate and continuous observations at the field scale and to mimic vertical migration and entrapment of realistic CO 2 plumes in the presence of a background hydraulic gradient, we conducted two unique long-term experiments in a 2.44more » m × 0.5 m tank. X-ray attenuation allowed measuring the evolution of a CO 2 -surrogate fluid saturation, thus providing direct insight into capillarity-dominated and buoyancy-dominated flow processes occurring under successive drainage and imbibition conditions. The comparison of saturation distributions between two experimental campaigns suggests that layered-type heterogeneity plays an important role on nonwetting phase (NWP) migration and trapping, because it leads to (i) longer displacement times (3.6 months versus 24 days) to reach stable trapping conditions, (ii) limited vertical migration of the plume (with center of mass at 39% versus 55% of aquifer thickness), and (iii) immobilization of a larger fraction of injected NWP mass (67.2% versus 51.5% of injected volume) as compared to the homogenous scenario. Finally, while these observations confirm once more the role of geological heterogeneity in controlling buoyant flows in the subsurface, they also highlight the importance of characterizing it at scales that are below seismic resolution (1–10 m).« less

Imaging and quantification of spreading and trapping of carbon dioxide in saline aquifers using meter-scale laboratory experiments

NASA Astrophysics Data System (ADS)

Trevisan, Luca; Pini, Ronny; Cihan, Abdullah; Birkholzer, Jens T.; Zhou, Quanlin; González-Nicolás, Ana; Illangasekare, Tissa H.

2017-01-01

The role of capillary forces during buoyant migration of CO2 is critical toward plume immobilization within the postinjection phase of a geological carbon sequestration operation. However, the inherent heterogeneity of the subsurface makes it very challenging to evaluate the effects of capillary forces on the storage capacity of these formations and to assess in situ plume evolution. To overcome the lack of accurate and continuous observations at the field scale and to mimic vertical migration and entrapment of realistic CO2 plumes in the presence of a background hydraulic gradient, we conducted two unique long-term experiments in a 2.44 m × 0.5 m tank. X-ray attenuation allowed measuring the evolution of a CO2-surrogate fluid saturation, thus providing direct insight into capillarity-dominated and buoyancy-dominated flow processes occurring under successive drainage and imbibition conditions. The comparison of saturation distributions between two experimental campaigns suggests that layered-type heterogeneity plays an important role on nonwetting phase (NWP) migration and trapping, because it leads to (i) longer displacement times (3.6 months versus 24 days) to reach stable trapping conditions, (ii) limited vertical migration of the plume (with center of mass at 39% versus 55% of aquifer thickness), and (iii) immobilization of a larger fraction of injected NWP mass (67.2% versus 51.5% of injected volume) as compared to the homogenous scenario. While these observations confirm once more the role of geological heterogeneity in controlling buoyant flows in the subsurface, they also highlight the importance of characterizing it at scales that are below seismic resolution (1-10 m).

Abiotic CO2 reduction during geologic carbon sequestration facilitated by Fe(II)-bearing minerals

NASA Astrophysics Data System (ADS)

Nielsen, L. C.; Maher, K.; Bird, D. K.; Brown, G. E.; Thomas, B.; Johnson, N. C.; Rosenbauer, R. J.

2012-12-01

Redox reactions involving subsurface minerals and fluids and can lead to the abiotic generation of hydrocarbons from CO2 under certain conditions. Depleted oil reservoirs and saline aquifers targeted for geologic carbon sequestration (GCS) can contain significant quantities of minerals such as ferrous chlorite, which could facilitate the abiotic reduction of carbon dioxide to n-carboxylic acids, hydrocarbons, and amorphous carbon (C0). If such reactions occur, the injection of supercritical CO2 (scCO2) could significantly alter the oxidation state of the reservoir and cause extensive reorganization of the stable mineral assemblage via dissolution and reprecipitation reactions. Naturally occurring iron oxide minerals such as magnetite are known to catalyze CO2 reduction, resulting in the synthesis of organic compounds. Magnetite is thermodynamically stable in Fe(II) chlorite-bearing mineral assemblages typical of some reservoir formations. Thermodynamic calculations demonstrate that GCS reservoirs buffered by the chlorite-kaolinite-carbonate(siderite/magnesite)-quartz assemblage favor the reduction of CO2 to n-carboxylic acids, hydrocarbons, and C0, although the extent of abiotic CO2 reduction may be kinetically limited. To investigate the rates of abiotic CO2 reduction in the presence of magnetite, we performed batch abiotic CO2 reduction experiments using a Dickson-type rocking hydrothermal apparatus at temperatures (373 K) and pressures (100 bar) within the range of conditions relevant to GCS. Blank experiments containing CO2 and H2 were used to rule out the possibility of catalytic activity of the experimental apparatus. Reaction of brine-suspended magnetite nanoparticles with scCO2 at H2 partial pressures typical of reservoir rocks - up to 100 and 0.1 bars respectively - was used to investigate the kinetics of magnetite-catalyzed abiotic CO2 reduction. Later experiments introducing ferrous chlorite (ripidolite) were carried out to determine the potential for heterogeneous catalysis in GCS systems.

Characteristics of CO2 release from forest soil in the mountains near Beijing.

PubMed

Sun, Xiang Yang; Gao, Cheng Da; Zhang, Lin; Li, Su Yan; Qiao, Yong

2011-04-01

CO2 release from forest soil is a key driver of carbon cycling between the soil and atmosphere ecosystem. The rate of CO2 released from soil was measured in three forest stands (in the mountainous region near Beijing, China) by the alkaline absorption method from 2004 to 2006. The rate of CO2 released did not differ among the three stands. The CO2 release rate ranged from - 341 to 1,193 mg m(-2) h(-1), and the mean value over all three forests and sampling times was 286 mg m(-2) h(-1). CO2 release was positively correlated with soil water content and the soil temperature. Diurnally, CO2 release was higher in the day than at night. Seasonally, CO2 release was highest in early autumn and lowest in winter; in winter, negative values of CO2 release suggested that CO2 was absorbed by soil.

Deep aquifer prokaryotic community responses to CO2 geosequestration

NASA Astrophysics Data System (ADS)

Mu, A.; Moreau, J. W.

2015-12-01

Little is known about potential microbial responses to supercritical CO2 (scCO2) injection into deep subsurface aquifers, a currently experimental means for mitigating atmospheric CO2 pollution being trialed at several locations around the world. One such site is the Paaratte Formation of the Otway Basin (~1400 m below surface; 60°C; 2010 psi), Australia. Microbial responses to scCO2 are important to understand as species selection may result in changes to carbon and electron flow. A key aim is to determine if biofilm may form in aquifer pore spaces and reduce aquifer permeability and storage. This study aimed to determine in situ, using 16S rRNA gene, and functional metagenomic analyses, how the microbial community in the Otway Basin geosequestration site responded to experimental injection of 150 tons of scCO2. We demonstrate an in situ sampling approach for detecting deep subsurface microbial community changes associated with geosequestration. First-order level analyses revealed a distinct shift in microbial community structure following the scCO2 injection event, with proliferation of genera Comamonas and Sphingobium. Similarly, functional profiling of the formation revealed a marked increase in biofilm-associated genes (encoding for poly-β-1,6-N-acetyl-D-glucosamine). Global analysis of the functional gene profile highlights that scCO2 injection potentially degraded the metabolism of CH4 and lipids. A significant decline in carboxydotrophic gene abundance (cooS) and an anaerobic carboxydotroph OTU (Carboxydocella), was observed in post-injection samples. The potential impacts on the flow networks of carbon and electrons to heterotrophs are discussed. Our findings yield insights for other subsurface systems, such as hydrocarbon-rich reservoirs and high-CO2 natural analogue sites.

Modelling deuterium release from tungsten after high flux high temperature deuterium plasma exposure

NASA Astrophysics Data System (ADS)

Grigorev, Petr; Matveev, Dmitry; Bakaeva, Anastasiia; Terentyev, Dmitry; Zhurkin, Evgeny E.; Van Oost, Guido; Noterdaeme, Jean-Marie

2016-12-01

Tungsten is a primary candidate for plasma facing materials for future fusion devices. An important safety concern in the design of plasma facing components is the retention of hydrogen isotopes. Available experimental data is vast and scattered, and a consistent physical model of retention of hydrogen isotopes in tungsten is still missing. In this work we propose a model of non-equilibrium hydrogen isotopes trapping under fusion relevant plasma exposure conditions. The model is coupled to a diffusion-trapping simulation tool and is used to interpret recent experiments involving high plasma flux exposures. From the computational analysis performed, it is concluded that high flux high temperature exposures (T = 1000 K, flux = 1024 D/m2/s and fluence of 1026 D/m2) result in generation of sub-surface damage and bulk diffusion, so that the retention is driven by both sub-surface plasma-induced defects (bubbles) and trapping at natural defects. On the basis of the non-equilibrium trapping model we have estimated the amount of H stored in the sub-surface region to be ∼10-5 at-1, while the bulk retention is about 4 × 10-7 at-1, calculated by assuming the sub-surface layer thickness of about 10 μm and adjusting the trap concentration to comply with the experimental results for the integral retention.

Dynamics of nonreactive solute transport in the permafrost environment

NASA Astrophysics Data System (ADS)

Svyatskiy, D.; Coon, E. T.; Moulton, J. D.

2017-12-01

As part of the DOE Office of Science Next Generation Ecosystem Experiment, NGEE-Arctic, researchers are developing process-rich models to understand and predict the evolution of water sources and hydrologic flow pathways resulting from degrading permafrost. The sources and interaction of surface and subsurface water and flow paths are complex in space and time due to strong interplay between heterogeneous subsurface parameters, the seasonal to decadal evolution of the flow domain, climate driven melting and release of permafrost ice as a liquid water source, evolving surface topography and highly variable meteorological data. In this study, we seek to characterize the magnitude of vertical and lateral subsurface flows in a cold, wet tundra, polygonal landscape characteristic of the Barrow Peninsula, AK. To better understand the factors controlling water flux partitioning in these low gradient landscapes, NGEE researchers developed and are applying the Advanced Terrestrial Simulator (ATS), which fully couples surface and subsurface flow and energy processes, snow distribution and atmospheric forcing. Here we demonstrate the integration of a new solute transport model within the ATS, which enables the interpretation of applied and natural tracer experiments and observations aimed at quantifying water sources and flux partitioning. We examine the role of ice wedge polygon structure, freeze-thaw processes and soil properties on the seasonal transport of water within and through polygons features, and compare results to tracer experiments on 2D low-centered and high-centered transects corresponding to artificial as well as realistic topographical data from sites in polygonal tundra. These simulations demonstrate significant difference between flow patterns between permafrost and non-permafrost environments due to active layer freeze-thaw processes.

Effects of Droplet Size on Intrusion of Sub-Surface Oil Spills

NASA Astrophysics Data System (ADS)

Adams, Eric; Chan, Godine; Wang, Dayang

2014-11-01

We explore effects of droplet size on droplet intrusion and transport in sub-surface oil spills. Negatively buoyant glass beads released continuously to a stratified ambient simulate oil droplets in a rising multiphase plume, and distributions of settled beads are used to infer signatures of surfacing oil. Initial tests used quiescent conditions, while ongoing tests simulate currents by towing the source and a bottom sled. Without current, deposited beads have a Gaussian distribution, with variance increasing with decreasing particle size. Distributions agree with a model assuming first order particle loss from an intrusion layer of constant thickness, and empirically determined flow rate. With current, deposited beads display a parabolic distribution similar to that expected from a source in uniform flow; we are currently comparing observed distributions with similar analytical models. Because chemical dispersants have been used to reduce oil droplet size, our study provides one measure of their effectiveness. Results are applied to conditions from the `Deep Spill' field experiment, and the recent Deepwater Horizon oil spill, and are being used to provide ``inner boundary conditions'' for subsequent far field modeling of these events. This research was made possible by grants from Chevron Energy Technology Co., through the Chevron-MITEI University Partnership Program, and BP/The Gulf of Mexico Research Initiative, GISR.

Fayalite Dissolution and Siderite Formation in Water-Saturated Supercritical CO2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qafoku, Odeta; Kovarik, Libor; Kukkadapu, Ravi K.

2012-11-25

Olivines, a significant constituent of basaltic rocks, have the potential to immobilize permanently CO2 after it is injected in the deep subsurface, due to carbonation reactions occurring between CO2 and the host rock. To investigate the reactions of fayalitic olivine with supercritical CO2 (scCO2) and formation of mineral carbonates, experiments were conducted at temperatures of 35 °C to 80 °C, 90 atm pressure and anoxic conditions. For every temperature, the dissolution of fayalite was examined both in the presence of liquid water and H2O-saturated scCO2. The experiments were conducted in a high pressure batch reactor at reaction time extending upmore » to 85 days. The newly formed products were characterized using a comprehensive suite of bulk and surface characterization techniques X-ray diffraction, Transmission/Emission Mössbauer Spectroscopy, Scanning Electron Microscopy coupled with Focused Ion Beam, and High Resolution Transmission Electron Microscopy. Siderite with rhombohedral morphology was formed at 35 °C, 50 °C, and 80 °C in the presence of liquid water and scCO2. In H2O-saturated scCO2, the formation of siderite was confirmed only at high temperature (80 °C). Characterization of reacted samples in H2O-saturated scCO2 with high resolution TEM indicated that siderite formation initiated inside voids created during the initial steps of fayalite dissolution. Later stages of fayalite dissolution result in the formation of siderite in layered vertical structures, columns or pyramids with a rhombus base morphology.« less

Pseudowollastonite Carbonation Could Enable New Frontiers in Carbon Storage

NASA Astrophysics Data System (ADS)

Plattenberger, D.; Tao, Z.; Ling, F. T.; Peters, C. A.; Clarens, A. F.

2017-12-01

One of the primary challenges of CO2 mineral trapping is that precipitation reactions are reversible. A wide range of solid magnesium, iron, or calcium carbonates (such as magnesite, MgCO3) can be synthesized by reacting mineral silicates (such as olivine, Mg2SiO4) with CO2 to produce mineral carbonates. However, if CO2 remains present at high concentrations, as would be the case in many subsurface environments, the carbonate minerals could re-dissolve, making the precipitated carbonates impermanent forms of storage. In this work, we study pseudowollastonite (CaSiO3), a crystalline form of calcium silicate that is common in slags, cement, and calcium-rich volcanic formations, for its potential to produce other secondary mineral phases that may be resistant to dissolution under low pH conditions. These secondary mineral precipitation phases have morphologies and X-ray diffraction patterns that resemble both calcium silicate hydrate gels as well as crystalline calcium silicate carbonate hydrates. The combination of these phases forms a complex system that may resist acid attack while providing strength and limiting flow in the subsurface environment. High pressure and temperature column experiments carried out in our lab show that pseudowollastonite carbonation effectively lowers permeability in columns of sintered glass beads. Many of the pore throats are clogged by precipitates, as seen using micro X-ray tomography of intact columns and electron microscopy of thin sections. The spatial distribution of the products suggests that calcite forms toward the inlet of the columns where the pCO2 is highest. This forms a barrier that reduces, but does not eliminate, the availability of CO2 deeper in the porous media where the secondary phases precipitate. The existence of the calcite zone drives the reduction in permeability and the depth of this zone is self-limiting, which could have important implications for limiting leakage and unwanted migration of CO2 in some instances.

Hydrochemical Impacts of CO2 Leakage on Fresh Groundwater: a Field Scale Experiment

NASA Astrophysics Data System (ADS)

Lions, J.; Gal, F.; Gombert, P.; Lafortune, S.; Darmoul, Y.; Prevot, F.; Grellier, S.; Squarcioni, P.

2013-12-01

One of the questions related to the emerging technology for Carbon Geological Storage concerns the risk of CO2 migration beyond the geological storage formation. In the event of leakage toward the surface, the CO2 might affect resources in neighbouring formations (geothermal or mineral resources, groundwater) or even represent a hazard for human activities at the surface or in the subsurface. In view of the preservation of the groundwater resources mainly for human consumption, this project studies the potential hydrogeochemical impacts of CO2 leakage on fresh groundwater quality. One of the objectives is to characterize the bio-geochemical mechanisms that may impair the quality of fresh groundwater resources in case of CO2 leakage. To reach the above mentioned objectives, this project proposes a field experiment to characterize in situ the mechanisms that could impact the water quality, the CO2-water-rock interactions and also to improve the monitoring methodology by controlled CO2 leakage in shallow aquifer. The tests were carried out in an experimental site in the chalk formation of the Paris Basin. The site is equipped with an appropriate instrumentation and was previously characterized (8 piezometers, 25 m deep and 4 piezairs 11 m deep). The injection test was preceded by 6 months of monitoring in order to characterize hydrodynamics and geochemical baselines of the site (groundwater, vadose and soil). Leakage into groundwater is simulated via the injection of a small quantity of food-grade CO2 (~20 kg dissolved in 10 m3 of water) in the injection well at a depth of about 20 m. A plume of dissolved CO2 is formed and moves downward according to the direction of groundwater flow and probably by degassing in part to the surface. During the injection test, hydrochemical monitoring of the aquifer is done in situ and by sampling. The parameters monitored in the groundwater are the piezometric head, temperature, pH and electrical conductivity. Analysis on water samples provide chemical elements (major, minor and trace metals), dissolved gases, microbiological diversity and isotopes (13C). The evolution of the composition of the groundwater in terms of major elements, trace elements and isotope signatures is interpreted in terms of geochemical mechanisms, and the water-rock-CO2 interactions are characterized. Modification of the chemical composition of water in the aquifer due to CO2 injection is assessed in term of groundwater quality i.e. metal element release and the possibility of exceeding references and quality of water for human consumption. One outcome of the CIPRES project will be to highlight mechanisms that can impact groundwater quality when a CO2 leakage occurs and to propose recommendations to prevent or/and eliminate negative effects and any risks to the environment and human health. This project is partially funded by the French Research Agency (ANR).

Experimental and simulation studies of iron oxides for geochemical fixation of CO2-SO2 gas mixtures

USGS Publications Warehouse

Garcia, Susana; Rosenbauer, Robert J.; Palandri, James; Maroto-Valer, M. Mercedes

2011-01-01

Iron-bearing minerals are reactive phases of the subsurface environment and could potentially trap CO2–SO2gas mixtures derived from fossil fuel combustion processes by their conversion to siderite (FeCO3) and dissolved sulfate. Changes in fluid and mineral compositions resulting from reactions, involving the co-injection of SO2 with CO2 were observed both theoretically and experimentally. Experiments were conducted with a natural hematite (α-Fe2O3) sample. A high pressure-high temperature apparatus was used to simulate conditions in geologic formations deeper than 800 m, where CO2 is in the supercritical state. Solid samples were allowed to react with a NaCl–NaOH brine and SO2-bearing CO2-dominated gas mixtures. The predicted equilibrium mineral assemblage at 100 °C and 250 bar became hematite, dawsonite (NaAl(OH)2CO3), siderite (FeCO3) and quartz (SiO2). Experimentally, siderite and dawsonite, derived from the presence of kaolinite (Al2Si2O5(OH)4) in the parent material, were present in residual solids at longer reaction time intervals, which agreed well with results from the modelling work.

CO2 leakage from carbon dioxide capture and storage (CCS) systems affects organic matter cycling in surface marine sediments.

PubMed

Rastelli, Eugenio; Corinaldesi, Cinzia; Dell'Anno, Antonio; Amaro, Teresa; Greco, Silvestro; Lo Martire, Marco; Carugati, Laura; Queirós, Ana M; Widdicombe, Stephen; Danovaro, Roberto

2016-12-01

Carbon dioxide capture and storage (CCS), involving the injection of CO 2 into the sub-seabed, is being promoted worldwide as a feasible option for reducing the anthropogenic CO 2 emissions into the atmosphere. However, the effects on the marine ecosystems of potential CO 2 leakages originating from these storage sites have only recently received scientific attention, and little information is available on the possible impacts of the resulting CO 2 -enriched seawater plumes on the surrounding benthic ecosystem. In the present study, we conducted a 20-weeks mesocosm experiment exposing coastal sediments to CO 2 -enriched seawater (at 5000 or 20,000 ppm), to test the effects on the microbial enzymatic activities responsible for the decomposition and turnover of the sedimentary organic matter in surface sediments down to 15 cm depth. Our results indicate that the exposure to high-CO 2 concentrations reduced significantly the enzymatic activities in the top 5 cm of sediments, but had no effects on subsurface sediment horizons (from 5 to 15 cm depth). In the surface sediments, both 5000 and 20,000 ppm CO 2 treatments determined a progressive decrease over time in the protein degradation (up to 80%). Conversely, the degradation rates of carbohydrates and organic phosphorous remained unaltered in the first 2 weeks, but decreased significantly (up to 50%) in the longer term when exposed at 20,000 ppm of CO 2 . Such effects were associated with a significant change in the composition of the biopolymeric carbon (due to the accumulation of proteins over time in sediments exposed to high-pCO 2 treatments), and a significant decrease (∼20-50% at 5000 and 20,000 ppm respectively) in nitrogen regeneration. We conclude that in areas immediately surrounding an active and long-lasting leak of CO 2 from CCS reservoirs, organic matter cycling would be significantly impacted in the surface sediment layers. The evidence of negligible impacts on the deeper sediments should be considered with caution and further investigated simulating the intrusion of CO 2 from a subsurface source, as occurring during real CO 2 leakages from CCS sites. Copyright © 2016 Elsevier Ltd. All rights reserved.

Leaching of organic acids from macromolecular organic matter by non-supercritical CO2

NASA Astrophysics Data System (ADS)

Sauer, P.; Glombitza, C.; Kallmeyer, J.

2012-04-01

The storage of CO2 in underground reservoirs is discussed controversly in the scientific literature. The worldwide search for suitable storage formations also considers coal-bearing strata. CO2 is already injected into seams for enhanced recovery of coal bed methane. However, the effects of increased CO2 concentration, especially on organic matter rich formations, are rarely investigated. The injected CO2 will dissolve in the pore water, causing a decrease in pH and resulting in acidic formation waters. Huge amounts of low molecular weight organic acids (LMWOAs) are chemically bound to the macromolecular matrix of sedimentary organic matter and may be liberated by hydrolysis, which is enhanced by the acidic porewater. Recent investigations outlined the importance of LMWOAs as a feedstock for microbial life in the subsurface [1]. Therefore, injection of CO2 into coal formations may result in enhanced nutrient supply for subsurface microbes. To investigate the effect of high concentrations of dissolved CO2 on the release of LMWOAs from coal we developed an inexpensive high-pressure high temperature system that allows manipulating the partial pressure of dissolved gases at pressures and temperatures up to 60 MPa and 120° C, respectively. In a reservoir vessel, gases are added to saturate the extraction medium to the desired level. Inside the extraction vessel hangs a flexible and inert PVDF sleeve (polyvinylidene fluoride, almost impermeable for gases), holding the sample and separating it from the pressure fluid. The flexibility of the sleeve allows for subsampling without loss of pressure. Coal samples from the DEBITS-1 well, Waikato Basin, NZ (R0 = 0.29, TOC = 30%). were extracted at 90° C and 5 MPa, either with pure or CO2-saturated water. Subsamples were taken at different time points during the extraction. The extracted LMWOAs such as formate, acetate and oxalate were analysed by ion chromatography. Yields of LMWOAs were higher with pure water than with CO2-saturated water, revealing a suppressing effect of CO2. Both extractions had higher yields than those reported for soxhlet extraction [2]. LMWOAs found in the extraction fluid may not just result from hydrolysis but also from different secondary reactions. It was suggested that oxalate in aqueous extracts of coals is a result of the decomposition of 1,2-dihydroxy-carboxylic acids [3]. We assume that for oxalate (and maybe for other LMWOAs as well) the extraction yield is not only affected by hydrolysis but also by secondary reactions, which may be inhibited or suppressed in the presence of CO2 in the extraction medium. During soxhlet extraction the sample only gets into contact with freshly distilled water, not with an acidic fluid. This may explain the lower yields.

Computational Modeling of the Geologic Sequestration of Carbon Dioxide

EPA Science Inventory

Geologic sequestration of CO2 is a component of C capture and storage (CCS), an emerging technology for reducing CO2 emissions to the atmosphere, and involves injection of captured CO2 into deep subsurface formations. Similar to the injection of hazardous wastes, before injection...

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balashov, Victor N.; Brantley, Susan L.; Guthrie, George D.

One idea for mitigating the increase in fossil- fuel generated carbon dioxide (CO 2) in the atmosphere is to inject CO 2 into subsurface saline sandstone reservoirs, thereby storing it in those geologic formations and out of the atmosphere.

Columnar and subsurface silicide growth with novel molecular beam epitaxy techniques

NASA Technical Reports Server (NTRS)

Fathauer, R. W.; George, T.; Pike, W. T.

1992-01-01

We have found novel growth modes for epitaxial CoSi2 at high temperatures coupled with Si-rich flux ratios or low deposition rates. In the first of these modes, codeposition of metal and Si at 600-800 C with excess Si leads to the formation of epitaxial silicide columns surrounded by single-crystal Si. During the initial stages of the deposition, the excess Si grows homoepitaxially in between the silicide, which forms islands, so that the lateral growth of the islands is confined. Once a template layer is established by this process, columns of silicide form as a result of selective epitaxy of silicide on silicide and Si on Si. This growth process allows nanometer control over silicide particles in three dimensions. In the second of these modes, a columnar silicide seed layer is used as a template to nucleate subsurface growth of CoSi2. With a 100 nm Si layer covering CoSi2 seeds, Co deposited at 800C and 0.01 nm/s diffuses down to grow on the buried seeds rather than nucleating surface silicide islands. For thicker Si caps or higher deposition rates, the surface concentration of Co exceeds the critical concentration for nucleation of islands, preventing this subsurface growth mode from occurring. Using this technique, single-crystal layers of CoSi2 buried under single-crystal Si caps have been grown.

Pore networks and polymer rearrangement on a drug-eluting stent as revealed by correlated confocal Raman and atomic force microscopy.

PubMed

Biggs, Kevin B; Balss, Karin M; Maryanoff, Cynthia A

2012-05-29

Drug release from and coating morphology on a CYPHER sirolimus-eluting coronary stent (SES) during in vitro elution were studied by correlated confocal Raman and atomic force microscopy (CRM and AFM, respectively). Chemical surface and subsurface maps of the SES were generated in the same region of interest by CRM and were correlated with surface topography measured by AFM at different elution times. For the first time, a direct correlation between drug-rich regions and the coating morphology was made on a drug-eluting medical device, linking drug release with pore formation, pore throats, and pore networks. Drug release was studied on a drug-eluting stent (DES) system with a multicomponent carrier matrix (poly(n-butyl methacrylate) [PBMA] and poly(ethylene-co-vinyl acetate) [PEVA]). The polymer was found to rearrange postelution because confluence of the carrier polymer matrix reconstituted the voids created by drug release.

Geological subsurface will contribute significantly to the implementation of the energy policy towards renewables in Germany

NASA Astrophysics Data System (ADS)

Martens, Sonja; Kühn, Michael

2015-04-01

The demands to exploit the geological subsurface are increasing. In addition to the traditional production of raw materials such as natural gas and petroleum, or potable groundwater extraction the underground will most likely also be used to implement the climate and energy policy objectives in the context of the energy transition to renewables. These include the storage of energy from renewable sources (e.g. hydrogen and methane), the use of geothermal energy and possibly the long-term storage of carbon dioxide to reduce the release of greenhouse gases into the atmosphere. The presentation addresses the question which realistic contribution can be expected from the geo-resource subsurface for the energy revolution, the detachment of fossil and nuclear fuels as well as the reduction of CO2 emissions. The study of Henning and Palzer [1] that models the energy balance of the electricity and heat sector including all renewable energy converters, storage components and loads for a future German energy system shows that provision with 100% renewables is economically feasible by 2050. Based on their work, our estimates underline that already in 2015 more than 100% of the required methane storage capacities therein are available and more than 100% of the heat pump demands might be covered by shallow and deep geothermal energy production in the future. In addition we show that a newly developed energy storage system [2-3] could be applied to store 20-60% of the surplus energy from renewables expected for 2050 with integrated gas storage of methane and CO2. [1] Henning H-M, Palzer A (2014) A comprehensive model for the German electricity and heat sector in a future energy system with a dominant contribution from renewable energy technologies -- Part I: Methodology. Renewable and Sustainable Energy Reviews 30, 1003-1018. doi: 10.1016/j.rser.2013.09.012 [2] Kühn M, Nakaten N, Streibel M, Kempka T (2014) CO2 geological storage and utilization for a carbon neutral "power-to-gas-to-power" cycle to even out fluctuations of renewable energy provision. Energy Procedia 63, 8044-8049. doi: 10.1016/j.egypro.2014.11.841 [3] Kühn M, Streibel M, Nakaten N, Kempka T (2014) Integrated underground gas storage of CO2 and CH4 to decarbonise the "power-to-gas-to-gas-to-power" technology. Energy Procedia 59, 9-15. doi: 10.1016/j.egypro.2014.10.342

Numerical Modeling of the Pumping Tests at the Ketzin Pilot Site for CO2 Injection: Model Calibration and Heterogeneity Effects

NASA Astrophysics Data System (ADS)

Chen, F.; Wiese, B.; Zhou, Q.; Birkholzer, J. T.; Kowalsky, M. B.

2013-12-01

The Stuttgart formation used for ongoing CO2 injection at the Ketzin pilot test site in Germany is highly heterogeneous in nature. The site characterization data, including 3D seismic amplitude images, the regional geology data, and the core measurements and geophysical logs of the wells show the formation is composed of permeable sandstone channels of varying thickness and length embedded in less permeable mudstones. Most of the sandstone channels are located in the upper 10-15 m of the formation, with only a few sparsely distributed sandstone channels in the bottom 70-m layer. Three-dimensional seismic data help to identify the large-scale facies distribution patterns in the Stuttgart formation, but are unable to resolve internal structures at a smaller scale (e.g. ~100 m). Heterogeneity has a large effect on the pressure propagation measured during a suite of pumping tests conducted in 2007-2008 and also impacts strongly the CO2 arrival times observed during the ongoing CO2 injection experiment. The arrival time of the CO2 plume at the observation well Ktzi 202was 12.5 times greater than at the other observation well Ktzi 200, even though the distance to the injection well is only 2.2 times farther than that of Ktzi 200. To characterize subsurface properties and help predict the behavior of injected CO2 in subsequent experiments, we develop a TOUGH2/EOS9 model for modeling the hydraulic pumping tests and use the inverse modeling tool iTOUGH2 for automatic model calibration. The model domain is parameterized using multiple zones, with each zone assumed to have uniform rock properties. The calibrated model produces system responses that are in good agreement with the measured pressure drawdown data, indicating that it captures the essential flow processes occurring during the pumping tests. The estimated permeability distribution shows that the heterogeneity is significant and that the study site is situated a semi-closed system with one or two sides open to permeable regions and the others effectively blocked by low-permeability regions. A low-permeability zone appears at the northern boundary of the model. Of the three wells that are analyzed, permeable channels are found to connect Ktzi 202 with Ktzi 200/Ktzi 201, while a low-permeability zone is observed between Ktzi 201 and Ktzi 200. The calibrated results are consistent with the crosshole ERT data and can help explain the position of a CO2 plume, inferred from 3D seismic surveys in a subsequent CO2 injection experiment. Because the CO2 transport that occurs during a CO2 injection and the pressure propagation that occurs during pumping tests are sensitive to different scales of subsurface heterogeneity, direct application of a model calibrated from pumping test data is inappropriate for predicting CO2 arrival. However, by including a thin layer of highly permeable sandstone, we present a proof-of-concept model that produces CO2 arrival times comparable to those observed at the site.

An 'outrageous hypothesis' for Mars - Episodic oceans

NASA Astrophysics Data System (ADS)

Kerr, R. A.

1993-02-01

The conventional view of Mars is that, during the past 3 billion years, the atmosphere has been so thin and cold that the planet's water has remained locked up underground as ice. However, Baker et al. (1991) proposed a radically different and far-reaching alternative: a Mars that is periodically shrouded in an earthlike atmosphere, with a temporary ocean and massive ice sheets. This hypothesis was proposed in order to explain the assortment of surface features sent back by the Viking spacecraft in 1970, such as huge channels, apparent ocean shorelines, and possible glacial landforms. To support this hypothesis, Baker and his coworkers invoked a spate of catastrophic floods, all cutting their channels at the same geological moment due a great outburst of Mars's volcanic activity which could have melted some subsurface ice and belched out CO2. This gas, together with some additional CO2 released as the water interacted with the surface, caused a strong greenhouse warming, causing melting of underground ice and the formation of an ocean.

Long-Term Effect of Fault-Controlled CO2 Alteration on the Weakening and Strengthening of Reservoir and Seal Lithologies at Crystal Geyser, Green River, Utah

NASA Astrophysics Data System (ADS)

Major, J. R.; Eichhubl, P.; Dewers, T. A.

2014-12-01

An understanding of the coupled chemical and mechanical properties and behavior of reservoir and seal rocks is critical for assessing both the short and long term security of sequestered CO2. A combined structural diagenesis approach using observations from natural analogs has great advantages for understanding these properties over longer time scales than is possible using laboratory or numerical experiments. Current numerical models evaluating failure of reservoirs and seals during and after CO2 injection in the subsurface are just beginning to account for such coupled processes. Well-characterized field studies of natural analogs such as Crystal Geyser, Utah, are essential for providing realistic input parameters, calibration, and testing of numerical models across a range of spatial and temporal scales. Fracture mechanics testing was performed on a suite of naturally altered and unaltered reservoir and seal rocks exposed at the Crystal Geyser field site. These samples represent end-products of CO2-related alteration over geologic (>103 yr) time scales. Both the double torsion and short rod test methods yield comparable results on the same samples. Tests demonstrate that CO2-related alteration has weakened one reservoir sandstone lithology by approximately 50%, but the subcritical index is not significantly affected. An altered siltstone sample also shows a reduction in fracture toughness values and lowered subcritical index in comparison to unaltered siltstone. In contrast, elevated calcite content in shales due to CO2 alteration has increased fracture toughness. Similarly, fracture toughness was increased in what is otherwise a weak, poorly cemented sandstone unit due to increased calcite cement. Combined, these results demonstrate that CO2-related alteration generally weakens rock to fracturing (i.e. lowers fracture toughness), except in cases where calcite cementation is significantly increased. The natural system at Crystal Geyser demonstrates that water-CO2-rock interaction driven by changes in the geochemical environment have measurably altered rock geomechanical properties and that some rock units may become more prone to failure, ultimately leading to fracturing and leakage of subsurface reservoirs. These results also have application for CO2-based enhanced oil recovery.

Nanoscale Controls on CO2-water-rock Interactions in Saline Reservoirs

NASA Astrophysics Data System (ADS)

Deyoreo, J.; Depaolo, D. J.

2009-12-01

It is becoming increasingly widely recognized that geologic sequestration of CO2, when combined with economical means of capture, may be one of the most effective approaches to reducing net CO2 emissions to the atmosphere over the next century. Injection of CO2 into saline geologic formations involves forcing a buoyant, low-viscosity fluid into a more dense, higher viscosity fluid. The difference in wetting properties of the two fluids, their partial miscibility, the fact that CO2 and H2O form an acid, and the heterogeneity of geologic formations combine to make the flow and transport details fascinating but difficult to fully characterize and predict. A major question is whether the flow of CO2 into subsurface formations, the efficiency of pore space filling, and the trapping efficiency can be not only predicted but controlled over the decades of injection that might be associated with the life of a power plant. The major technological gaps to controlling and ultimately sequestering subsurface CO2 can be traced to far-from-equilibrum processes that originate at the molecular and nanoscale, but are expressed as complex emergent behavior at larger scales. Essential knowledge gaps involve the effects of nanoscale confinement on material properties, flow and chemical reactions, the effects of nanoparticles, mineral surface dynamics, and microbiota on mineral dissolution/precipitation and fluid flow, and the dynamics of fluid-fluid and fluid-mineral interfaces. To address these scientific and technical challenges, the Energy Frontier Research Center recently established, involving collaboration between LBNL, ORNL, MIT, UC Berkeley, UC Davis and LLNL, will attempt to bring new approaches to the study of nanoscale phenomena in fluid-rock systems to bear on the problem of CO2 behavior in saline formations. The stated goal is to use molecular, nanoscale, and pore-network scale approaches to control flow, dissolution, and precipitation in deep subsurface rock formations to achieve the efficient filling of pore space while maximizing solubility and mineral trapping and reducing potential leakage. Advanced knowledge of these small-scale processes is an important step toward developing a next-generation predictive capability for reactive transport of CO2-brine systems. The Center involves scientists with expertise in hydrology, geochemistry, materials science, mineralogy, chemistry, microbiology, geophysics, and reactive transport modeling and simulation. This presentation will describe the initial stages of some of the research, which in total involves the use of synchrotron light sources, neutron scattering methods, NanoSIMS, molecular dynamics simulations, thermochemistry, molecular biology, nanotechnology, laboratory scale experiments, and advanced computation applied to flow and reactive transport in heterogeneous porous media. The Center for Nanoscale Control of Geologic CO2 key personnel: Director - D. DePaolo, Co-Director - J. DeYoreo; Research Area Leads - K. Knauss (LBNL), G. Waychunas (LBNL), J. Banfield (UCB/LBNL), A Navrotsky (UC Davis), F.J. Ryerson (LLNL); G. Sposito (UCB/LBNL), T. Tokunaga (LBNL), D. Cole (ORNL), C. Steefel (LBNL), D. Rothman (MIT), S. Pride (LBNL).

Micromechanical Tests and Geochemical Modeling to Evaluate Evolution of Rock Alteration by CO2-Water Mixtures

NASA Astrophysics Data System (ADS)

Aman, M.; Sun, Y.; Ilgen, A.; Espinoza, N.

2015-12-01

Injection of large volumes of CO2 into geologic formations can help reduce the atmospheric CO2 concentration and lower the impact of burning fossil fuels. However, the injection of CO2 into the subsurface shifts the chemical equilibrium between the mineral assemblage and the pore fluid. This shift will situationally facilitate dissolution and reprecipitation of mineral phases, in particular intergranular cements, and can potentially affect the long term mechanical stability of the host formation. The study of these coupled chemical-mechanical reservoir rock responses can help identify and control unexpected emergent behavior associated with geological CO2 storage.Experiments show that micro-mechanical methods are useful in capturing a variety of mechanical parameters, including Young's modulus, hardness and fracture toughness. In particular, micro-mechanical measurements are well-suited for examining thin altered layers on the surfaces of rock specimens, as well as capturing variability on the scale of lithofacies. We performed indentation and scratching tests on sandstone and siltstone rocks altered in natural CO2-brine environments, as well as on analogous samples altered under high pressure, temperature, and dissolved CO2 conditions in a controlled laboratory experiment. We performed geochemical modeling to support the experimental observations, in particular to gain the insight into mineral dissolution/precipitation as a result of the rock-water-CO2reactions. The comparison of scratch measurements performed on specimens both unaltered and altered by CO2 over geologic time scales results in statistically different values for fracture toughness and scratch hardness, indicating that long term exposure to CO2 caused mechanical degradation of the reservoir rock. Geochemical modeling indicates that major geochemical change caused by CO2 invasion of Entrada sandstone is dissolution of hematite cement, and its replacement with siderite and dolomite during the alteration process.

Geochemical Influence on Microbial Communities at CO2-Leakage Analog Sites.

PubMed

Ham, Baknoon; Choi, Byoung-Young; Chae, Gi-Tak; Kirk, Matthew F; Kwon, Man Jae

2017-01-01

Microorganisms influence the chemical and physical properties of subsurface environments and thus represent an important control on the fate and environmental impact of CO 2 that leaks into aquifers from deep storage reservoirs. How leakage will influence microbial populations over long time scales is largely unknown. This study uses natural analog sites to investigate the long-term impact of CO 2 leakage from underground storage sites on subsurface biogeochemistry. We considered two sites with elevated CO 2 levels (sample groups I and II) and one control site with low CO 2 content (group III). Samples from sites with elevated CO 2 had pH ranging from 6.2 to 4.5 and samples from the low-CO 2 control group had pH ranging from 7.3 to 6.2. Solute concentrations were relatively low for samples from the control group and group I but high for samples from group II, reflecting varying degrees of water-rock interaction. Microbial communities were analyzed through clone library and MiSeq sequencing. Each 16S rRNA analysis identified various bacteria, methane-producing archaea, and ammonia-oxidizing archaea. Both bacterial and archaeal diversities were low in groundwater with high CO 2 content and community compositions between the groups were also clearly different. In group II samples, sequences classified in groups capable of methanogenesis, metal reduction, and nitrate reduction had higher relative abundance in samples with relative high methane, iron, and manganese concentrations and low nitrate levels. Sequences close to Comamonadaceae were abundant in group I, while the taxa related to methanogens, Nitrospirae , and Anaerolineaceae were predominant in group II. Our findings provide insight into subsurface biogeochemical reactions that influence the carbon budget of the system including carbon fixation, carbon trapping, and CO 2 conversion to methane. The results also suggest that monitoring groundwater microbial community can be a potential tool for tracking CO 2 leakage from geologic storage sites.

Geochemical Influence on Microbial Communities at CO2-Leakage Analog Sites

PubMed Central

Ham, Baknoon; Choi, Byoung-Young; Chae, Gi-Tak; Kirk, Matthew F.; Kwon, Man Jae

2017-01-01

Microorganisms influence the chemical and physical properties of subsurface environments and thus represent an important control on the fate and environmental impact of CO2 that leaks into aquifers from deep storage reservoirs. How leakage will influence microbial populations over long time scales is largely unknown. This study uses natural analog sites to investigate the long-term impact of CO2 leakage from underground storage sites on subsurface biogeochemistry. We considered two sites with elevated CO2 levels (sample groups I and II) and one control site with low CO2 content (group III). Samples from sites with elevated CO2 had pH ranging from 6.2 to 4.5 and samples from the low-CO2 control group had pH ranging from 7.3 to 6.2. Solute concentrations were relatively low for samples from the control group and group I but high for samples from group II, reflecting varying degrees of water-rock interaction. Microbial communities were analyzed through clone library and MiSeq sequencing. Each 16S rRNA analysis identified various bacteria, methane-producing archaea, and ammonia-oxidizing archaea. Both bacterial and archaeal diversities were low in groundwater with high CO2 content and community compositions between the groups were also clearly different. In group II samples, sequences classified in groups capable of methanogenesis, metal reduction, and nitrate reduction had higher relative abundance in samples with relative high methane, iron, and manganese concentrations and low nitrate levels. Sequences close to Comamonadaceae were abundant in group I, while the taxa related to methanogens, Nitrospirae, and Anaerolineaceae were predominant in group II. Our findings provide insight into subsurface biogeochemical reactions that influence the carbon budget of the system including carbon fixation, carbon trapping, and CO2 conversion to methane. The results also suggest that monitoring groundwater microbial community can be a potential tool for tracking CO2 leakage from geologic storage sites. PMID:29170659

CO2 hydrate: Synthesis, composition, structure, dissociation behavior, and a comparison to structure I CH4 hydrate

USGS Publications Warehouse

Circone, S.; Stern, L.A.; Kirby, S.H.; Durham, W.B.; Chakoumakos, B.C.; Rawn, C.J.; Rondinone, A.J.; Ishii, Y.

2003-01-01

Structure I (sI) carbon dioxide (CO2) hydrate exhibits markedly different dissociation behavior from sI methane (CH4) hydrate in experiments in which equilibrated samples at 0.1 MPa are heated isobarically at 13 K/h from 210 K through the H2O melting point (273.15 K). The CO2 hydrate samples release only about 3% of their gas content up to temperatures of 240 K, which is 22 K above the hydrate phase boundary. Up to 20% is released by 270 K, and the remaining CO2 is released at 271.0 plusmn; 0.5 K, where the sample temperature is buffered until hydrate dissociation ceases. This reproducible buffering temperature for the dissociation reaction CO2??nH2O = CO2(g) + nH2O(1 to s) is measurably distinct from the pure H2O melting point at 273.15 K, which is reached as gas evolution ceases. In contrast, when si CH4 hydrate is heated at the same rate at 0.1 MPa, >95% of the gas is released within 25 K of the equilibrium temperature (193 K at 0.1 MPa). In conjunction with the dissociation study, a method for efficient and reproducible synthesis of pure polycrystalline CO2 hydrate with suitable characteristics for material properties testing was developed, and the material was characterized. CO2 hydrate was synthesized from CO2 liquid and H2O solid and liquid reactants at pressures between 5 and 25 MPa and temperatures between 250 and 281 K. Scanning electron microscopy (SEM) examination indicates that the samples consist of dense crystalline hydrate and 50-300 ??m diameter pores that are lined with euhedral cubic hydrate crystals. Deuterated hydrate samples made by this same procedure were analyzed by neutron diffraction at temperatures between 4 and 215 K; results confirm that complete conversion of water to hydrate has occurred and that the measured unit cell parameter and thermal expansion are consistent with previously reported values. On the basis of measured weight gain after synthesis and gas yields from the dissociation experiments, approximately all cages in the hydrate structure are filled such that n ??? 5.75.

Bioleaching mechanism of Co and Li from spent lithium-ion battery by the mixed culture of acidophilic sulfur-oxidizing and iron-oxidizing bacteria.

PubMed

Xin, Baoping; Zhang, Di; Zhang, Xian; Xia, Yunting; Wu, Feng; Chen, Shi; Li, Li

2009-12-01

The bioleaching mechanism of Co and Li from spent lithium-ion batteries by mixed culture of sulfur-oxidizing and iron-oxidizing bacteria was investigated. It was found that the highest release of Li occurred at the lowest pH of 1.54 with elemental sulfur as an energy source, the lowest occurred at the highest pH of 1.69 with FeS(2). In contrast, the highest release of Co occurred at higher pH and varied ORP with S + FeS(2), the lowest occurred at almost unchanged ORP with S. It is suggested that acid dissolution is the main mechanism for Li bioleaching independent of energy matters types, however, apart from acid dissolution, Fe(2+) catalyzed reduction takes part in the bioleaching process as well. Co(2+) was released by acid dissolution after insoluble Co(3+) was reduced into soluble Co(2+) by Fe(2+) in both FeS(2) and FeS(2) + S systems. The proposed bioleaching mechanism mentioned above was confirmed by the further results obtained from the experiments of bioprocess-stimulated chemical leaching and from the changes in structure and component of bioleaching residues characterized by XPS, SEM and EDX.

Heterogeneity-enhanced gas phase formation in shallow aquifers during leakage of CO2-saturated water from geologic sequestration sites

NASA Astrophysics Data System (ADS)

Plampin, Michael R.; Lassen, Rune N.; Sakaki, Toshihiro; Porter, Mark L.; Pawar, Rajesh J.; Jensen, Karsten H.; Illangasekare, Tissa H.

2014-12-01

A primary concern for geologic carbon storage is the potential for leakage of stored carbon dioxide (CO2) into the shallow subsurface where it could degrade the quality of groundwater and surface water. In order to predict and mitigate the potentially negative impacts of CO2 leakage, it is important to understand the physical processes that CO2 will undergo as it moves through naturally heterogeneous porous media formations. Previous studies have shown that heterogeneity can enhance the evolution of gas phase CO2 in some cases, but the conditions under which this occurs have not yet been quantitatively defined, nor tested through laboratory experiments. This study quantitatively investigates the effects of geologic heterogeneity on the process of gas phase CO2 evolution in shallow aquifers through an extensive set of experiments conducted in a column that was packed with layers of various test sands. Soil moisture sensors were utilized to observe the formation of gas phase near the porous media interfaces. Results indicate that the conditions under which heterogeneity controls gas phase evolution can be successfully predicted through analysis of simple parameters, including the dissolved CO2 concentration in the flowing water, the distance between the heterogeneity and the leakage location, and some fundamental properties of the porous media. Results also show that interfaces where a less permeable material overlies a more permeable material affect gas phase evolution more significantly than interfaces with the opposite layering.

Carbon dioxide sequestration monitoring and verification via laser based detection system in the 2 mum band

NASA Astrophysics Data System (ADS)

Humphries, Seth David

Carbon Dioxide (CO2) is a known contributor to the green house gas effect. Emissions of CO2 are rising as the global demand for inexpensive energy is placated through the consumption and combustion of fossil fuels. Carbon capture and sequestration (CCS) may provide a method to prevent CO2 from being exhausted to the atmosphere. The carbon may be captured after fossil fuel combustion in a power plant and then stored in a long term facility such as a deep geologic feature. The ability to verify the integrity of carbon storage at a location is key to the success of all CCS projects. A laser-based instrument has been built and tested at Montana State University (MSU) to measure CO2 concentrations above a carbon storage location. The CO2 Detection by Differential Absorption (CODDA) Instrument uses a temperature-tunable distributed feedback (DFB) laser diode that is capable of accessing a spectral region, 2.0027 to 2.0042 mum, that contains three CO2 absorption lines and a water vapor absorption line. This instrument laser is aimed over an open-air, two-way path of about 100 m, allowing measurements of CO2 concentrations to be made directly above a carbon dioxide release test site. The performance of the instrument for carbon sequestration site monitoring is studied using a newly developed CO2 controlled release facility. The field and CO2 releases are managed by the Zero Emissions Research Technology (ZERT) group at MSU. Two test injections were carried out through vertical wells simulating seepage up well paths. Three test injections were done as CO2 escaped up through a slotted horizontal pipe simulating seepage up through geologic fault zones. The results from these 5 separate controlled release experiments over the course of three summers show that the CODDA Instrument is clearly capable of verifying the integrity of full-scale CO2 storage operations.

An experimental study of basaltic glass-H2O-CO2 interaction at 22 and 50 ° C: Implications for subsurface storage of CO2

NASA Astrophysics Data System (ADS)

Galeczka, Iwona; Wolff-Boenisch, Domenik; Oelkers, Eric H.; Gislason, Sigurdur R.

2014-05-01

A novel high pressure column flow reactor (HPCFR) was used to investigate the evolution of fluid chemistry along a 2.3 meter flow path during 37-104 days of pure water- and CO2-charged water- (0.3 M CO2(aq)) basaltic glass interaction experiments at 22 and 50 ° C. The scale of the HPCFR, the ability to sample a reactive fluid at discrete spatial intervals under pressure and the possibility to measure the dissolved inorganic carbon and pH in situ all render the HPCFR unique in comparison with other reactors constructed for studies of CO2-charged water-rock interaction. During the pure water-basaltic glass interaction experiment, the pH of the injected water evolved rapidly from 6.7 to 9-9.5 and most of the dissolved iron was consumed by secondary mineral formation, similar to natural basaltic groundwater systems. In contrast to natural systems, however, the dissolved aluminium concentration remained relatively high along the entire flow path. The reactive fluid was undersaturated with respect to basaltic glass and carbonate minerals, but supersaturated with respect to zeolites, clays, and Fe hydroxides. Basaltic glass dissolution in the CO2-charged water was closer to stoichiometry than in pure water. The mobility of metals increased significantly in the reactive fluid and the concentration of some metals, including Mn, Fe, Cr, Al, and As exceeded the WHO (World Health Organisation) allowable drinking water limits. Iron was mobile and the aqueous Fe2+/Fe3+ ratio increased along the flow path. Basaltic glass dissolution in the CO2-charged water did not overcome the pH buffer capacity of the fluid. The pH rose only from an initial pH of 3.4 to 4.5 along the first 18.5 cm of the column, then remained constant during the remaining 2.1 meters of the flow path. Increasing the temperature of the CO2-charged fluid from 22 to 50 ° C increased the relative amount of dissolved divalent iron along the flow path. After a significant initial increase along the first metre of the column, the dissolved aluminium concentration decreased consistent with its incorporation into secondary minerals. The dissolved chromium concentration evolution mimicked that of Al at 50 ° C, suggesting substitution of trivalent Cr for Al in secondary phases. According to PHREEQC calculations, the CO2-charged fluid was always undersaturated with respect to carbonate minerals within the column, but supersaturated with respect to clays and Fe hydroxides at 22 ° C and with respect to clays and Al hydroxides at 50 ° C. Substantial differences were found between modelled and measured dissolved element concentrations in the fluids during the experiments. These differences underscore the need to improve computational models before they can be used to predict with confidence the fate and consequences of carbon dioxide injected into the subsurface.

Controlled experiments for dense gas diffusion: Experimental design and execution, model comparison

DOE Office of Scientific and Technical Information (OSTI.GOV)

Egami, R.; Bowen, J.; Coulombe, W.

1995-07-01

An experimental baseline CO2 release experiment at the DOE Spill Test Facility on the Nevada Test Site in Southern Nevada is described. This experiment was unique in its use of CO2 as a surrogate gas representative of a variety of specific chemicals. Introductory discussion places the experiment in historical perspective. CO2 was selected as a surrogate gas to provide a data base suitable for evaluation of model scenarios involving a variety of specific dense gases. The experiment design and setup are described, including design rationale and quality assurance methods employed. Resulting experimental data are summarized. Data usefulness is examined throughmore » a preliminary comparison of experimental results with simulations performed using the SLAV and DEGADIS dense gas models.« less

Organic Carbon Release from Groundwater Sediments under Changing Geochemical Conditions

NASA Astrophysics Data System (ADS)

Tinnacher, R. M.; Bhattacharyya, A.; Fox, P. M.; Nico, P. S.

2016-12-01

Due to climate change, local weather patterns are expected to change, especially with respect to precipitation, the frequency of extreme storm water events, and `drought-like' conditions. This in turn, may affect groundwater recharge, the geochemical conditions in natural groundwater systems, and the chemical and microbiological processes involved in organic matter degradation. Besides the complexity of organic matter structures and local limitations in nutrients, the association of organic carbon with sediment minerals can strongly limit organic matter bioaccessability and degradability. In this study, we investigate how variations in groundwater chemistry, e.g. with respect to dissolved CO2 concentrations, may potentially affect the release of natural organic carbon from groundwater sediments, and render organic matter more bioaccessible. In lab-scale experiments under anaerobic conditions, aquifer sediments from the floodplain of the Colorado River (Rifle, USA) were brought into contact with fresh, organic-carbon free groundwater solutions, at natural or reduced CO2 concentration levels. During the repeated exchange of solutions at two temperature settings (room-temperature and 4 °C), supernatant solutions were characterized in terms of pH, dissolved metal and organic carbon (OC) concentrations, and potential changes in released OC characteristics. Sediment samples were evaluated for possible differences in Fe-speciation before and after the experiment based on EXAFS (bulk Fe K-edge). Preliminary results for 20 exchanges of groundwater solutions show a repeated release of low OC concentrations ( 0.5-2 mg OC/g sediment; 0.05-0.2% of sediment-associated OC) without any apparent depletion in the overall source term over 50 days. After 14 days, room-temperature samples released slightly higher OC concentrations than samples kept at 4 °C. An increase in solution pH, after switching to a `CO2-free' groundwater solution, did not trigger a higher OC release. Last, specific UV absorbance measurements for room-temperature samples suggest changes in released OC characteristics due to repeated solution exchanges. Additional sample characterization is ongoing, with the goal to elucidate potential changes in released OC characteristics over the course of the experiment.

Efficacy of oxygen-supplying capacity of Azolla in a controlled life support system

NASA Astrophysics Data System (ADS)

Chen, Min; Deng, Sufang; Yang, Youquan; Huang, Yibing; Liu, Chongchu

2012-02-01

Azolla shows high growth and propagation rates, strong photosynthetic O2-releasing ability and high nutritional value. It is suitable as a salad vegetable and can be cultured on a multi-layered wet bed. Hence, it possesses potential as a fresh vegetable, and to release O2 and absorb CO2 in a Controlled Ecological Life Support System in space. In this study, we investigated the O2-providing characteristics of Azolla in a closed chamber under manned, controlled conditions to lay a foundation for use of Azolla as a biological component in ground simulation experiments for space applications. A closed test chamber, representing a Controlled Ecological Life Support System including an Azolla wet-culture device, was built to measure the changes in atmospheric O2 and CO2 concentrations inside the chamber in the presence of coexisting Azolla, fish and men. The amount of O2 consumed by fish was 0.0805-0.0831 L kg-1 h-1 and the level of CO2 emission was 0.0705-0.0736 L kg-1 h-1; O2 consumption by the two trial volunteers was 19.71 L h-1 and the volume of respiration-released CO2 was 18.90 L h-1. Under 7000-8000 Lx artificial light and Azolla wet-culture conditions, human and fish respiration and Azolla photosynthesis were complementary, thus the atmospheric O2 and CO2 concentrations inside chamber were maintained in equilibrium. The increase in atmospheric CO2 concentration in the closed chamber enhanced the net photosynthesis efficiency of the Azolla colony. This study showed that Azolla has strong photosynthetic O2-releasing ability, which equilibrates the O2 and CO2 concentrations inside the chamber in favor of human survival and verifies the potential of Azolla for space applications.

National assessment of geologic carbon dioxide storage resources: methodology implementation

USGS Publications Warehouse

Blondes, Madalyn S.; Brennan, Sean T.; Merrill, Matthew D.; Buursink, Marc L.; Warwick, Peter D.; Cahan, Steven M.; Corum, Margo D.; Cook, Troy A.; Craddock, William H.; DeVera, Christina A.; Drake II, Ronald M.; Drew, Lawrence J.; Freeman, P.A.; Lohr, Celeste D.; Olea, Ricardo A.; Roberts-Ashby, Tina L.; Slucher, Ernie R.; Varela, Brian A.

2013-01-01

In response to the 2007 Energy Independence and Security Act, the U.S. Geological Survey (USGS) conducted a national assessment of potential geologic storage resources for carbon dioxide (CO2). Storage of CO2 in subsurface saline formations is one important method to reduce greenhouse gas emissions and curb global climate change. This report provides updates and implementation details of the assessment methodology of Brennan and others (2010, http://pubs.usgs.gov/of/2010/1127/) and describes the probabilistic model used to calculate potential storage resources in subsurface saline formations.

Application of open-path Fourier transform infrared spectroscopy for atmospheric monitoring of a CO2 back-production experiment at the Ketzin pilot site (Germany).

PubMed

Sauer, Uta; Borsdorf, H; Dietrich, P; Liebscher, A; Möller, I; Martens, S; Möller, F; Schlömer, S; Schütze, C

2018-02-03

During a controlled "back-production experiment" in October 2014 at the Ketzin pilot site, formerly injected CO 2 was retrieved from the storage formation and directly released to the atmosphere via a vent-off stack. Open-path Fourier transform infrared (OP FTIR) spectrometers, on-site meteorological parameter acquisition systems, and distributed CO 2 point sensors monitored gas dispersion processes in the near-surface part of the atmospheric boundary layer. The test site provides a complex and challenging mosaic-like surface setting for atmospheric monitoring which can also be found at other storage sites. The main aims of the atmospheric monitoring of this experiment were (1) to quantify temporal and spatial variations in atmospheric CO 2 concentrations around the emitting vent-off stack and (2) to test if and how atmospheric monitoring can cope with typical environmental and operational challenges. A low environmental risk was encountered during the whole CO 2 back-production experiment. The study confirms that turbulent wind conditions favor atmospheric mixing processes and are responsible for rapid dilution of the released CO 2 leading to decreased detectability at all sensors. In contrast, calm and extremely stable wind conditions (especially occurring during the night) caused an accumulation of gases in the near-ground atmospheric layer with the highest amplitudes in measured gas concentration. As an important benefit of OP FTIR spectroscopic measurements and their ability to detect multiple gas species simultaneously, emission sources could be identified to a much higher certainty. Moreover, even simulation models using simplified assumptions help to find suitable monitoring network designs and support data analysis for certain wind conditions in such a complex environment.

Large CO 2 and CH 4 emissions from polygonal tundra during spring thaw in northern Alaska

DOE PAGES

Raz-Yaseef, Naama; Torn, Margaret S.; Wu, Yuxin; ...

2016-12-05

The few prethaw observations of tundra carbon fluxes suggest that there may be large spring releases, but little is known about the scale and underlying mechanisms of this phenomenon. To address these questions, we combined in this paper ecosystem eddy flux measurements from two towers near Barrow, Alaska, with mechanistic soil-core thawing experiment. During a 2 week period prior to snowmelt in 2014, large fluxes were measured, reducing net summer uptake of CO 2 by 46% and adding 6% to cumulative CH 4 emissions. Emission pulses were linked to unique rain-on-snow events enhancing soil cracking. Controlled laboratory experiment revealed thatmore » as surface ice thaws, an immediate, large pulse of trapped gases is emitted. Finally, these results suggest that the Arctic CO 2 and CH 4 spring pulse is a delayed release of biogenic gas production from the previous fall and that the pulse can be large enough to offset a significant fraction of the moderate Arctic tundra carbon sink.« less

Updating soil CO2 emission experiments to assess climate change effects and extracellular soil respiration

NASA Astrophysics Data System (ADS)

Vidal Vazquez, Eva; Paz Ferreiro, Jorge

2014-05-01

Experimental work is an essential component in training future soil scientists. Soil CO2 emission is a key issue because of the potential impacts of this process on the greenhouse effect. The amount of organic carbon stored in soils worldwide is about 1600 gigatons (Gt) compared to 750 Gt in the atmosphere mostly in the form of CO2. Thus, if soil respiration increased slightly so that just 10% of the soil carbon pool was converted to CO2, atmospheric CO2 concentrations in the atmosphere could increase by one-fifth. General circulation model predictions indicate atmosphere warming between 2 and 5°C (IPCC 2007) and precipitation changes ranging from about -15 to +30%. Traditionally, release of CO2 was thought to occur only in an intracellular environment; however, recently CO2 emissions have been in irradiated soil, in the absence of microorganisms (Maire et al., 2013). Moreover, soil plays a role in the stabilization of respiration enzymes promoting CO2 release after microorganism death. Here, we propose to improve CO2 emission experiments commonly used in soil biology to investigate: 1) effects of climatic factors on soil CO2 emissions, and 2) rates of extracellular respiration in soils and how these rates are affected by environmental factors. Experiment designed to assess the effect of climate change can be conducted either in field conditions under different ecosystems (forest, grassland, cropland) or in a greenhouse using simple soil chambers. The interactions of climate change in CO2 emissions are investigated using climate-manipulation experiment that can be adapted to field or greenhouse conditions (e.g. Mc Daniel et al., 2013). The experimental design includes a control plot (without soil temperature and rain manipulation) a warming treatment as well as wetting and/or drying treatments. Plots are warmed to the target temperature by procedures such as infrared heaters (field) or radiant cable (greenhouse). To analyze extracellular respiration, rates of CO2 emissions from sterilized soils and their unsterilized counterparts are compared. Moreover, different pH treatments are compared to analyze how soil pH affects extracellular CO2 release. Students benefit from experimental learning. Practical courses, being either in the field or indoors are of vital importance to bring soil processes to life and to evaluate implications for environment and climate change. IPCC, 2007: Climate Change 2007: The Physical Science Basis. Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change (Solomon, S., D. Qin, M. Manning, Z. Chen, M. Marquis, K.B. Averyt, M. Tignor and H.L. Miller (eds.). Cambridge University Press, Cambridge, United Kingdom, 996 pp. Maire, V., G. Alvarez, J. Colombet, A. Comby, R. Despinasse, E. Dubreucq, M. Joly, A.-C. Lehours, V. Perrier, T. Shahzad, and S. Fontaine. 2013. An unknown oxidative metabolism substantially contributes to soil CO2 emissions. Biogeochemistry, 10, 1155-1167, 2013

Direct Experiments on the Ocean Disposal of Fossil Fuel CO2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barry, James, P.

2010-05-26

Funding from DoE grant # FG0204-ER63721, Direct Experiments on the Ocean Disposal of Fossil Fuel CO2, supposed several postdoctoral fellows and research activities at MBARI related to ocean CO2 disposal and the biological consequences of high ocean CO2 levels on marine organisms. Postdocs supported on the project included Brad Seibel, now an associate professor at the University of Rhode Island, Jeff Drazen, now an associate professor at the University of Hawaii, and Eric Pane, who continues as a research associate at MBARI. Thus, the project contributed significantly to the professional development of young scientists. In addition, we made significant progressmore » in several research areas. We continued several deep-sea CO2 release experiments using support from DoE and MBARI, along with several collaborators. These CO2 release studies had the goal of broadening our understanding of the effects of high ocean CO2 levels on deep sea animals in the vicinity of potential release sites for direct deep-ocean carbon dioxide sequestration. Using MBARI ships and ROVs, we performed these experiments at depths of 3000 to 3600 m, where liquid CO2 is heavier than seawater. CO2 was released into small pools (sections of PVC pipe) on the seabed, where it dissolved and drifted downstream, bathing any caged animals and sediments in a CO2-rich, low-pH plume. We assessed the survival of organisms nearby. Several publications arose from these studies (Barry et al. 2004, 2005; Carman et al. 2004; Thistle et al. 2005, 2006, 2007; Fleeger et al. 2006, 2010; Barry and Drazen 2007; Bernhard et al. 2009; Sedlacek et al. 2009; Ricketts et al. in press; Barry et al, in revision) concerning the sensitivity of animals to low pH waters. Using funds from DoE and MBARI, we designed and fabricated a hyperbaric trap-respirometer to study metabolic rates of deep-sea fishes under high CO2 conditions (Drazen et al, 2005), as well as a gas-control aquarium system to support laboratory studies of the effects of high CO2 waters on marine animals (Barry et al. 2008). This system is capable of controlling oxygen, pH, and temperature of seawater for use in studies of the physiological responses of animals under acidified conditions. We have investigated the tolerance of deep- and shallow-living crabs to high CO2 levels (Pane and Barry 2007; Pane et al. 2008), and are now working on brachiopods (Barry et al. in prep.) and a comparison of deep and shallow living sea urchins. This research program, supported in part by DoE has contributed to a number of other publications authored or co-authored by Barry (Caldeira et al. 2005; Brewer and Barry 2008; Barry et al. 2006, 2010a,b,c; National Research Council, in press; Hoffman et al. in press) as well as over 40 invited talks since 2004, including Congressional briefings and testimony at U.S. Senate Hearings on Ocean Acidification. Through the grant period, the research emphasis shifted from studies of the effects of direct deep-sea carbon dioxide sequestration on deep-sea animals, to a broader conceptual framework of the effects of ocean acidification (whether purposeful or passive) on the physiology and survival of deep and shallow living marine animals. We feel that this has been a very productive program and are grateful to DoE for its support.« less

The influence of open fracture anisotropy on CO2 movement within geological storage complexes

NASA Astrophysics Data System (ADS)

Bond, C. E.; Wightman, R.; Ringrose, P. S.

2012-12-01

Carbon mitigation through the geological storage of carbon dioxide is dependent on the ability of geological formations to store CO2 trapping it within a geological storage complex. Secure long-term containment needs to be demonstrated, due to both political and social drivers, meaning that this containment must be verifiable over periods of 100-105 years. The effectiveness of sub-surface geological storage systems is dependent on trapping CO2 within a volume of rock and is reliant on the integrity of the surrounding rocks, including their chemical and physical properties, to inhibit migration to the surface. Oil and gas reservoir production data, and field evidence show that fracture networks have the potential to act as focused pathways for fluid movement. Fracture networks can allow large volumes of fluid to migrate to the surface within the time scales of interest. In this paper we demonstrate the importance of predicting the effects of fracture networks in storage, using a case study from the In Salah CO2 storage site, and show how the fracture permeability is closely controlled by the stress regime that determines the open fracture network. Our workflow combines well data of imaged fractures, with a discrete fracture network (DFN) model of tectonically induced fractures, within the horizon of interest. The modelled and observed fractures have been compared and combined with present day stress data to predict the open fracture network and its implications for anisotropic movement of CO2 in the sub-surface. The created fracture network model has been used to calculate the 2D permeability tensor for the reservoir for two scenarios: 1) a model in which all fractures are permeable, based on the whole DFN model and 2) those fractures determined to be in dilatational failure under the present day stress regime, a sub-set of the DFN. The resulting permeability anisotropy tensors show distinct anisotropies for the predicted CO2 movement within the reservoir. These predictions have been compared with InSAR imagery of surface uplift, used as an indicator of fluid pressure and movement in the sub-surface, around the CO2 injection wells. The analysis shows that the permeability tensor with the greatest anisotropy, that for the DFN sub-set of open fractures, matches well with the anisotropy in surface uplift imaged by InSAR. We demonstrate that predicting fracture networks alone does not predict fluid movement in the sub-surface, and that fracture permeability is closely controlled by the stress regime that determines the open fracture network. Our results show that a workflow of fracture network prediction combined with present day stress analysis can be used to successfully predict CO2 movement in the sub-surface at an active injection site.

Simulating CO2 Leakage and Seepage From Geologic Carbon Sequestration Sites: Implications for Near-Surface Monitoring

NASA Astrophysics Data System (ADS)

Oldenburg, C. M.; Lewicki, J. L.; Zhang, Y.

2003-12-01

The injection of CO2 into deep geologic formations for the purpose of carbon sequestration entails risk that CO2 will leak upward from the target formation and ultimately seep out of the ground surface. We have developed a coupled subsurface and atmospheric surface layer modeling capability based on TOUGH2 to simulate CO2 leakage and seepage. Simulation results for representative subsurface and surface layer conditions are used to specify the requirements of potential near-surface monitoring strategies relevant to both health, safety, and environmental risk assessment as well as sequestration verification. The coupled model makes use of the standard multicomponent and multiphase framework of TOUGH2 and extends the model domain to include an atmospheric surface layer. In the atmospheric surface layer, we assume a logarithmic velocity profile for the time-averaged wind and make use of Pasquill-Gifford and Smagorinski dispersion coefficients to model surface layer dispersion. Results for the unsaturated zone and surface layer show that the vadose zone pore space can become filled with pure CO2 even for small leakage fluxes, but that CO2 concentrations above the ground surface are very low due to the strong effects of dispersion caused by surface winds. Ecological processes such as plant photosynthesis and root respiration, as well as biodegradation in soils, strongly affect near-surface CO2 concentrations and fluxes. The challenge for geologic carbon sequestration verification is to discern the leakage and seepage signal from the ecological signal. Our simulations point to the importance of subsurface monitoring and the need for geochemical (e.g., isotopic) analyses to distinguish leaking injected fossil CO2 from natural ecological CO2. This work was supported by the Office of Science, U.S. Department of Energy under contract No. DE-AC03-76SF00098.

Adsorption, dissociation and diffusion of hydrogen on the ZrCo surface and subsurface: A comprehensive study using first principles approach

NASA Astrophysics Data System (ADS)

Chattaraj, D.; Kumar, Nandha; Ghosh, Prasenjit; Majumder, C.; Dash, Smruti

2017-11-01

With increasing demand for hydrogen economy driven world, the fundamental research of hydrogen-metal interactions has gained momentum. In this work we report a systematic theoretical study of the stability of different surfaces of intermetallic ZrCo that is a possible candidate as a getter bed for tritium. Our first principles ab initio thermodynamic calculations predict that amongst the (100), (110) and (111) surfaces, the stoichiometric (110) surface is the most stable one over a wide range of Co chemical potential. We have also studied adsorption, dissociation and diffusion of hydrogen on the (110) surface. On the basis of total energy, it is seen that adsorption of molecular hydrogen (H2) on the surface is much weaker than atomic hydrogen. The H2 decomposition on ZrCo surface can easily take place and the dissociation barrier is calculated to be 0.70 eV. The strength of binding of H atom on the surface is more or less independent of surface coverage till 1.0 ML of H. The thermodynamic stability of atomic H adsorbed on the surface, in subsurface and bulk decreases from surface to bulk to subsurface. Though the H atoms are mobile on the surface, their diffusion to the subsurface involves a barrier of about 0.79 eV.

Thermodynamic and Kinetic Response of Microbial Reactions to High CO2.

PubMed

Jin, Qusheng; Kirk, Matthew F

2016-01-01

Geological carbon sequestration captures CO 2 from industrial sources and stores the CO 2 in subsurface reservoirs, a viable strategy for mitigating global climate change. In assessing the environmental impact of the strategy, a key question is how microbial reactions respond to the elevated CO 2 concentration. This study uses biogeochemical modeling to explore the influence of CO 2 on the thermodynamics and kinetics of common microbial reactions in subsurface environments, including syntrophic oxidation, iron reduction, sulfate reduction, and methanogenesis. The results show that increasing CO 2 levels decreases groundwater pH and modulates chemical speciation of weak acids in groundwater, which in turn affect microbial reactions in different ways and to different extents. Specifically, a thermodynamic analysis shows that increasing CO 2 partial pressure lowers the energy available from syntrophic oxidation and acetoclastic methanogenesis, but raises the available energy of microbial iron reduction, hydrogenotrophic sulfate reduction and methanogenesis. Kinetic modeling suggests that high CO 2 has the potential of inhibiting microbial sulfate reduction while promoting iron reduction. These results are consistent with the observations of previous laboratory and field studies, and highlight the complexity in microbiological responses to elevated CO 2 abundance, and the potential power of biogeochemical modeling in evaluating and quantifying these responses.

Thermodynamic and Kinetic Response of Microbial Reactions to High CO2

PubMed Central

Jin, Qusheng; Kirk, Matthew F.

2016-01-01

Geological carbon sequestration captures CO2 from industrial sources and stores the CO2 in subsurface reservoirs, a viable strategy for mitigating global climate change. In assessing the environmental impact of the strategy, a key question is how microbial reactions respond to the elevated CO2 concentration. This study uses biogeochemical modeling to explore the influence of CO2 on the thermodynamics and kinetics of common microbial reactions in subsurface environments, including syntrophic oxidation, iron reduction, sulfate reduction, and methanogenesis. The results show that increasing CO2 levels decreases groundwater pH and modulates chemical speciation of weak acids in groundwater, which in turn affect microbial reactions in different ways and to different extents. Specifically, a thermodynamic analysis shows that increasing CO2 partial pressure lowers the energy available from syntrophic oxidation and acetoclastic methanogenesis, but raises the available energy of microbial iron reduction, hydrogenotrophic sulfate reduction and methanogenesis. Kinetic modeling suggests that high CO2 has the potential of inhibiting microbial sulfate reduction while promoting iron reduction. These results are consistent with the observations of previous laboratory and field studies, and highlight the complexity in microbiological responses to elevated CO2 abundance, and the potential power of biogeochemical modeling in evaluating and quantifying these responses. PMID:27909425

Next generation of CO2 enhanced water recovery with subsurface energy storage in China

NASA Astrophysics Data System (ADS)

Li, Qi; Kühn, Michael; Ma, Jianli; Niu, Zhiyong

2017-04-01

Carbon dioxide (CO2) utilization and storage (CCUS) is very popular in comparison with traditional CO2 capture and storage (CCS) in China. In particular, CO2 storage in deep saline aquifers with enhanced water recovery (CO2-EWR) [1] is gaining more and more attention as a cleaner production technology. The CO2-EWR was written into the "U.S.-China Joint Announcement on Climate Change" released November 11, 2014. "Both sides will work to manage climate change by demonstrating a new frontier for CO2 use through a carbon capture, use, and sequestration (CCUS) project that will capture and store CO2 while producing fresh water, thus demonstrating power generation as a net producer of water instead of a water consumer. This CCUS project with enhanced water recovery will eventually inject about 1.0 million tonnes of CO2 and create approximately 1.4 million cubic meters of freshwater per year." In this article, at first we reviewed the history of the CO2-EWR and addressed its current status in China. Then, we put forth a new generation of the CO2-EWR with emphasizing the collaborative solutions between carbon emission reductions and subsurface energy storage or renewable energy cycle [2]. Furthermore, we figured out the key challenging problems such as water-CCUS nexus when integrating the CO2-EWR with the coal chemical industry in the Junggar Basin, Xinjiang, China [3-5]. Finally, we addressed some crucial problems and strategic consideration of the CO2-EWR in China with focuses on its technical bottleneck, relative advantage, early opportunities, environmental synergies and other related issues. This research is not only very useful for the current development of CCUS in the relative "cold season" but also beneficial for the energy security and clean production in China. [1] Li Q, Wei Y-N, Liu G, Shi H (2015) CO2-EWR: a cleaner solution for coal chemical industry in China. Journal of Cleaner Production 103:330-337. doi:10.1016/j.jclepro.2014.09.073 [2] Streibel M., Nakaten N., Kempka T., Kühn M. (2013) Analysis of an integrated carbon cycle for storage of renewables. Energy Procedia 40, 202-211. doi: 10.1016/j.egypro.2013.08.024. [3] Li Q, Wei Y-N, Liu G, Lin Q (2014) Combination of CO2 Geological Storage with Deep Saline Water Recovery in Western China: Insights from Numerical Analyses. Applied Energy 116:101-110. doi:10.1016/j.apenergy.2013.11.050 [4] Wei N, Li X, Fang Z, Bai B, Li Q, Liu S, Jia Y (2015) Regional Resource Distribution of Onshore Carbon Geological Utilization in China. Journal of CO2 Utilization 11:20-30. doi:10.1016/j.jcou.2014.12.005 [5] Li Q, Wei Y-N, Chen Z-A (2016) Water-CCUS Nexus: Challenges and Opportunities of China's Coal Chemical Industry. Clean Technologies and Environmental Policy 18 (3):775-786. doi:10.1007/s10098-015-1049-z

Association between mean and interannual equatorial Indian Ocean subsurface temperature bias in a coupled model

NASA Astrophysics Data System (ADS)

Srinivas, G.; Chowdary, Jasti S.; Gnanaseelan, C.; Prasad, K. V. S. R.; Karmakar, Ananya; Parekh, Anant

2018-03-01

In the present study the association between mean and interannual subsurface temperature bias over the equatorial Indian Ocean (EIO) is investigated during boreal summer (June through September; JJAS) in the National Centers for Environmental Prediction (NCEP) Climate Forecast System (CFSv2) hindcast. Anomalously high subsurface warm bias (greater than 3 °C) over the eastern EIO (EEIO) region is noted in CFSv2 during summer, which is higher compared to other parts of the tropical Indian Ocean. Prominent eastward current bias in the upper 100 m over the EIO region induced by anomalous westerly winds is primarily responsible for subsurface temperature bias. The eastward currents transport warm water to the EEIO and is pushed down to subsurface due to downwelling. Thus biases in both horizontal and vertical currents over the EIO region support subsurface warm bias. The evolution of systematic subsurface warm bias in the model shows strong interannual variability. These maximum subsurface warming episodes over the EEIO are mainly associated with La Niña like forcing. Strong convergence of low level winds over the EEIO and Maritime continent enhanced the westerly wind bias over the EIO during maximum warming years. This low level convergence of wind is induced by the bias in the gradient in the mean sea level pressure with positive bias over western EIO and negative bias over EEIO and parts of western Pacific. Consequently, changes in the atmospheric circulation associated with La Niña like conditions affected the ocean dynamics by modulating the current bias thereby enhancing the subsurface warm bias over the EEIO. It is identified that EEIO subsurface warming is stronger when La Niña co-occurred with negative Indian Ocean Dipole events as compared to La Niña only years in the model. Ocean general circulation model (OGCM) experiments forced with CFSv2 winds clearly support our hypothesis that ocean dynamics influenced by westerly winds bias is primarily responsible for the strong subsurface warm bias over the EEIO. This study advocates the importance of understanding the ability of the models in representing the large scale air-sea interactions over the tropics and their impact on ocean biases for better monsoon forecast.

Monitoring of leaked CO2 through sediment, water column and atmosphere in sub-seabed CCS experiment

NASA Astrophysics Data System (ADS)

Shitashima, K.; Sakamoto, A.; Maea, Y.

2013-12-01

CO2 capture and storage in sub-seabed geological formations (sub-seabed CCS) is currently being studied as a feasible option to mitigate the accumulation of anthropogenic CO2 in the atmosphere. In implementing sub-seabed CCS, detecting and monitoring the impact of the sequestered CO2 on the ocean environment is highly important. The first controlled CO2 release experiment, entitled 'Quantifying and Monitoring Potential Ecosystem Impacts of Geological Carbon Storage (QICS)', took place in Ardmucknish Bay, Oban, in May-July 2012. We applied the in-situ pH/pCO2/ORP sensor to the QICS experiment for detection and monitoring of leaked CO2, and carried out several observations. The on-line sensor that was connected by 400m of RS422 cable was deployed close to the CO2 leakage (bubbling) point, and the fluctuations of pH, pCO2 and ORP were monitored in real-time in a observation van on land. Three sets of off-line sensors were also placed on seafloor in respective points (release point, and two low impacted regions at 25m and 75m distant) for three months. The long-term monitoring of pH in sediment at 50cm depth under the seafloor was conducted. The spear type electrode was stabbed into sediment by diver near the CO2 leakage point. Wide-area mapping surveys of pH, pCO2 and ORP in seawater around the leakage point were carried out by AUV (REMUS-100) that some chemical sensors were installed in. The AUV cruised along the grid line in two layers of 4m and 2m above the seafloor during both of periods of low tide and high tide. Atmospheric CO2 in sea surface above the leakage point was observed by the LI-COR CO2 Analyzer. The analyzer was attached to the bow of ship, and the ship navigated a wide-area along a grid observation line during both of periods of low tide and high tide.

Effective CO2 sequestration monitoring using joint inversion result of seismic and electromagnetic data

NASA Astrophysics Data System (ADS)

Noh, K.; Jeong, S.; Seol, S. J.; Byun, J.; Kwon, T.

2015-12-01

Man-made carbon dioxide (CO2) released into the atmosphere is a significant contributor to the greenhouse gas effect and related global warming. Sequestration of CO2 into saline aquifers has been proposed as one of the most practical options of all geological sequestration possibilities. During CO2 geological sequestration, monitoring is indispensable to delineate the change of CO2 saturation and migration of CO2 in the subsurface. Especially, monitoring of CO2 saturation in aquifers provides useful information for determining amount of injected CO2. Seismic inversion can provide the migration of CO2 plume with high resolution because velocity is reduced when CO2 replaces the pore fluid during CO2 injection. However, the estimation of CO2 saturation using the seismic method is difficult due to the lower sensitivity of the velocity to the saturation when the CO2 saturation up to 20%. On the other hand, marine controlled-source EM (mCSEM) inversion is sensitive to the resistivity changes resulting from variations in CO2 saturation, even though it has poor resolution than seismic method. In this study, we proposed an effective CO2 sequestration monitoring method using joint inversion of seismic and mCSEM data based on a cross-gradient constraint. The method was tested with realistic CO2 injection models in a deep brine aquifer beneath a shallow sea which is selected with consideration for the access convenience for the installation of source and receiver and an environmental safety. Resistivity images of CO2 plume by the proposed method for different CO2 injection stages have been significantly improved over those obtained from individual EM inversion. In addition, we could estimate a reliable CO2 saturation by rock physics model (RPM) using the P-wave velocity and the improved resistivity. The proposed method is a basis of three-dimensional estimation of reservoir parameters such as porosity and fluid saturation, and the method can be also applied for detecting a reservoir and calculating the accurate oil and gas reserves.

Modelling carbon in permafrost soils from preindustrial to the future

NASA Astrophysics Data System (ADS)

Kleinen, T.; Brovkin, V.

2015-12-01

The carbon release from thawing permafrost soils constitutes one of the large uncertainties in the carbon cycle under future climate change. Analysing the problem further, this uncertainty results from an uncertainty about the total amount of C that is stored in frozen soils, combined with an uncertainty about the areas where soils might thaw under a particular climate change scenario, as well as an uncertainty about the decomposition product since some of the decomposed C might result the release of CH4 as well as CO2. We use the land surface model JSBACH, part of the Max Planck Institute Earth System Model MPI-ESM, to quantify the release of soil carbon from thawing permafrost soils. We have extended the soil carbon model YASSO by introducing carbon storages in frozen soils, with increasing fractions of C being available to decomposition as permafrost thaws. In order to quantify the amount of carbon released as CH4, as opposed to CO2, we have also implemented a TOPMODEL-based wetland scheme, as well as anaerobic C decomposition and methane transport. We initialise the soil C pools for the preindustrial climate state from the Northern Circumpolar Soil Carbon Database to insure initial C pool sizes close to measurements. We then determine changes in soil C storage in transient model experiments following historical and future climate changes under RCP 8.5. Based on these experiments, we quantify the greenhouse gas release from permafrost C decomposition, determining both CH4 and CO2 emissions.

Calculation note for an underground leak which remains underground

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goldberg, H.J.

1997-05-20

This calculation note supports the subsurface leak accident scenario which remains subsurface. It is assumed that a single walled pipe carrying waste from tank 106-C ruptures, releasing the liquid waste into the soil. In this scenario, the waste does not form a surface pool, but remains subsurface. However, above the pipe is a berm, 0.762 m (2.5 ft) high and 2.44 m (8 ft) wide, and the liquid released from the leak rises into the berm. The slurry line, which transports a source term of higher activity than the sluice line, leaks into the soil at a rate of 5%more » of the maximum flow rate of 28.4 L/s (450 gpm) for twelve hours. The dose recipient was placed a perpendicular distance of 100 m from the pipe. Two source terms were considered, mitigated and unmitigated release as described in section 3.4.1 of UANF-SD-WM-BIO-001, Addendum 1. The unmitigated consisted of two parts of AWF liquid and one part AWF solid. The mitigated release consisted of two parts SST liquid, eighteen parts AWF liquid, nine parts SST solid, and one part AWF solid. The isotopic breakdown of the release in these cases is presented. Two geometries were considered in preliminary investigations, disk source, and rectangular source. Since the rectangular source results from the assumption that the contamination is wicked up into the berm, only six inches of shielding from uncontaminated earth is present, while the disk source, which remains six inches below the level of the surface of the land is often shielded by a thick shield due to the slant path to the dose point. For this reason, only the rectangular source was considered in the final analysis. The source model was a rectangle 2.134 m (7 ft) thick, 0.6096 m (2 ft) high, and 130.899 m (131 ft) long. The top and sides of this rectangular source was covered with earth of density 1.6 g/cm{sup 3} to a thickness of 15.24 cm (6 in). This soil is modeled as 40% void space. The source consisted of earth of the same density with the void spaces filled with the liquid waste which added 0.56 g/cm{sup 3} to the density. The dose point was 100 m (328 ft) away from the berm in a perpendicular direction off the center. The computer code MICROSKYSHINEO was used to calculate the skyshine from the source. This code calculates exposure rate at the receptor point. The photon spectrum from 2 MeV to 0.15 MeV, obtained from ISOSHLD, was used as input, although this did not differ substantially from the results obtained from using Co, 137mBa, and 154Eu. However, this methodology allowed the bremsstrahlung contribution to be included in the skyshine calculation as well as in the direct radiation calculation.« less

Nature of the Active Sites for CO Reduction on Copper Nanoparticles; Suggestions for Optimizing Performance.

PubMed

Cheng, Tao; Xiao, Hai; Goddard, William A

2017-08-30

Recent experiments show that the grain boundaries (GBs) of copper nanoparticles (NPs) lead to an outstanding performance in reducing CO 2 and CO to alcohol products. We report here multiscale simulations that simulate experimental synthesis conditions to predict the structure of a 10 nm Cu NP (158 555 atoms). To identify active sites, we first predict the CO binding at a large number of sites and select four exhibiting CO binding stronger than the (211) step surface. Then, we predict the formation energy of the *OCCOH intermediate as a descriptor for C-C coupling, identifying two active sites, both of which have an under-coordinated surface square site adjacent to a subsurface stacking fault. We then propose a periodic Cu surface (4 by 4 supercell) with a similar site that substantially decreases the formation energy of *OCCOH, by 0.14 eV.

Electrical Signatures of Ethanol-Liquid Mixtures: Implications for Monitoring Biofuels Migration in the Subsurface

EPA Science Inventory

Ethanol (EtOH), an emerging contaminant with potential direct and indirect environmental effects, poses threats to water supplies when spilled in large volumes. A series of experiments was directed at understanding the electrical geophysical signatures arising from groundwater co...

Adaptive management for subsurface pressure and plume control in application to geological CO2 storage

NASA Astrophysics Data System (ADS)

Gonzalez-Nicolas, A.; Cihan, A.; Birkholzer, J. T.; Petrusak, R.; Zhou, Q.; Riestenberg, D. E.; Trautz, R. C.; Godec, M.

2016-12-01

Industrial-scale injection of CO2 into the subsurface can cause reservoir pressure increases that must be properly controlled to prevent any potential environmental impact. Excessive pressure buildup in reservoir may result in ground water contamination stemming from leakage through conductive pathways, such as improperly plugged abandoned wells or distant faults, and the potential for fault reactivation and possibly seal breaching. Brine extraction is a viable approach for managing formation pressure, effective stress, and plume movement during industrial-scale CO2 injection projects. The main objectives of this study are to investigate suitable different pressure management strategies involving active brine extraction and passive pressure relief wells. Adaptive optimized management of CO2 storage projects utilizes the advanced automated optimization algorithms and suitable process models. The adaptive management integrates monitoring, forward modeling, inversion modeling and optimization through an iterative process. In this study, we employ an adaptive framework to understand primarily the effects of initial site characterization and frequency of the model update (calibration) and optimization calculations for controlling extraction rates based on the monitoring data on the accuracy and the success of the management without violating pressure buildup constraints in the subsurface reservoir system. We will present results of applying the adaptive framework to test appropriateness of different management strategies for a realistic field injection project.

Development of a Carbon Sequestration Visualization Tool using Google Earth Pro

NASA Astrophysics Data System (ADS)

Keating, G. N.; Greene, M. K.

2008-12-01

The Big Sky Carbon Sequestration Partnership seeks to prepare organizations throughout the western United States for a possible carbon-constrained economy. Through the development of CO2 capture and subsurface sequestration technology, the Partnership is working to enable the region to cleanly utilize its abundant fossil energy resources. The intent of the Los Alamos National Laboratory Big Sky Visualization tool is to allow geochemists, geologists, geophysicists, project managers, and other project members to view, identify, and query the data collected from CO2 injection tests using a single data source platform, a mission to which Google Earth Pro is uniquely and ideally suited . The visualization framework enables fusion of data from disparate sources and allows investigators to fully explore spatial and temporal trends in CO2 fate and transport within a reservoir. 3-D subsurface wells are projected above ground in Google Earth as the KML anchor points for the presentation of various surface subsurface data. This solution is the most integrative and cost-effective possible for the variety of users in the Big Sky community.

Experimentally investigate ionospheric depletion chemicals in artificially created ionosphere

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu Yu; Cao Jinxiang; Wang Jian

2012-09-15

A new approach for investigating ionosphere chemical depletion in the laboratory is introduced. Air glow discharge plasma closely resembling the ionosphere in both composition and chemical reactions is used as the artificially created ionosphere. The ionospheric depletion experiment is accomplished by releasing chemicals such as SF{sub 6}, CCl{sub 2}F{sub 2}, and CO{sub 2} into the model discharge. The evolution of the electron density is investigated by varying the plasma pressure and input power. It is found that the negative ion (SF{sub 6}{sup -}, CCl{sub 2}F{sub 2}{sup -}) intermediary species provide larger reduction of the electron density than the positive ionmore » (CO{sub 2}{sup +}) intermediary species. The negative ion intermediary species are also more efficient in producing ionospheric holes because of their fast reaction rates. Airglow enhancement attributed to SF{sub 6} and CO{sub 2} releases agrees well with the published data. Compared to the traditional methods, the new scheme is simpler to use, both in the release of chemicals and in the electron density measurements. It is therefore more efficient for investigating the release of chemicals in the ionosphere.« less

Does the presence of bacteria effect basaltic glass dissolution rates? 1: Dead Pseudomonas reactants

NASA Astrophysics Data System (ADS)

Stockmann, Gabrielle J.; Shirokova, Liudmila S.; Pokrovsky, Oleg S.; Oelkers, Eric H.; Benezeth, Pascale

2010-05-01

Basaltic glass and crystalline basalt formations in Iceland have been suggested for industrial CO2 storage due to their porous and permeable properties and high reactivity. Acid CO2-saturated waters in contact with basaltic glass will lead to rapid dissolution of the glass and release of divalent cations, (Ca2+, Mg2+, Fe2+) that can react to form stable carbonates and thereby trap the CO2. However, the basalt formations in Iceland not only contains glass and mineral assemblages, but also host microbiological communities that either by their presence or by active involvement in chemical reactions could affect the amount of basaltic glass being dissolved and CO2 being trapped. Samples of natural bacteria communities from the CO2 storage grounds in Iceland were collected, separated, and purified using agar plate technique and cultured under laboratory conditions in nutrient broth-rich media. Heterotrophic aerobic Gram-negative strain of Pseudomonas reactants was selected for a series of flow-through experiments aimed at evaluation of basaltic glass dissolution rate in the presense of increasing amounts of dead bacteria and their lysis products. The experiments were carried out using mixed-flow reactors at pH 4, 6, 8 and 10 at 25 °C. Each of the four reactors contained 1 gram of basaltic glass of the size fraction 45-125 μm. This glass was dissolved in ~ 0.01 M buffer solutions (acetate, MES, bicarbonate and carbonate+bicarbonate mixture) of the desired pH. All experiments ran 2 months, keeping the flowrate and temperature stable and only changing the concentration of dead bacteria in the inlet solutions (from 0 to 430 mg/L). Experiments were performed in sterile conditions, and bacterial growth was prevented by adding NaN3 to the inlet solutions. Routine culturing of bacteria on the agar plates confirmed the sterility of experiments. Samples of outlet solutions were analyzed for major cations and trace elements by ICP-MS. Results demonstrate a slight decrease in the Si, Ca, and Mg release rates from basaltic glass with increasing concentration of dead bacteria at pH 4 and 6, but no effect at pH 8 and 10. The Al dissolution rate is lowered by up to one order of magnitude at all four pH values by the presence of dead bacteria. Comparison of SEM photos of the basaltic glass before and after experiments show no visible change of the glass surface. These results suggest that the presence of dead Pseudomonas reactants in the basaltic formations of Iceland will likely affect negligible the dissolution of basaltic glass during CO2 sequestration. The main effect of bacterial presence seems to be 1) the increase of the concentration of DOC that can complex metals and thus facilitate cation release from the solid phase and/or 2) adsorption of released metals at the surface of the biomass thus decreasing the overall element export rate.

Combined Experimental and Computational Approach to Predict the Glass-Water Reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pierce, Eric M.; Bacon, Diana H.

2011-10-01

The use of mineral and glass dissolution rates measured in laboratory experiments to predict the weathering of primary minerals and volcanic and nuclear waste glasses in field studies requires the construction of rate models that accurately describe the weathering process over geologic timescales. Additionally, the need to model the long-term behavior of nuclear waste glass for the purpose of estimating radionuclide release rates requires that rate models be validated with long-term experiments. Several long-term test methods have been developed to accelerate the glass-water reaction [drip test, vapor hydration test, product consistency test B, and pressurized unsaturated flow (PUF)], thereby reducingmore » the duration required to evaluate long-term performance. Currently, the PUF test is the only method that mimics the unsaturated hydraulic properties expected in a subsurface disposal facility and simultaneously monitors the glass-water reaction. PUF tests are being conducted to accelerate the weathering of glass and validate the model parameters being used to predict long-term glass behavior. A one-dimensional reactive chemical transport simulation of glass dissolution and secondary phase formation during a 1.5-year-long PUF experiment was conducted with the Subsurface Transport Over Reactive Multiphases (STORM) code. Results show that parameterization of the computer model by combining direct bench scale laboratory measurements and thermodynamic data provides an integrated approach to predicting glass behavior over the length of the experiment. Over the 1.5-year-long test duration, the rate decreased from 0.2 to 0.01 g/(m2 day) based on B release for low-activity waste glass LAWA44. The observed decrease is approximately two orders of magnitude higher than the decrease observed under static conditions with the SON68 glass (estimated to be a decrease by four orders of magnitude) and suggests that the gel-layer properties are less protective under these dynamic conditions.« less

Combined Experimental and Computational Approach to Predict the Glass-Water Reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pierce, Eric M; Bacon, Diana

2011-01-01

The use of mineral and glass dissolution rates measured in laboratory experiments to predict the weathering of primary minerals and volcanic and nuclear waste glasses in field studies requires the construction of rate models that accurately describe the weathering process over geologic time-scales. Additionally, the need to model the long-term behavior of nuclear waste glass for the purpose of estimating radionuclide release rates requires that rate models are validated with long-term experiments. Several long-term test methods have been developed to accelerate the glass-water reaction [drip test, vapor hydration test, product consistency test-B, and pressurized unsaturated flow (PUF)], thereby reducing themore » duration required to evaluate long-term performance. Currently, the PUF test is the only method that mimics the unsaturated hydraulic properties expected in a subsurface disposal facility and simultaneously monitors the glass-water reaction. PUF tests are being conducted to accelerate the weathering of glass and validate the model parameters being used to predict long-term glass behavior. A one-dimensional reactive chemical transport simulation of glass dissolution and secondary phase formation during a 1.5-year long PUF experiment was conducted with the subsurface transport over reactive multi-phases code. Results show that parameterization of the computer model by combining direct bench-scale laboratory measurements and thermodynamic data provides an integrated approach to predicting glass behavior over the length of the experiment. Over the 1.5-year long test duration, the rate decreased from 0.2 to 0.01 g/(m2 d) base on B release. The observed decrease is approximately two orders of magnitude higher than the decrease observed under static conditions with the SON68 glass (estimated to be a decrease by 4 orders of magnitude) and suggest the gel-layer properties are less protective under these dynamic conditions.« less

Feasibility of Autonomous Monitoring of CO2 Leakage in Aquifers: Results From Controlled Laboratory Experiments

NASA Astrophysics Data System (ADS)

Versteeg, R.; Leger, E.; Dafflon, B.

2016-12-01

Geologic sequestration of CO2 is one of the primary proposed approaches for reducing total atmospheric CO2 concentrations. MVAA (Monitoring, Verification, Accounting and Assessment) of CO2 sequestration is an essential part of the geologic CO2 sequestration cycle. MVAA activities need to meet multiple operational, regulatory and environmental objectives, including ensuring the protection of underground sources of drinking water. Anticipated negative consequences of CO2 leakage into groundwater, besides possible brine contamination and release of gaseous CO2, include a significant increase of dissolved CO2 into shallow groundwater systems, which will decrease groundwater pH and can potentially mobilize naturally occurring trace metals and ions that are commonly absorbed to or contained in sediments. Autonomous electrical geophysical monitoring in aquifers has the potential of allowing for rapid and automated detection of CO2 leakage. However, while the feasibility of such monitoring has been demonstrated by a number of different field experiments, automated interpretation of complex electrical resistivity data requires the development of quantitative relationships between complex electrical resistivity signatures and dissolved CO2 in the aquifer resulting from leakage Under a DOE SBIR funded effort we performed multiple tank scale experiments in which we investigated complex electrical resistivity signatures associated with dissolved CO2 plumes in saturated sediments. We also investigated the feasibility of distinguishing CO2 leakage signatures from signatures associated with other processes such as salt water movement, temperature variations and other variations in chemical or physical conditions. In addition to these experiments we also numerically modeled the tank experiments. These experiments showed that (a) we can distinguish CO2 leakage signatures from other signatures, (b) CO2 leakage signatures have a consistent characteristic, (c) laboratory experiments are in agreement with field results, and (d) we can numerically simulate the main characteristics of CO2 leakage and associated electrical geophysical signatures.

An evaluation of the residual toxicity and chemistry of a sodium hydroxide-based ballast water treatment system for freshwater ships

USGS Publications Warehouse

Elskus, Adria; Ingersoll, Christopher G.; Kemble, Nile E.; Echols, Kathy R.; Brumbaugh, William G.; Henquinet, Jeffrey; Watten, Barnaby J.

2015-01-01

Nonnative organisms in the ballast water of freshwater ships must be killed to prevent the spread of invasive species. The ideal ballast water treatment system (BWTS) would kill 100% of ballast water organisms with minimal residual toxicity to organisms in receiving waters. In the present study, the residual toxicity and chemistry of a BWTS was evaluated. Sodium hydroxide was added to elevate pH to >11.5 to kill ballast water organisms, then reduced to pH <9 by sparging with wet-scrubbed diesel exhaust (the source of CO2). Cladocerans (Ceriodaphnia dubia), amphipods (Hyalella azteca), and fathead minnows (Pimephales promelas) were exposed for 2 d to BWTS water under an air atmosphere (pH drifted to ≥9) or a 2.5% CO2 atmosphere (pH 7.5–8.2), then transferred to control water for 5 d to assess potential delayed toxicity. Chemical concentrations in the BWTS water met vessel discharge guidelines with the exception of concentrations of copper. There was little to no residual toxicity to cladocerans or fish, but the BWTS water was toxic to amphipods. Maintaining a neutral pH and diluting BWTS water by 50% eliminated toxicity to the amphipods. The toxicity of BWTS water would likely be minimal because of rapid dilution in the receiving water, with subsurface release likely preventing pH rise. This BWTS has the potential to become a viable method for treating ballast water released into freshwater systems.

METHANE AND WATER ON MARS: MAPS OF ACTIVE REGIONS AND THEIR SEASONAL VARIABILITY

NASA Astrophysics Data System (ADS)

Villanueva, G. L.; Mumma, M. J.; Novak, R. E.

2009-12-01

We have detected methane on Mars, and measured it simultaneously with water using powerful ground-based telescopes [1, 2]. Its presence in such a strongly oxidized atmosphere (CO2: 95.3%) requires recent release; the ultimate origin of this methane is uncertain, but it could either be abiotic or biotic. On Earth, methane is produced primarily by biology, with a small fraction produced by abiotic means. The sources and sinks of hydrogen-bearing species (e.g., H2O and CH4) on Mars are still poorly known. In particular, the roles of the regolith and the sub-surface hydrogen reservoirs in the Martian water cycle have been broadly studied, but have not been conclusively quantified. If water is being released from the sub-surface or shares a common source with other H-bearing species, we might see correlations among them. Previous searches for such correlations have been precluded because of the lack of simultaneity of the measurements and the intrinsic variability of water on Mars, which is a condensable whose total local abundance is partitioned among several competing phases controlled largely by temperature (ensuring its variability on a variety of time scales, from diurnal to seasonal to epochal). We sampled multiple spectral lines of methane and water vapor on Mars in a campaign spanning seven years (three Mars years; 1999-2006) and sampling three seasons on Mars. Data were ac-quired using long-slit infrared spectrometers: CSHELL (Cryogenic Echelle Spectrograph) at NASA-IRTF (Infrared Telescope Facility) and NIRSPEC (Near Infrared Spectrograph) at Keck 2. These instruments offer spatially-resolved spectra with the high spectral resolving power (λ/δλ ~ 40,000) needed to reduce confusion among telluric, Martian, and Fraunhofer lines (in reflected solar radiation). Since 2005, we greatly improved our data processing algorithms and increased the sensitivity of our measurements by an order of magnitude. Using these new techniques, we detected multiple lines of methane on Mars [1] and discovered two new band sys-tems of isotopic CO2 (at 3.3 and 3.7 μm) that can interfere with signatures of CH4 and HDO [3, 4]. The spectral signatures of these isotopic CO2 transitions may affect searches based on low spectral resolution methods, but they do not affect the searches reported herein. We present the spatial distributions of methane and water-vapor on Mars extracted from our seven-year spectral database, and we compare these with geological parameters. Both gases are depleted at vernal equinox but are enhanced in warm seasons (spring/summer), though often with dissimilar spatial distributions. In Northern Summer we observe a polar outburst of water but no methane, while in Southern Spring we observe release of abundant methane but little water. Regions of methane release appear mainly over ancient terrain (Noachian/Hesperian, older than 3 billion years) known to have a rich hydration history. [1] Mumma et al. (2009) Science 323:1041-1045. [2] Villanueva et al. (2009), submitted. [3] Villanueva et al. (2008) Icarus 195(1):34-44. [4] Villanueva et al. (2008) JQSRT 109(6):883-894.

Subsurface Monitoring of CO2 Sequestration - A Review and Look Forward

NASA Astrophysics Data System (ADS)

Daley, T. M.

2012-12-01

The injection of CO2 into subsurface formations is at least 50 years old with large-scale utilization of CO2 for enhanced oil recovery (CO2-EOR) beginning in the 1970s. Early monitoring efforts had limited measurements in available boreholes. With growing interest in CO2 sequestration beginning in the 1990's, along with growth in geophysical reservoir monitoring, small to mid-size sequestration monitoring projects began to appear. The overall goals of a subsurface monitoring plan are to provide measurement of CO2 induced changes in subsurface properties at a range of spatial and temporal scales. The range of spatial scales allows tracking of the location and saturation of the plume with varying detail, while finer temporal sampling (up to continuous) allows better understanding of dynamic processes (e.g. multi-phase flow) and constraining of reservoir models. Early monitoring of small scale pilots associated with CO2-EOR (e.g., the McElroy field and the Lost Hills field), developed many of the methodologies including tomographic imaging and multi-physics measurements. Large (reservoir) scale sequestration monitoring began with the Sleipner and Weyburn projects. Typically, large scale monitoring, such as 4D surface seismic, has limited temporal sampling due to costs. Smaller scale pilots can allow more frequent measurements as either individual time-lapse 'snapshots' or as continuous monitoring. Pilot monitoring examples include the Frio, Nagaoka and Otway pilots using repeated well logging, crosswell imaging, vertical seismic profiles and CASSM (continuous active-source seismic monitoring). For saline reservoir sequestration projects, there is typically integration of characterization and monitoring, since the sites are not pre-characterized resource developments (oil or gas), which reinforces the need for multi-scale measurements. As we move beyond pilot sites, we need to quantify CO2 plume and reservoir properties (e.g. pressure) over large scales, while still obtaining high resolution. Typically the high-resolution (spatial and temporal) tools are deployed in permanent or semi-permanent borehole installations, where special well design may be necessary, such as non-conductive casing for electrical surveys. Effective utilization of monitoring wells requires an approach of modular borehole monitoring (MBM) were multiple measurements can be made. An example is recent work at the Citronelle pilot injection site where an MBM package with seismic, fluid sampling and distributed fiber sensing was deployed. For future large scale sequestration monitoring, an adaptive borehole-monitoring program is proposed.

Subsurface fate and transport of sulfamethoxazole, 4-nonylphenol, and 17β-estradiol

USGS Publications Warehouse

Barber, L.B.; Meyer, M.T.; LeBlanc, D.R.; Kolpin, Dana W.; Radley, Paul; Chapelle, F.; Rubio, F.

2008-01-01

Subsurface fate and transport of the antibiotic sulfamethoxazole (SX), the non-ionic surfactant degradation product 4-nonylphenol (NP), and the sex hormone 17β-estradiol (E2) were evaluated in a plume of contaminated groundwater at Cape Cod, Massachusetts, USA. The plume is the result of 60 years of wastewater treatment plant effluent disposal into rapid infiltration beds. Natural-gradient, in situ tracer experiments were used to evaluate subsurface transport of SX, NP, and E2 (injected at 300, 530, and 0.55 µg/L, respectively) relative to the conservative tracer bromide. Two geochemical zones were evaluated: (1) uncontaminated groundwater overlying the plume, and (2) contaminated groundwater within the plume that has recently become oxic after decades of anoxic conditions. The uncontaminated groundwater is characterized by a microbial community unacclimated to treated wastewater, whereas the contaminated groundwater is characterized by microbes acclimated to wastewater contaminants. Results from the tracer tests in both zones showed that the antibiotic SX was co-transported with the conservative tracer bromide, with little retardation or mass removal. In contrast, NP and E2, which are more hydrophobic and biodegradable, showed sorption (relative retardation factors ranged up to 5.9) and mass loss at both the uncontaminated and contaminated sites.

A mesocosm study of the effects of wet-dry cycles on nutrient release from constructed wetlands in agricultural landscapes.

PubMed

Smith, Allyson S; Jacinthe, Pierre-Andre

2014-01-01

Given the projection that wet-dry periods will be more frequent in the US Midwest, a study was conducted to understand the impact of these hydro-climatic alterations on nutrient dynamics in wetlands constructed on former croplands in the region. Soil cores were collected from two constructed wetlands and a wooded riparian area (surface: 0-20 cm; subsurface: 40-60 cm) downslope from an agricultural field. Cores were either kept moist or subjected to a 5-week drying treatment, after which all cores were flooded for 36 days. Initial nitrate flux was significantly (p < 0.001) higher in the dry than in the moist treatment (44.5 vs. 1.9 mg N m(-2) per day), likely due to mineralization of organic matter. The NO3(-) released was rapidly denitrified (N2O flux: 18.9 mg N m(-2) per day), except in the subsurface soil cores in which processing of available N (N2O flux: 0.33 mg N m(-2) per day) was limited by low microbial activity (4 times lower CO2 production rate). The dry treatment also resulted in significantly (p < 0.01) higher inorganic P (Pi) flux (3.1 versus 1 mg P m(-2) per day in moist cores), with water-extractable soil P being the best predictor (r(2): 0.93, p < 0.03) of that flux. Despite a decline in redox potential (as low as -36.4 mv) and progressive increase in pore-water dissolved Fe, no relationship between floodwater Pi and dissolved Fe was observed, suggesting either limited contribution of reductive dissolution to Pi dynamics or rapid adsorption of the Pi released within the cores. Compared to the moist cores, geochemical modeling showed a consistent shift toward greater solubility of the calcium-phosphate minerals controlling pore-water Pi concentration in the dry treatment cores. These results suggest that dissolution of Ca-phosphate minerals could be a key factor controlling Pi mobility in constructed wetlands subjected to wet-dry cycles.

Supercritical CO2 uptake by nonswelling phyllosilicates

PubMed Central

Tokunaga, Tetsu K.; Ashby, Paul D.; Kim, Yongman; Voltolini, Marco; Gilbert, Benjamin; DePaolo, Donald J.

2018-01-01

Interactions between supercritical (sc) CO2 and minerals are important when CO2 is injected into geologic formations for storage and as working fluids for enhanced oil recovery, hydraulic fracturing, and geothermal energy extraction. It has previously been shown that at the elevated pressures and temperatures of the deep subsurface, scCO2 alters smectites (typical swelling phyllosilicates). However, less is known about the effects of scCO2 on nonswelling phyllosilicates (illite and muscovite), despite the fact that the latter are the dominant clay minerals in deep subsurface shales and mudstones. Our studies conducted by using single crystals, combining reaction (incubation with scCO2), visualization [atomic force microscopy (AFM)], and quantifications (AFM, X-ray photoelectron spectroscopy, X-ray diffraction, and off-gassing measurements) revealed unexpectedly high CO2 uptake that far exceeded its macroscopic surface area. Results from different methods collectively suggest that CO2 partially entered the muscovite interlayers, although the pathways remain to be determined. We hypothesize that preferential dissolution at weaker surface defects and frayed edges allows CO2 to enter the interlayers under elevated pressure and temperature, rather than by diffusing solely from edges deeply into interlayers. This unexpected uptake of CO2, can increase CO2 storage capacity by up to ∼30% relative to the capacity associated with residual trapping in a 0.2-porosity sandstone reservoir containing up to 18 mass % of illite/muscovite. This excess CO2 uptake constitutes a previously unrecognized potential trapping mechanism. PMID:29339499

Supercritical CO2 uptake by nonswelling phyllosilicates.

PubMed

Wan, Jiamin; Tokunaga, Tetsu K; Ashby, Paul D; Kim, Yongman; Voltolini, Marco; Gilbert, Benjamin; DePaolo, Donald J

2018-01-30

Interactions between supercritical (sc) CO 2 and minerals are important when CO 2 is injected into geologic formations for storage and as working fluids for enhanced oil recovery, hydraulic fracturing, and geothermal energy extraction. It has previously been shown that at the elevated pressures and temperatures of the deep subsurface, scCO 2 alters smectites (typical swelling phyllosilicates). However, less is known about the effects of scCO 2 on nonswelling phyllosilicates (illite and muscovite), despite the fact that the latter are the dominant clay minerals in deep subsurface shales and mudstones. Our studies conducted by using single crystals, combining reaction (incubation with scCO 2 ), visualization [atomic force microscopy (AFM)], and quantifications (AFM, X-ray photoelectron spectroscopy, X-ray diffraction, and off-gassing measurements) revealed unexpectedly high CO 2 uptake that far exceeded its macroscopic surface area. Results from different methods collectively suggest that CO 2 partially entered the muscovite interlayers, although the pathways remain to be determined. We hypothesize that preferential dissolution at weaker surface defects and frayed edges allows CO 2 to enter the interlayers under elevated pressure and temperature, rather than by diffusing solely from edges deeply into interlayers. This unexpected uptake of CO 2 , can increase CO 2 storage capacity by up to ∼30% relative to the capacity associated with residual trapping in a 0.2-porosity sandstone reservoir containing up to 18 mass % of illite/muscovite. This excess CO 2 uptake constitutes a previously unrecognized potential trapping mechanism. Copyright © 2018 the Author(s). Published by PNAS.

Supercritical CO 2 uptake by nonswelling phyllosilicates

DOE PAGES

Wan, Jiamin; Tokunaga, Tetsu K.; Ashby, Paul D.; ...

2018-01-16

Interactions between supercritical (sc) CO 2 and minerals are important when CO 2 is injected into geologic formations for storage and as working fluids for enhanced oil recovery, hydraulic fracturing, and geothermal energy extraction. It has previously been shown that at the elevated pressures and temperatures of the deep subsurface, scCO 2 alters smectites (typical swelling phyllosilicates). However, less is known about the effects of scCO 2 on nonswelling phyllosilicates (illite and muscovite), despite the fact that the latter are the dominant clay minerals in deep subsurface shales and mudstones. Our studies conducted by using single crystals, combining reaction (incubationmore » with scCO 2 ), visualization [atomic force microscopy (AFM)], and quantifications (AFM, X-ray photoelectron spectroscopy, X-ray diffraction, and off-gassing measurements) revealed unexpectedly high CO 2 uptake that far exceeded its macroscopic surface area. Results from different methods collectively suggest that CO 2 partially entered the muscovite interlayers, although the pathways remain to be determined. We hypothesize that preferential dissolution at weaker surface defects and frayed edges allows CO 2 to enter the interlayers under elevated pressure and temperature, rather than by diffusing solely from edges deeply into interlayers. This unexpected uptake of CO 2, can increase CO 2 storage capacity by up to ~30% relative to the capacity associated with residual trapping in a 0.2-porosity sandstone reservoir containing up to 18 mass % of illite/muscovite. This excess CO 2 uptake constitutes a previously unrecognized potential trapping mechanism.« less

The hysteresis response of soil CO 2 concentration and soil respiration to soil temperature

DOE PAGES

Zhang, Quan; Katul, Gabriel G.; Oren, Ram; ...

2015-07-20

Diurnal hysteresis between soil temperature (T s) and both CO 2 concentration ([CO 2]) and soil respiration rate (R s) were reported across different field experiments. However, the causes of these hysteresis patterns remain a subject of debate, with biotic and abiotic factors both invoked as explanations. Here, to address these issues, a CO 2 gas transport model is developed by combining a layer-wise mass conservation equation for subsurface gas phase CO 2, Fickian diffusion for gas transfer, and a CO 2 source term that depends on soil temperature, moisture, and photosynthetic rate. Using this model, a hierarchy of numericalmore » experiments were employed to disentangle the causes of the hysteretic [CO 2]-T s and CO 2 flux T s (i.e., F-T s) relations. Model results show that gas transport alone can introduce both [CO 2]-T s and F-T s hystereses and also confirm prior findings that heat flow in soils lead to [CO 2] and F being out of phase with T s, thereby providing another reason for the occurrence of both hystereses. The area (A hys) of the [CO 2]-T s hysteresis near the surface increases, while the A hys of the Rs-Ts hysteresis decreases as soils become wetter. Moreover, a time-lagged carbon input from photosynthesis deformed the [CO 2]-T s and R s-T s patterns, causing a change in the loop direction from counterclockwise to clockwise with decreasing time lag. An asymmetric 8-shaped pattern emerged as the transition state between the two loop directions. Lastly, tracing the pattern and direction of the hysteretic [CO 2]-T s and R s-T s relations can provide new ways to fingerprint the effects of photosynthesis stimulation on soil microbial activity and detect time lags between rhizospheric respiration and photosynthesis.« less

Gas hydrate formation in the deep sea: In situ experiments with controlled release of methane, natural gas, and carbon dioxide

USGS Publications Warehouse

Brewer, P.G.; Orr, F.M.; Friederich, G.; Kvenvolden, K.A.; Orange, D.L.

1998-01-01

We have utilized a remotely operated vehicle (ROV) to initiate a program of research into gas hydrate formation in the deep sea by controlled release of hydrocarbon gases and liquid CO2 into natural sea water and marine sediments. Our objectives were to investigate the formation rates and growth patterns of gas hydrates in natural systems and to assess the geochemical stability of the reaction products over time. The novel experimental procedures used the carrying capacity, imaging capability, and control mechanisms of the ROV to transport gas cylinders to depth and to open valves selectively under desired P-T conditions to release the gas either into contained natural sea water or into sediments. In experiments in Monterey Bay, California, at 910 m depth and 3.9??C water temperature we find hydrate formation to be nearly instantaneous for a variety of gases. In sediments the pattern of hydrate formation is dependent on the pore size, with flooding of the pore spaces in a coarse sand yielding a hydrate cemented mass, and gas channeling in a fine-grained mud creating a veined hydrate structure. In experiments with liquid CO2 the released globules appeared to form a hydrate skin as they slowly rose in the apparatus. An initial attempt to leave the experimental material on the sea floor for an extended period was partially successful; we observed an apparent complete dissolution of the liquid CO2 mass, and an apparent consolidation of the CH4 hydrate, over a period of about 85 days.

Linked metatranscriptomic and geochemical data indicate microbial succession in naturally reduced aquifer sediments dominated by H2-oxidizing Comamonadaceae

NASA Astrophysics Data System (ADS)

Jewell, T. N. M.; Karaoz, U.; Bill, M.; Chakraborty, R.; Brodie, E.; Williams, K. H.; Beller, H. R.

2015-12-01

In this study, we sought to better understand what natural organic matter fuels heterotrophic microbial communities in the anoxic subsurface at the Rifle (CO) site and what genes may be diagnostic of that activity. We conducted a 20-day microcosm experiment with naturally reduced zone (NRZ) sediments and collected replicate samples every 5 days for omics (metagenome and metatranscriptome) and biogeochemical measurements (e.g., continuous CO2 production, H2, CH4, acetate, DOC, Fe(II), sulfate, NH4+, spectroscopic analyses of sediment OM). No electron donors were added other than the NRZ sediment, which is enriched in organic matter relative to typical Rifle aquifer material. The microcosms were constructed and incubated under anaerobic conditions in serum bottles with a N2headspace. Biogeochemical measurements indicate that the decomposition of native organic matter occurred in different phases, including depletion of DOC and release of CO2 during the first week of incubation, followed by a pulse of acetogenesis and methanogenesis after 2 weeks (with acetogenesis dominating carbon flux after 2 weeks). While H2 remained below detection levels throughout the study, a peak of [NiFe] uptake hydrogenase, acetyl-CoA synthetase, urease, and nitrate reductase transcripts belonging to the Comamonadaceae family occurred at day 15. Some members of Comamonadaceae are facultative H2-oxidizing chemolithoautotrophs and fix carbon via the acetogenic Wood-Ljungdahl pathway. Comamonadaceae plateaued at 73% of the metagenome at this time and represented 69% of the metatranscriptome, succeeding the S-oxidizing Sulfurimonas genus. Sulfurimonas species were the dominant group at day 0, accounting for 43% of the metagenome and 25% of the metatranscriptome, decreasing to 11% in both the metagenome and metatranscriptome by day 10. Less abundant but still present were transcripts for genes involved in cellulose degradation (glycosyl hydrolases), and glycolysis (phosphofructokinase), consistent with plant biomass degradation. Although further analysis will be required to elucidate the complex and dynamic biogeochemical interactions occurring in this system, it is clear that dramatic metabolic changes occurred over time that markedly altered the nature and magnitude of carbon flux.

Active CO2 Reservoir Management for Carbon Capture, Utilization, and Sequestration: Impact on Permitting, Monitoring, and Public Acceptance

NASA Astrophysics Data System (ADS)

Buscheck, T. A.; Chen, M.; Sun, Y.; Hao, Y.; Court, B.; Celia, M. A.; Wolery, T.; Aines, R. D.

2011-12-01

CO2 capture and sequestration (CCS) integrated with geothermal energy production in deep geological formations can play an important role in reducing CO2 emissions to the atmosphere and thereby mitigate global climate change. For industrial-scale CO2 injection in saline formations, pressure buildup can limit storage capacity and security. Active CO2 Reservoir Management (ACRM) combines brine production with CO2 injection to relieve pressure buildup, increase injectivity, manipulate CO2 migration, constrain brine leakage, and enable beneficial utilization of produced brine. Therefore, ACRM can be an enabler of carbon capture, utilization, and sequestration (CCUS). Useful products may include freshwater, cooling water, make-up water for pressure support in oil, gas, and geothermal reservoir operations, and geothermal energy production. Implementation barriers to industrial-scale CCS include concerns about (1) CO2 sequestration security and assurance, (2) pore-space competition with neighboring subsurface activities, (3) CO2 capture costs, and (4) water-use demands imposed by CCS operations, which is particularly important where water resources are already scarce. CCUS, enabled by ACRM, has the potential of addressing these barriers. Pressure relief from brine production can substantially reduce the driving force for potential CO2 and brine migration, as well as minimize interference with neighboring subsurface activities. Electricity generated from geothermal energy can offset a portion of the parasitic energy and financial costs of CCS. Produced brine can be used to generate freshwater by desalination technologies, such as RO, provide a source for saltwater cooling systems or be used as make-up water for oil, gas, or geothermal reservoir operations, reducing the consumption of valuable freshwater resources. We examine the impact of brine production on reducing CO2 and brine leakage. A volumetric balance between injected and produced fluids minimizes the spatial extent of the pressure perturbation, substantially reducing both the Area of Review (AoR) and interactions with neighboring subsurface activities. This will reduce pore-space competition between neighboring subsurface activities, allowing for independent planning, assessment, and permitting. Because post-injection pressure buildup is virtually eliminated, this could have a major impact on post-injection monitoring requirements. Reducing the volume of rock over which brine can migrate may significantly affect site characterization requirements, as well as the impact of parametric and conceptual model uncertainties, such as those related to abandoned wells. ACRM-CCUS has the potential of playing a beneficial role in site-characterization, permitting, and monitoring activities, and in gaining public acceptance. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Muon Tomography for Geological Repositories.

NASA Astrophysics Data System (ADS)

Woodward, D.; Kudryavtsev, V.; Gluyas, J.; Clark, S. J.; Thompson, L. F.; Klinger, J.; Spooner, N. J.; Blackwell, T. B.; Pal, S.; Lincoln, D. L.; Paling, S. M.; Mitchell, C. N.; Benton, C.; Coleman, M. L.; Telfer, S.; Cole, A.; Nolan, S.; Chadwick, P.

2015-12-01

Cosmic-ray muons are subatomic particles produced in the upper atmosphere in collisions of primary cosmic rays with atoms in air. Due to their high penetrating power these muons can be used to image the content (primarily density) of matter they pass through. They have already been used to image the structure of pyramids, volcanoes and other objects. Their applications can be extended to investigating the structure of, and monitoring changes in geological formations and repositories, in particular deep subsurface sites with stored CO2. Current methods of monitoring subsurface CO2, such as repeat seismic surveys, are episodic and require highly skilled personnel to operate. Our simulations based on simplified models have previously shown that muon tomography could be used to continuously monitor CO2 injection and migration and complement existing technologies. Here we present a simulation of the monitoring of CO2 plume evolution in a geological reservoir using muon tomography. The stratigraphy in the vicinity of the reservoir is modelled using geological data, and a numerical fluid flow model is used to describe the time evolution of the CO2 plume. A planar detection region with a surface area of 1000 m2 is considered, at a vertical depth of 776 m below the seabed. We find that one year of constant CO2 injection leads to changes in the column density of about 1%, and that the CO2 plume is already resolvable with an exposure time of less than 50 days. The attached figure show a map of CO2 plume in angular coordinates as reconstructed from observed muons. In parallel with simulation efforts, a small prototype muon detector has been designed, built and tested in a deep subsurface laboratory. Initial calibrations of the detector have shown that it can reach the required angular resolution for muon detection. Stable operation in a small borehole within a few months has been demonstrated.

Mobility of arsenic in the sub-surface environment: An integrated hydrogeochemical study and sorption model of the sandy aquifer materials

NASA Astrophysics Data System (ADS)

Nath, Bibhash; Chakraborty, Sudipta; Burnol, André; Stüben, Doris; Chatterjee, Debashis; Charlet, Laurent

2009-01-01

SummaryGroundwater and aquifer materials have been characterized geochemically at a field site located in the Chakdaha municipality of West Bengal, India. Sorption experiments were also carried out on a sandy aquifer material to understand the mobility of arsenic (As) in the sub-surface environments. The result shows that the areas associated with high groundwater As (mean: 1.8 μM) is typically associated with low Eh (mean: -129 mV), and high Fe (mean: 0.11 mM), where Fe 2+/Fe(OH) 3 couple is controlling groundwater redox potential. Analysis of the aquifer material total concentrations showed the dominance of As (range: 8.9-22 mg kg -1), Fe (range: 3.0-9.7% as Fe 2O 3) and Mn (range: 0.05-0.18% as MnO) in the silt-/clay-rich sediments; whereas fine-/medium-sand rich sediment contains considerably lower amount of As (<8.1 mg kg -1), Fe (range: 1.6-3.9% as Fe 2O 3) and Mn (range: 0.02-0.08% as MnO). The acid extractable As do not correlate with ascorbate extractable Fe-oxyhydroxide, however Fe-oxyhydroxide is generally high in the sediments from low groundwater As areas. Chemical speciation computations indicated Fe(II), Ca(II), Mg(II) and Mn(II) to be at equilibrium (with respect to calcite, dolomite and rhodochrosite) or slightly over-saturated (with respect to siderite). These carbonate minerals may therefore participate to the As immobilization. The measured total organic carbon (˜1%) and groundwater temperature (26-32 °C) coupled with sorption studies strongly favors microbially mediated Fe(III)-oxyhydroxide reduction as the dominant mechanism for the release of As in the groundwater. Oscillations of As, Mn and Fe concentrations with depth reflected pCO 2 oscillations consecutive to microbial respiration intensity.

CO2 Driven Mineral Transformations in Fractured Reservoir

NASA Astrophysics Data System (ADS)

Schaef, T.

2015-12-01

Engineering fracture systems in low permeable formations to increase energy production, accelerate heat extraction, or to enhance injectivity for storing anthropogenic CO2, is a challenging endeavor. To complicate matters, caprocks, essential components of subsurface reservoirs, need to maintain their sealing integrity in this modified subsurface system. Supercritical CO2 (scCO2), a proposed non-aqueous based working fluid, is capable of driving mineral transformations in fracture environments. Water dissolution in scCO2 significantly impacts the reactivity of this fluid, largely due to the development of thin adsorbed H2O films on the surfaces of exposed rocks and minerals. Adsorbed H2O films are geochemically complex microenvironments that host mineral dissolution and precipitation processes that could be tailored to influence overall formation permeability. Furthermore, manipulating the composition of injected CO2 (e.g., moisture content and/or reactive gases such as O2, NOx, or SOx) could stimulate targeted mineral transformations that enhance or sustain reservoir performance. PNNL has developed specialized experimental techniques that can be used to characterize chemical reactions occurring between minerals and pressurized gases. For example, hydration of a natural shale sample (Woodford Shale) has been characterized by an in situ infrared spectroscopic technique as water partitions from the scCO2 onto the shale. Mineral dissolution and carbonate precipitation reactions were tracked by monitoring changes of Si-O and C-O stretching bands, respectively Structural changes indicated expandable clays in the shale such as montmorillonite are intercalated with scCO2, a process not observed with the non-expandable kaolinite component. Extreme scale ab initio molecular dynamics simulations were used in conjunction with model mineral systems to identify the driving force and mechanism of water films. They showed that the film nucleation and formation on minerals is driven by both enthalpic and entropic requirements. Collectively, the synergy between laboratory observations, state-of-the-art atomistic simulations and reservoir modeling has generated important insights for the design and engineering of subsurface reservoirs for CO2 storage and energy extraction.

Light-stress avoidance mechanisms in a Sphagnum-dominated wet coastal Arctic tundra ecosystem in Alaska.

PubMed

Zona, D; Oechel, Walter C; Richards, James H; Hastings, Steven; Kopetz, Irene; Ikawa, Hiroki; Oberbauer, Steven

2011-03-01

The Arctic experiences a high-radiation environment in the summer with 24-hour daylight for more than two months. Damage to plants and ecosystem metabolism can be muted by overcast conditions common in much of the Arctic. However, with climate change, extreme dry years and clearer skies could lead to the risk of increased photoxidation and photoinhibition in Arctic primary producers. Mosses, which often exceed the NPP of vascular plants in Arctic areas, are often understudied. As a result, the effect of specific environmental factors, including light, on these growth forms is poorly understood. Here, we investigated net ecosystem exchange (NEE) at the ecosystem scale, net Sphagnum CO2 exchange (NSE), and photoinhibition to better understand the impact of light on carbon exchange from a moss-dominated coastal tundra ecosystem during the summer season 2006. Sphagnum photosynthesis showed photoinhibition early in the season coupled with low ecosystem NEE. However, later in the season, Sphagnum maintained a significant CO2 uptake, probably for the development of subsurface moss layers protected from strong radiation. We suggest that the compact canopy structure of Sphagnum reduces light penetration to the subsurface layers of the moss mat and thereby protects the active photosynthetic tissues from damage. This stress avoidance mechanism allowed Sphagnum to constitute a significant percentage (up to 60%) of the ecosystem net daytime CO2 uptake at the end of the growing season despite the high levels of radiation experienced.

Geoelectrical image of the subsurface for CO2 geological storage in the Changhua site, Taiwan

NASA Astrophysics Data System (ADS)

Chiang, C. W.; Chiao, C. H.; Yang, M. W.; Yu, C. W.; Yang, C. H.; Chen, C. C.

2016-12-01

Global warming has recently become an important worldwide issue. Reduction of carbon dioxide (CO2) emission is recommended by Intergovernmental Panel on Climate Change, which geological storage is one of possible way to reduce the CO2 issue. The Taichung Power Plant is a coal-fired power plant operated by the Taiwan Power Company in Taichung, Taiwan, which is the largest coal-fired power station in the world. The power plant emits approximately 40 million tons annually which is also the world's largest CO2 emitter. Geophysical techniques are presented as the most useful tool to characterize the reservoir. The electrical resistivity tool was carried out applying audio-magnetotelluric (AMT) method, which could provide the depth resolution for evaluating the subsurface. A first survey of 20 AMT soundings was acquired to study the viability of the method to characterize the subsurface. Stations were deployed at approximately 500 m intervals and the data were recorded in the frequency range of 104-100 Hz. The dimensionality analysis proved the validity of the 1-D or 2-D assumption. The visualized model shows a layered electrical resistivity structure from shallow to depth of 3000 m. The preliminary result corresponds to seismic reflection and geological investigations that suggests a simple geological structure without complex geological processes in the area. It could be a suitable site for geological storage.

Reactive transport modeling to study changes in water chemistry induced by CO2 injection at the Frio-I Brine Pilot

USGS Publications Warehouse

Xu, T.; Kharaka, Y.K.; Doughty, C.; Freifeld, B.M.; Daley, T.M.

2010-01-01

To demonstrate the potential for geologic storage of CO2 in saline aquifers, the Frio-I Brine Pilot was conducted, during which 1600 tons of CO2 were injected into a high-permeability sandstone and the resulting subsurface plume of CO2 was monitored using a variety of hydrogeological, geophysical, and geochemical techniques. Fluid samples were obtained before CO2 injection for baseline geochemical characterization, during the CO2 injection to track its breakthrough at a nearby observation well, and after injection to investigate changes in fluid composition and potential leakage into an overlying zone. Following CO2 breakthrough at the observation well, brine samples showed sharp drops in pH, pronounced increases in HCO3- and aqueous Fe, and significant shifts in the isotopic compositions of H2O and dissolved inorganic carbon. Based on a calibrated 1-D radial flow model, reactive transport modeling was performed for the Frio-I Brine Pilot. A simple kinetic model of Fe release from the solid to aqueous phase was developed, which can reproduce the observed increases in aqueous Fe concentration. Brine samples collected after half a year had lower Fe concentrations due to carbonate precipitation, and this trend can be also captured by our modeling. The paper provides a method for estimating potential mobile Fe inventory, and its bounding concentration in the storage formation from limited observation data. Long-term simulations show that the CO2 plume gradually spreads outward due to capillary forces, and the gas saturation gradually decreases due to its dissolution and precipitation of carbonates. The gas phase is predicted to disappear after 500 years. Elevated aqueous CO2 concentrations remain for a longer time, but eventually decrease due to carbonate precipitation. For the Frio-I Brine Pilot, all injected CO2 could ultimately be sequestered as carbonate minerals. ?? 2010 Elsevier B.V.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wan, Jiamin; Tokunaga, Tetsu K.; Ashby, Paul D.

Interactions between supercritical (sc) CO 2 and minerals are important when CO 2 is injected into geologic formations for storage and as working fluids for enhanced oil recovery, hydraulic fracturing, and geothermal energy extraction. It has previously been shown that at the elevated pressures and temperatures of the deep subsurface, scCO 2 alters smectites (typical swelling phyllosilicates). However, less is known about the effects of scCO 2 on nonswelling phyllosilicates (illite and muscovite), despite the fact that the latter are the dominant clay minerals in deep subsurface shales and mudstones. Our studies conducted by using single crystals, combining reaction (incubationmore » with scCO 2 ), visualization [atomic force microscopy (AFM)], and quantifications (AFM, X-ray photoelectron spectroscopy, X-ray diffraction, and off-gassing measurements) revealed unexpectedly high CO 2 uptake that far exceeded its macroscopic surface area. Results from different methods collectively suggest that CO 2 partially entered the muscovite interlayers, although the pathways remain to be determined. We hypothesize that preferential dissolution at weaker surface defects and frayed edges allows CO 2 to enter the interlayers under elevated pressure and temperature, rather than by diffusing solely from edges deeply into interlayers. This unexpected uptake of CO 2, can increase CO 2 storage capacity by up to ~30% relative to the capacity associated with residual trapping in a 0.2-porosity sandstone reservoir containing up to 18 mass % of illite/muscovite. This excess CO 2 uptake constitutes a previously unrecognized potential trapping mechanism.« less

Enhanced CO2 electroreduction efficiency through secondary coordination effects on a pincer iridium catalyst.

PubMed

Ahn, Steven T; Bielinski, Elizabeth A; Lane, Elizabeth M; Chen, Yanqiao; Bernskoetter, Wesley H; Hazari, Nilay; Palmore, G Tayhas R

2015-04-07

An iridium(III) trihydride complex supported by a pincer ligand with a hydrogen bond donor in the secondary coordination sphere promotes the electrocatalytic reduction of CO2 to formate in water/acetonitrile with excellent Faradaic efficiency and low overpotential. Preliminary mechanistic experiments indicate formate formation is facile while product release is a kinetically difficult step.

Decadal-scale variability of diffuse CO2 emissions and seismicity revealed from long-term monitoring (1995–2013) at Mammoth Mountain, California, USA

USGS Publications Warehouse

Werner, Cynthia A.; Bergfeld, Deborah; Farrar, Chris; Doukas, Michael P.; Kelly, Peter; Kern, Christoph

2014-01-01

Mammoth Mountain, California, is a dacitic volcano that has experienced several periods of unrest since 1989. The onset of diffuse soil CO2 emissions at numerous locations on the flanks of the volcano began in 1989–1990 following an 11-month period of heightened seismicity. CO2 emission rates were measured yearly from 1995 to 2013 at Horseshoe Lake (HSL), the largest tree kill area on Mammoth Mountain, and measured intermittently at four smaller degassing areas around Mammoth from 2006 to 2013. The long-term record at HSL shows decadal-scale variations in CO2 emissions with two peaks in 2000–2001 and 2011–2012, both of which follow peaks in seismicity by 2–3 years. Between 2000 and 2004 emissions gradually declined during a seismically quiet period, and from 2004 to 2009 were steady at ~ 100 metric tonnes per day (t d− 1). CO2emissions at the four smaller tree-kill areas also increased by factors of 2–3 between 2006 and 2011–2012, demonstrating a mountain-wide increase in degassing. Delays between the peaks in seismicity and degassing have been observed at other volcanic and hydrothermal areas worldwide, and are thought to result from an injection of deep CO2-rich fluid into shallow subsurface reservoirs causing a pressurization event with a delayed transport to the surface. Such processes are consistent with previous studies at Mammoth, and here we highlight (1) the mountain-wide response, (2) the characteristic delay of 2–3 years, and (3) the roughly decadal reoccurrence interval for such behavior. Our best estimate of total CO2 degassing from Mammoth Mountain was 416 t d− 1 in 2011 during the peak of emissions, over half of which was emitted from HSL. The cumulative release of CO2 between 1995 and 2013 from diffuse emissions is estimated to be ~ 2–3 Mt, and extrapolation back to 1989 gives ~ 4.8 Mt. This amount of CO2 release is similar to that produced by the mid-sized (VEI 3) 2009 eruption of Redoubt Volcano in Alaska (~ 2.3 Mt over 11 months), and significantly lower than long-term emissions from hydrothermal areas such as Solfatara in Campi Flegrei, Italy (16 Mt over 28 years).

CO2 exsolution - challenges and opportunities in subsurface flow management

NASA Astrophysics Data System (ADS)

Zuo, Lin; Benson, Sally

2014-05-01

In geological carbon sequestration, a large amount of injected CO2 will dissolve in brine over time. Exsolution occurs when pore pressures decline and CO2 solubility in brine decreases, resulting in the formation of a separate CO2 phase. This scenario occurs in storage reservoirs by upward migration of carbonated brine, through faults, leaking boreholes or even seals, driven by a reverse pressure gradient from CO2 injection or ground water extraction. In this way, dissolved CO2 could migrate out of storage reservoirs and form a gas phase at shallower depths. This paper summarizes the results of a 4-year study regarding the implications of exsolution on storage security, including core-flood experiments, micromodel studies, and numerical simulation. Micromodel studies have shown that, different from an injected CO2 phase, where the gas remains interconnected, exsolved CO2 nucleates in various locations of a porous medium, forms disconnected bubbles and propagates by a repeated process of bubble expansion and snap-off [Zuo et al., 2013]. A good correlation between bubble size distribution and pore size distribution is observed, indicating that geometry of the pore space plays an important role in controlling the mobility of brine and exsolved CO2. Core-scale experiments demonstrate that as the exsolved gas saturation increases, the water relative permeability drops significantly and is disproportionately reduced compared to drainage relative permeability [Zuo et al., 2012]. The CO2 relative permeability remains very low, 10-5~10-3, even when the exsolved CO2 saturation increases to over 40%. Furthermore, during imbibition with CO2 saturated brines, CO2 remains trapped even under relatively high capillary numbers (uv/σ~10-6) [Zuo et al., submitted]. The water relative permeability at the imbibition endpoint is 1/3~1/2 of that with carbonated water displacing injected CO2. Based on the experimental evidence, CO2 exsolution does not appear to create significant risks for storage security. Falta et al. [2013] show that if carbonated brine migrates upwards and exsolution occurs, brine migration would be greatly reduced and limited by the presence of exsolved CO2 and the consequent low relatively permeability to brine. Similarly, if an exsolved CO2 phase were to evolve in seals, for example, after CO2 injection stops, the effect would be to reduce the permeability to brine and the CO2 would have very low mobility. This flow blocking effect is also studied with water/oil/CO2 [Zuo et al., 2013]. Experiments show that exsolved CO2 performs as a secondary residual phase in porous media that effectively blocks established water flow paths and deviates water to residual oil zones, thereby increasing recovery. Overall, our studies suggest that CO2 exsolution provides an opportunity for mobility control in subsurface processes. However, the lack of simulation capability that accounts for differences between gas injection and gas exsolution creates challenges for modeling and hence, designing studies to exploit the mobility reduction capabilities of CO2 exsolution. Using traditional drainage multiphase flow parameterization in simulations involving exsolution will lead to large errors in transport rates. Development of process dependent parameterizations of multiphase flow properties will be a key next step and will help to unlock the benefits from gas exsolution. ACKNOWLEDGEMENT This work is funded by the Global Climate and Energy Project (GCEP) at Stanford University. This work was also supported by U.S. EPA, Science To Achieve Results (STAR) Program, Grant #: 834383, 2010-2012. REFERENCES Falta, R., L. Zuo and S.M. Benson (2013). Migration of exsolved CO2 following depressurization of saturated brines. Journal of Greenhouse Gas Science and Technology, 3(6), 503-515. Zuo, L., S.C.M. Krevor, R.W. Falta, and S.M. Benson (2012). An experimental study of CO2 exsolution and relative permeability measurements during CO2 saturated water depressurization. Transp. Porous Media, 91(2), 459-478. Zuo, L., C. Zhang, R.W. Falta, and S.M. Benson (2013). Micromodel investigations of CO2 exsolution from carbonated water in sedimentary rocks. Adv. Water Res., 53, 188-197. Zuo, L., and S.M. Benson (2013). Exsolution enhanced oil recovery with concurrent CO2 sequestration. Energy Procedia, 37, 6957-6963. Zuo, L., and S.M. Benson. Different Effects of Imbibed and Exsolved Residually Trapped CO2 in Sandstone. Submitted to Geophysical Research Letters.

Syngas formation in methane flames and carbon monoxide release during quenching

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weinberg, Felix; Carleton, Fred; Houdmont, Raphael

Following a recent investigation into chemi-ionization and chemiluminescence during gradual aeration of small, laminar methane flames, we proposed that partial oxidation products, or syngas constituents, formed in the pre-flame zone well below the luminous region, were responsible for the observed effects. We therefore map temperature, CO, and H{sub 2} for geometries and conditions relevant to burners in domestic boiler systems, to assess the potential hazard of CO release into the ambient atmosphere, should any partial quenching occur. CO concentrations peaks of 5.5 volume % are recorded in the core surrounding the axis. Appreciable CO concentrations are also found in themore » absence of added air. Experiments on various burner port geometries and temperatures suggest that this is not due to air entrainment at the flame base but to diffusion from zones closer to the flame. Next, quenching surfaces such as grids, perforated plates and flame trap matrices of different metals are progressively lowered into the flame. To avoid flow line distortion, suction aspirates the quenched products. The highest emission rate occurs with the quenching plane some 4 mm above the burner; further lowering of the quenching surface causes flame extinction. The maximum CO release is close to converting 10% of the CH{sub 4} feed, with some variation with quenching material. Expressing this potential release in terms of, e.g. boiler power, predicts a potentially serious hazard. Results of numerical simulations adequately parallel the experimental sampling profiles and provide insights into local concentrations, as well as the spatially resolved CO flux, which is calculated for a parabolic inlet flow profile. Integration across the stream implies, on the basis of the simulation, a possible tripling of the experimental CO release, were quenching simply to release the local gas composition into the atmosphere. Comparison with experiment suggests some chemical interaction with the quenching surface. (author)« less

[Cobalt(III)-EDTA] - Reduction by Thermophilic Methanogen Methanothermobacter Thermautotrophicus

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singh, Rajesh; Dong, Hailiang; Liu, Deng

2015-06-30

Cobalt is a metal contaminant at high temperature radioactive waste disposal sites. In previous studies have largely focused on mesophilic microorganisms to remediate cobalt, despite the presence of thermophilic microorganisms at such sites. In this study,Methanothermobacter thermautotrophicus, a thermophilic methanogen, was used to reduce Co(III) in the form of [Co(III)–EDTA] -. Bioreduction experiments were conducted in a growth medium with H 2/CO 2 as a growth substrate at initial Co(III) concentrations of 1, 2, 4, 7, and 10 mM. At low Co(III) concentrations (< 4 mM), a complete reduction was observed within a week. Wet chemistry, X-ray absorption near-edge structuremore » (XANES) and electron paramagnetic resonance (EPR) analyses were all consistent in revealing the reduction kinetics. But, at higher concentrations (7 and 10 mM) the reduction extents only reached 69.8% and 48.5%, respectively, likely due to the toxic effect of Co(III) to the methanogen cells as evidenced by a decrease in total cellular protein at these Co(III) concentrations. Methanogenesis was inhibited by Co(III) bioreduction, possibly due to impaired cell growth and electron diversion from CO 2 to Co(III). Overall, our results demonstrated the ability of M. thermautotrophicus to reduce Co(III) to Co(II) and its potential application for remediating 60Co contaminant at high temperature subsurface radioactive waste disposal sites.« less

On the possibilty of clathrate hydrates on the Moon

NASA Technical Reports Server (NTRS)

Duxbury, N.; Nealson, K.; Romanovsky, V.

2000-01-01

One of the most important inferences of the Lunar Prospector mission data was the existence of subsurface water ice in the permanently shadowed craters near both lunar poles [Feldman et al., 1998]. We propose and substantiate an alternative explanation that hydrogen can exist in the shallow lunar subsurface in the form of clathrate hydrates: CH4 . 6H(2)o and/or CO2 . 6H(2)o.

CO2 Sparging Work Plan, LCP Chemicals

EPA Pesticide Factsheets

April 24, 2013 plan prepared by Mutch Associates, LLC for implementation of full-scale CO2 sparging of the subsurface caustic brine pool (CBP) at the LCP Chemicals site in Brunswick, Georgia. Region ID: 04 DocID: 10941341, DocDate: 04-24-2013

Metatranscriptomic Evidence of Chemolithoautotrophy in the Rifle (CO) Subsurface Relevant to C, S, N, and Fe Cycling

NASA Astrophysics Data System (ADS)

Beller, H. R.; Jewell, T. N. M.; Karaoz, U.; Thomas, B. C.; Banfield, J. F.; Brodie, E.; Williams, K. H.

2014-12-01

Although there is a limited understanding of the chemolithoautotrophic activity of aquifer microorganisms, such subsurface microbial activity could greatly influence the cycling of elements such as C, S, N, and Fe. Here, we present transcriptional (RNA-Seq) evidence of the emergence of such chemolithoautotrophic activities in groundwater filter samples from a 2-month experiment in which up to 1.5 mM nitrate (a native electron acceptor) was injected into a perennially suboxic/anoxic aquifer (Rifle, CO) containing a large reservoir of reduced Fe- and S-containing compounds. Illumina sequence data from rRNA-subtracted cDNA libraries was assembled and mapped to phylogenetically binned Rifle metagenome data. Indicative of the activity of Fe(II)-oxidizing bacteria, many high-abundance transcripts mapped to the Gallionellaceae family, whose known members are chemolithoautotrophic bacteria that catalyze Fe(II) oxidation. For example, included among the most abundant transcripts were a cold-shock protein and an acyl carrier protein with 96-98% protein sequence identity to Gallionella capsiferriformans and a nitrite reductase (nirS) gene likely belonging to a Sideroxydans relative. The apparent activity of Gallionellaceae members is consistent with 16S rRNA iTag analyses of these samples, which indicated that Gallionella-related taxa accounted for up to ~50% of these communities. Evidence of sulfide oxidation also was apparent in these samples. For example, highly expressed subunits of APS reductase were very similar to those of the obligately chemolithoautotrophic S- and Fe(II)-oxidizing Thiobacillus denitrificans in terms of sequence identity (98-99%) and synteny of the mapped scaffold. Also highly expressed were a ß-Proteobacterial Form II RubisCO gene and a hydrazine oxidoreductase gene (93% identity to the planctomycete KSU-1), the latter strongly indicative of anaerobic ammonia oxidation (anammox) activity, which has seldom been reported in aquifer environments. Such gene-level data on CO2 fixation and Fe(II), sulfide, and ammonium oxidation in the Rifle subsurface will contribute to genome-enabled modeling efforts aimed at developing a predictive understanding of biogeochemical processes at the site as part of LBNL's Sustainable Systems Scientific Focus Area (SFA) 2.0.

Incorporating Water Boiling in the Numerical Modelling of Thermal Remediation by Electrical Resistance Heating

NASA Astrophysics Data System (ADS)

Molnar, I. L.; Krol, M.; Mumford, K. G.

2017-12-01

Developing numerical models for subsurface thermal remediation techniques - such as Electrical Resistive Heating (ERH) - that include multiphase processes such as in-situ water boiling, gas production and recovery has remained a significant challenge. These subsurface gas generation and recovery processes are driven by physical phenomena such as discrete and unstable gas (bubble) flow as well as water-gas phase mass transfer rates during bubble flow. Traditional approaches to multiphase flow modeling soil remain unable to accurately describe these phenomena. However, it has been demonstrated that Macroscopic Invasion Percolation (MIP) can successfully simulate discrete and unstable gas transport1. This has lead to the development of a coupled Electro Thermal-MIP Model2 (ET-MIP) capable of simulating multiple key processes in the thermal remediation and gas recovery process including: electrical heating of soil and groundwater, water flow, geological heterogeneity, heating-induced buoyant flow, water boiling, gas bubble generation and mobilization, contaminant mass transport and removal, and additional mechanisms such as bubble collapse in cooler regions. This study presents the first rigorous validation of a coupled ET-MIP model against two-dimensional water boiling and water/NAPL co-boiling experiments3. Once validated, the model was used to explore the impact of water and co-boiling events and subsequent gas generation and mobilization on ERH's ability to 1) generate, expand and mobilize gas at boiling and NAPL co-boiling temperatures, 2) efficiently strip contaminants from soil during both boiling and co-boiling. In addition, a quantification of the energy losses arising from steam generation during subsurface water boiling was examined with respect to its impact on the efficacy of thermal remediation. While this study specifically targets ERH, the study's focus on examining the fundamental mechanisms driving thermal remediation (e.g., water boiling) renders these results applicable to a wide range of thermal and gas-based remediation techniques. 1. Mumford, K. G., et al. (2010), Adv. Water Resour. 2010, 33 (4), 504-513. 2. Krol, M. M., et al. (2011), Adv. Water Resour. 2011, 34 (4), 537-549. 3. Hegele, P. R. and Mumford, K. G. Journal of Contaminant Hydrology 2014, 165, 24-36.

Perchlorate Salts in the Martian Surface Environment - A Reexamination of the 1976 Viking Biology Results

NASA Astrophysics Data System (ADS)

Dillon, James; Quinn, R. C.

2010-01-01

The Viking Mars landers of 1976 conducted three biology experiments designed to detect the presence of microbial life in the Martian surface. The gas exchange experiment carried out by the Viking landers periodically sampled the gaseous headspace of Mars soil samples saturated with an organic/inorganic aqueous mixture, M4 nutrient. A gas chromatograph measured the change in concentrations of N2, O2, CO2, Kr, H2, and CH4 over various time intervals. The presence of metabolically active microbial life would be confirmed by the consumption or release of one of these gases. A significant release of O2 was detected after the addition of nutrient, however since the Gas Chromatograph - Mass Spectrometer experiment did not detect organics in the soil, this rapid release of O2 could not be attributed to microbial life, but rather a chemical reaction. The recent discovery of the oxidizer perchlorate in the Martian soil by the Phoenix Mars lander was investigated as the principal cause of this O2 release detected by the Viking gas exchange experiment. A variety of oxychloride salts ranging from hypochlorite to perchlorate were examined under conditions similar to the Viking experiment in order to determine if a rapid release of O2 would be detected upon addition of M4 nutrient. No oxychloride species examined decomposed with the kinetics required to support an oxychloride as the cause of the O2 response detected by the Viking experiment.

β-Na2TeO4: Phase Transition from an Orthorhombic to a Monoclinic Form. Reversible CO2 Capture.

PubMed

Galven, Cyrille; Pagnier, Thierry; Rosman, Noël; Le Berre, Françoise; Crosnier-Lopez, Marie-Pierre

2018-06-18

The present work concerns the tellurate Na 2 TeO 4 which has a 1D structure and could then present a CO 2 capture ability. It has been synthesized in a powder form via a solid-state reaction and structurally characterized by thermal X-ray diffraction experiments, Raman spectroscopy, and differential scanning calorimetry. The room temperature structure corresponds to the β-Na 2 TeO 4 orthorhombic form, and we show that it undergoes a reversible structural transition near 420 °C toward a monoclinic system. Ab initio computations were also performed on the room temperature structure, the Raman vibration modes calculated, and a normal mode attribution proposed. In agreement with our expectations, this sodium oxide is able to trap CO 2 by a two-step mechanism: Na + /H + exchange and carbonation of the released sodium as NaHCO 3 . This capture is reversible since CO 2 can be released upon heating by recombination of the mother phase.

Final Report: Molecular Mechanisms of Interfacial Reactivity in Near Surface and Extreme Geochemical Environments (DE-SC0009362)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dixon, David A

2016-03-27

The prediction of the long-term stability and safety of geologic sequestration of greenhouse gases requires a detailed understanding of subsurface transport and chemical interactions between the disposed greenhouse gases and the geologic media. In this regard, mineral-fluid interactions are of prime importance since reactions that occur on or near the interface can assist in the long term sequestration of CO2 by trapping in mineral phases such as carbonates, as well as influencing the subsurface migration of the disposed fluids via creation or plugging of pores or fractures in the host rock strata. Previous research on mineral-fluid interaction for subsurface CO2more » storage has focused almost entirely on the aqueous phase, i.e., reactivity with aqueous solutions or brines containing dissolved CO2. However, interactions with neat to water-saturated non-aqueous fluids are of equal if not greater importance since supercritical CO2 (scCO2) is less dense than the aqueous phase or oil which will create a buoyant scCO2 plume that ultimately will dominate the pore volume within the caprock, and the injected scCO2 will contain water soon after injection and this water can be highly reactive. Collectively, therefore, mineral interactions with water-saturated scCO2-dominated fluids are pivotal and could result in the stable sequestration of CO2 by trapping in mineral phases such as metal carbonates within otherwise permeable zones in the caprock. The primary objective is to unravel the molecular mechanisms governing the reactivity of mineral phases important in the geologic sequestration of CO2 with variably wet supercritical carbon dioxide as a function of T, P, and mineral structure using computational chemistry. This work is in close collaboration with the PNNL Geosciences effort. The focus of the work at The University of Alabama is computational studies of the formation of magnesium and calcium carbonates and oxides and their reactivity and providing computational support of the experimental efforts at PNNL, especially for energetics, structural properties, and interpretation of spectra.« less

Potential for iron oxides to control metal releases in CO2 sequestration scenarios

USGS Publications Warehouse

Berger, P.M.; Roy, W.R.

2011-01-01

The potential for the release of metals into groundwater following the injection of carbon dioxide (CO2) into the subsurface during carbon sequestration projects remains an open research question. Changing the chemical composition of even the relatively deep formation brines during CO2 injection and storage may be of concern because of the recognized risks associated with the limited potential for leakage of CO2-impacted brine to the surface. Geochemical modeling allows for proactive evaluation of site geochemistry before CO2 injection takes place to predict whether the release of metals from iron oxides may occur in the reservoir. Geochemical modeling can also help evaluate potential changes in shallow aquifers were CO2 leakage to occur near the surface. In this study, we created three batch-reaction models that simulate chemical changes in groundwater resulting from the introduction of CO2 at two carbon sequestration sites operated by the Midwest Geological Sequestration Consortium (MGSC). In each of these models, we input the chemical composition of groundwater samples into React??, and equilibrated them with selected mineral phases and CO 2 at reservoir pressure and temperature. The model then simulated the kinetic reactions with other mineral phases over a period of up to 100 years. For two of the simulations, the water was also at equilibrium with iron oxide surface complexes. The first model simulated a recently completed enhanced oil recovery (EOR) project in south-central Illinois in which the MGSC injected into, and then produced CO2, from a sandstone oil reservoir. The MGSC afterwards periodically measured the brine chemistry from several wells in the reservoir for approximately two years. The sandstone contains a relatively small amount of iron oxide, and the batch simulation for the injection process showed detectable changes in several aqueous species that were attributable to changes in surface complexation sites. After using the batch reaction configuration to match measured geochemical changes due to CO2 injection, we modeled potential changes in groundwater chemistry at the Illinois Basin - Decatur Project (IBDP) site in Decatur, Illinois, USA. At the IBDP, the MGSC will inject 1 million tonnes of CO2 over the course of three years at a depth of about 2 km below the surface into the Mt. Simon Formation. Sections of the Mt. Simon Formation contain up to 10 percent iron oxide, and therefore surface complexes on iron oxides should play a major role in controlling brine chemistry. The batch simulation of this system showed a significant decrease in pH after the injection of CO2 with corresponding changes in brine chemistry resulting from both mineral precipitation/dissolution reactions and changes in the chemistry on iron oxide surfaces. To ensure the safety of shallow drinking water sources, there are several shallow monitoring wells at the IBDP that the MGSC samples regularly to determine baseline chemical concentrations. Knowing what geochemical parameters are most sensitive to CO2 disturbances allows us to focus monitoring efforts. Modeling a major influx of CO2 into the shallow groundwater allowed us to determine that were an introduction of CO2 to occur, the only immediate effect will be dolomite dissolution and calcite precipitation. ?? 2011 Published by Elsevier Ltd.

Hillslope-scale experiment demonstrates role of convergence during two-step saturation

USGS Publications Warehouse

Gevaert, A. I.; Teuling, A. J.; Uijlenhoet, R.; DeLong, Stephen B.; Huxman, T. E.; Pangle, L. A.; Breshears, David D.; Chorover, J.; Pelletier, John D.; Saleska, S. R.; Zeng, X.; Troch, Peter A.

2014-01-01

Subsurface flow and storage dynamics at hillslope scale are difficult to ascertain, often in part due to a lack of sufficient high-resolution measurements and an incomplete understanding of boundary conditions, soil properties, and other environmental aspects. A continuous and extreme rainfall experiment on an artificial hillslope at Biosphere 2's Landscape Evolution Observatory (LEO) resulted in saturation excess overland flow and gully erosion in the convergent hillslope area. An array of 496 soil moisture sensors revealed a two-step saturation process. First, the downward movement of the wetting front brought soils to a relatively constant but still unsaturated moisture content. Second, soils were brought to saturated conditions from below in response to rising water tables. Convergent areas responded faster than upslope areas, due to contributions from lateral subsurface flow driven by the topography of the bottom boundary, which is comparable to impermeable bedrock in natural environments. This led to the formation of a groundwater ridge in the convergent area, triggering saturation excess runoff generation. This unique experiment demonstrates, at very high spatial and temporal resolution, the role of convergence on subsurface storage and flow dynamics. The results bring into question the representation of saturation excess overland flow in conceptual rainfall-runoff models and land-surface models, since flow is gravity-driven in many of these models and upper layers cannot become saturated from below. The results also provide a baseline to study the role of the co-evolution of ecological and hydrological processes in determining landscape water dynamics during future experiments in LEO.

Cu2+, Co2+ and Cr3+ doping of a calcium phosphate cement influences materials properties and response of human mesenchymal stromal cells.

PubMed

Schamel, Martha; Bernhardt, Anne; Quade, Mandy; Würkner, Claudia; Gbureck, Uwe; Moseke, Claus; Gelinsky, Michael; Lode, Anja

2017-04-01

The application of biologically active metal ions to stimulate cellular reactions is a promising strategy to accelerate bone defect healing. Brushite-forming calcium phosphate cements were modified with low doses of Cu 2+ , Co 2+ and Cr 3+ . The modified cements released the metal ions in vitro in concentrations which were shown to be non-toxic for cells. The release kinetics correlated with the solubility of the respective metal phosphates: 17-45 wt.-% of Co 2+ and Cu 2+ , but <1 wt.-% of Cr 3+ were released within 28days. Moreover, metal ion doping led to alterations in the exchange of calcium and phosphate ions with cell culture medium. In case of cements modified with 50mmol Cr 3+ /mol β-tricalcium phosphate (β-TCP), XRD and SEM analyses revealed a significant amount of monetite and a changed morphology of the cement matrix. Cell culture experiments with human mesenchymal stromal cells indicated that the observed cell response is not only influenced by the released metal ions but also by changed cement properties. A positive effect of modifications with 50mmol Cr 3+ or 10mmol Cu 2+ per mol β-TCP on cell behaviour was observed in indirect and direct culture. Modification with Co 2+ resulted in a clear suppression of cell proliferation and osteogenic differentiation. In conclusion, metal ion doping of the cement influences cellular activities in addition to the effect of released metal ions by changing properties of the ceramic matrix. Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of chemical environment and rock composition on fracture mechanics properties of reservoir lithologies in context of CO2 sequestration

NASA Astrophysics Data System (ADS)

Major, J. R.; Eichhubl, P.; Callahan, O. A.

2015-12-01

The coupled chemical and mechanical response of reservoir and seal rocks to injection of CO2 have major implications on the short and long term security of sequestered carbon. Many current numerical models evaluating behavior of reservoirs and seals during and after CO2 injection in the subsurface consider chemistry and mechanics separately and use only simple mechanical stability criteria while ignoring time-dependent failure parameters. CO2 injection irreversibly alters the subsurface chemical environment which can then affect geomechanical properties on a range of time scales by altering rock mineralogy and cements through dissolution, remobilization, and precipitation. It has also been documented that geomechanical parameters such as fracture toughness (KIC) and subcritical index (SCI) are sensitive to chemical environment. Double torsion fracture mechanics testing of reservoir lithologies under controlled environmental conditions relevant to CO2 sequestration show that chemical environment can measurably affect KIC and SCI. This coupled chemical-mechanical behavior is also influenced by rock composition, grains, amount and types of cement, and fabric. Fracture mechanics testing of the Aztec Sandstone, a largely silica-cemented, subarkose sandstone demonstrate it is less sensitive to chemical environment than Entrada Sandstone, a silty, clay-rich sandstone. The presence of de-ionized water lowers KIC by approximately 20% and SCI 30% in the Aztec Sandstone relative to tests performed in air, whereas the Entrada Sandstone shows reductions on the order of 70% and 90%, respectively. These results indicate that rock composition influences the chemical-mechanical response to deformation, and that the relative chemical reactivity of target reservoirs should be recognized in context of CO2 sequestration. In general, inert grains and cements such as quartz will be less sensitive to the changing subsurface environment than carbonates and clays.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Strickland, Christopher E.; Lawter, Amanda R.; Qafoku, Nikolla

Isotopes of iodine were generated during plutonium production from nine production reactors at the U.S. Department of Energy Hanford Site. The long half-life 129I generated at the Hanford Site during reactor operations was 1) stored in single-shell and double-shell tanks, 2) discharged to liquid disposal sites (e.g., cribs and trenches), 3) released to the atmosphere during fuel reprocessing operations, or 4) captured by off-gas absorbent devices (silver reactors) at chemical separations plants (PUREX, B-Plant, T-Plant, and REDOX). Releases of 129I to the subsurface have resulted in several large, though dilute, plumes in the groundwater, including the plume in the 200-UP-1more » operable unit. There is also 129I remaining in the vadose zone beneath disposal or leak locations. Because 129I is an uncommon contaminant, relevant remediation experience and scientific literature are limited.« less

Arabidopsis seed production limited by CO2 in simulated space experiments

NASA Technical Reports Server (NTRS)

Hoshizaki, T.

1984-01-01

Several generations of Arabidopsis thaliana were grown axenically from seed to seed on nutrient agar medium. The Arabidopsis plants produce seeds within 30 days after seeding, when grown either in containers open to the ambient atmosphere or in large sealed jars, but not in sealed test tubes. Moreover, the plant height was directly proportional to the size of the sealed container. Periodic analyses of the CO2 levels in the sealed containers has shown a decrease during the first week, but a tenfold increase in the following weeks. It is speculated that, by the end of the second week, the cotyledons entering the senescence stage would release ethylene into the culture atmosphere with a concomitant release of CO2, which in turn would induce further release of ethylene, hastening the senescence process in other tissues. Thus, in a controlled ecological life-support system of a space station, various components of the plant atmosphere may have to be maintained within the prescribed limits.

Development of PMMA membranes functionalized with hydroxypropyl-beta-cyclodextrins for controlled drug delivery using a supercritical CO(2)-assisted technology.

PubMed

Temtem, M; Pompeu, D; Jaraquemada, G; Cabrita, E J; Casimiro, T; Aguiar-Ricardo, A

2009-07-06

Cyclodextrin-containing polymers have proved themselves to be useful for controlled release. Herein we describe the preparation of membranes of poly(methylmethacrylate) (PMMA) containing hydroxypropyl-beta-cyclodextrins (HP-beta-CDs) using a supercritical CO(2)-assisted phase inversion method, for potential application as drug delivery devices. Results are reported on the membrane preparation, physical properties, and drug elution profile of a model drug. The polymeric membranes were obtained with HP-beta-CD contents ranging from 0 to 33.4 wt%, by changing the composition of the casting solution, and were further impregnated with ibuprofen using supercritical carbon dioxide (scCO(2)) in batch mode. The influence of the membrane functionalization in the controlled release of ibuprofen was studied by performing in vitro experiments in buffer solution pH at 7.4. The release of the anti-inflammatory drug could be tuned by varying the cyclodextrin content on the membranes.

Exploring the hydraulic fracturing parameter space: a novel high-pressure, high-throughput reactor system for investigating subsurface chemical transformations.

PubMed

Sumner, Andrew J; Plata, Desiree L

2018-02-21

Hydraulic fracturing coupled with horizontal drilling (HDHF) involves the deep-well injection of a fracturing fluid composed of diverse and numerous chemical additives designed to facilitate the release and collection of natural gas from shale plays. Analyses of flowback wastewaters have revealed organic contamination from both geogenic and anthropogenic sources. The additional detections of undisclosed halogenated chemicals suggest unintended in situ transformation of reactive additives, but the formation pathways for these are unclear in subsurface brines. To develop an efficient experimental framework for investigating the complex shale-well parameter space, we have reviewed and synthesized geospatial well data detailing temperature, pressure, pH, and halide ion values as well as industrial chemical disclosure and concentration data. Our findings showed subsurface conditions can reach pressures up to 4500 psi (310 bars) and temperatures up to 95 °C, while at least 588 unique chemicals have been disclosed by industry, including reactive oxidants and acids. Given the extreme conditions necessary to simulate the subsurface, we briefly highlighted existing geochemical reactor systems rated to the necessary pressures and temperatures, identifying throughput as a key limitation. In response, we designed and developed a custom reactor system capable of achieving 5000 psi (345 bars) and 90 °C at low cost with 15 individual reactors that are readily turned over. To demonstrate the system's throughput, we simultaneously tested 12 disclosed HDHF chemicals against a radical initiator compound in simulated subsurface conditions, ruling out a dozen potential transformation pathways in a single experiment. This review outlines the dynamic and diverse parameter range experienced by HDHF chemical additives and provides an optimized framework and novel reactor system for the methodical study of subsurface transformation pathways. Ultimately, enabling such studies will provide urgently needed clarity for water treatment downstream or releases to the environment.

Impact of intentionally injected carbon dioxide hydrate on deep-sea benthic foraminiferal survival.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bernhard, Joan M; Barry, James P; Buck, Kurt R

2009-08-01

Abstract Sequestration of carbon dioxide (CO2) in the ocean is being considered as a feasible mechanism to mitigate the alarming rate in its atmospheric rise. Little is known, however, about how the resulting hypercapnia and ocean acidification may affect marine fauna. In an effort to understand better the protistan reaction to such an environmental perturbation, the survivorship of benthic foraminifera, which is a prevalent group of protists, was studied in response to deep-sea CO2 release. The survival response of calcareous, agglutinated, and thecate foraminifera was determined in two experiments at ~3.1 and 3.3 km water depth in Monterey Bay (California,more » USA). Approximately five weeks after initial seafloor CO2 release, in situ incubations of the live-dead indicator CellTracker Green were executed within seafloor-emplaced pushcores. Experimental treatments included direct exposure to CO2 hydrate, two levels of lesser exposure adjacent to CO2 hydrate, and controls, which were far removed from the CO2 hydrate release. Results indicate that survivorship rates of agglutinated and thecate foraminifera were not significantly impacted by direct exposure but the survivorship of calcareous foraminifera was significantly lower in direct exposure treatments compared to controls. Observations suggest that, if large scale CO2 sequestration is enacted on the deep-sea floor, survival of two major groups of this prevalent protistan taxon will likely not be severely impacted, while calcareous foraminifera will face considerable challenges to maintain their benthic populations in areas directly exposed to CO2 hydrate.« less

Plastic-film mulching and urea types affect soil CO2 emissions and grain yield in spring maize on the Loess Plateau, China

NASA Astrophysics Data System (ADS)

Liu, Qiaofei; Chen, Yu; Li, Weiwei; Liu, Yang; Han, Juan; Wen, Xiaoxia; Liao, Yuncheng

2016-06-01

A 2-year field experiment was conducted on maize (Zea mays L.) to explore effective ways to decrease soil CO2 emissions and increase grain yield. Treatments established were: (1) no mulching with urea, (2) no mulching with controlled release fertiliser (CRF), (3) transparent plastic-film mulching (PMt) with urea, (4) PMt with CRF, (5) black plastic-film mulching (PMb) with urea, and (6) PMb with CRF. During the early growth stages, soil CO2 emissions were noted as PMt > PMb > no mulching, and this order was reversed in the late growth stages. This trend was the result of topsoil temperature dynamics. There were no significant correlations noted between soil CO2 emissions and soil temperature and moisture. Cumulative soil CO2 emissions were higher for the PMt than for the PMb, and grain yield was higher for the PMb treatments than for the PMt or no mulching treatments. The CRF produced higher grain yield and inhibited soil CO2 emissions. Soil CO2 emissions per unit grain yield were lower for the BC treatment than for the other treatments. In conclusion, the use of black plastic-film mulching and controlled release fertiliser not only increased maize yield, but also reduced soil CO2 emissions.

Quantifying the local influence at a tall tower site in nocturnal conditions

DOE PAGES

Werth, David; Buckley, Robert; Zhang, Gengsheng; ...

2015-10-17

The influence of the local terrestrial environment on nocturnal atmospheric CO 2 measurements at a 329-m television transmitter tower (and a component of a CO 2 monitoring network) was estimated in this paper with a tracer release experiment and a subsequent simulation of the releases. This was done to characterize the vertical transport of emissions from the surface to the uppermost tower level and how it is affected by atmospheric stability. The tracer release experiment was conducted over two nights in May of 2009 near the Department of Energy’s Savannah River Site (SRS) in South Carolina. Tracer was released onmore » two contrasting nights—slightly stable and moderately stable—from several upwind surface locations. Measurements at the 329-m level on both nights indicate that tracer was able to mix vertically within a relatively short (~24 km) distance, implying that nocturnal stable conditions do not necessarily prevent vertical dispersion in the boundary layer and that CO 2 measurements at the tower are at least partly influenced by nearby emissions. A simulation of the tracer release is used to calculate the tower footprint on the two nights to estimate the degree to which the local domain affects the tower readings. The effect of the nocturnal boundary layer on the area sampled by the tower can be seen clearly, as the footprints were affected by changes in stability. Finally, the contribution of local sources to the measurements at the tower was minimal, however, suggesting that nocturnal concentrations at upper levels are contributed mostly by regional sources.« less

Quantifying the local influence at a tall tower site in nocturnal conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Werth, David; Buckley, Robert; Zhang, Gengsheng

The influence of the local terrestrial environment on nocturnal atmospheric CO 2 measurements at a 329-m television transmitter tower (and a component of a CO 2 monitoring network) was estimated with a tracer release experiment and a subsequent simulation of the releases. This was done to characterize the vertical transport of emissions from the surface to the uppermost tower level and how it is affected by atmospheric stability. The tracer release experiment was conducted over two nights in May of 2009 near the Department of Energy’s Savannah River Site (SRS) in South Carolina. Tracer was released on two contrasting nights—slightlymore » stable and moderately stable—from several upwind surface locations. Measurements at the 329-m level on both nights indicate that tracer was able to mix vertically within a relatively short (~24 km) distance, implying that nocturnal stable conditions do not necessarily prevent vertical dispersion in the boundary layer and that CO 2 measurements at the tower are at least partly influenced by nearby emissions. A simulation of the tracer release is used to calculate the tower footprint on the two nights to estimate the degree to which the local domain affects the tower readings. The effect of the nocturnal boundary layer on the area sampled by the tower can be seen clearly, as the footprints were affected by changes in stability. The contribution of local sources to the measurements at the tower was minimal, however, suggesting that nocturnal concentrations at upper levels are contributed mostly by regional sources.« less

Quantifying the local influence at a tall tower site in nocturnal conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Werth, David; Buckley, Robert; Zhang, Gengsheng

The influence of the local terrestrial environment on nocturnal atmospheric CO 2 measurements at a 329-m television transmitter tower (and a component of a CO 2 monitoring network) was estimated in this paper with a tracer release experiment and a subsequent simulation of the releases. This was done to characterize the vertical transport of emissions from the surface to the uppermost tower level and how it is affected by atmospheric stability. The tracer release experiment was conducted over two nights in May of 2009 near the Department of Energy’s Savannah River Site (SRS) in South Carolina. Tracer was released onmore » two contrasting nights—slightly stable and moderately stable—from several upwind surface locations. Measurements at the 329-m level on both nights indicate that tracer was able to mix vertically within a relatively short (~24 km) distance, implying that nocturnal stable conditions do not necessarily prevent vertical dispersion in the boundary layer and that CO 2 measurements at the tower are at least partly influenced by nearby emissions. A simulation of the tracer release is used to calculate the tower footprint on the two nights to estimate the degree to which the local domain affects the tower readings. The effect of the nocturnal boundary layer on the area sampled by the tower can be seen clearly, as the footprints were affected by changes in stability. Finally, the contribution of local sources to the measurements at the tower was minimal, however, suggesting that nocturnal concentrations at upper levels are contributed mostly by regional sources.« less

Experimental study of CO2 dissolution a convection phenomenon at high pressure

NASA Astrophysics Data System (ADS)

Ben Salem, Imen; Chevalier, Sylvie; Faisal, Titly Farhana; Abderrahmane, Hamid; Sassi, Mohamed

2016-05-01

The density driven convection phenomenon has a significant role in enhancing the CO2 geological storage capacity. Deep saline aquifers are targeted for large scale geological sequestration. Once the CO2 is injected in saline aquifer, the supercritical CO2 rises up, forms a thin layer of free phase CO2, and the dissolution and molecular diffusion of the dissolved CO2 in brine begins. The CO2 saturated brine is denser than the original brine leading to gravitational convection of CO2 saturated brine. Convection accelerates the dissolution process and thus improves the safety and the efficiency of the sequestration. Laboratory experiments have been previously performed with experimental set-ups allowing the visualization of the phenomenon (1) eventually combined to the measurements of the dissolved CO2 mass transfer (2) as a function of the permeability of the medium. The visualization of the process was possible as Hele-Shaw cells at atmospheric pressure were used. Pressurized cylindrical vessel containing porous media allows measuring mass transfer of CO2 using the pressure decay concept (3) but visualization of the convection/dissolution was not possible for these setups. In this work, we performed experiments in a pressurized transparent cell similar to a Hele-Shaw cell but with bigger aperture. Permeability was varied by changing the size of the glass beads filling the cell. Bromocrysol green was used as a dye to track the pH change due to the presence of dissolved CO2 (1). The phenomenon is captured by a high resolution camera. We studied the effect of the pressure and of the permeability on the fingering pattern, the onset and the timescale of the phenomenon and the quantitative mass transfer of dissolved CO2. Experiments were validated on numerical simulations performed using STOMP (Subsurface Transport Over Multiple Phases) developed by the PNNL (Pacific Northwest National Laboratory) Hydrology group of the Department of Energy, USA. (1) Kneafsey, T.J., Pruess, K., 2010. Laboratory flow experiments for visualizing carbon dioxide-induced density-driven brine convection, Transport in Porous Media 82, 123-139. (2) Faisal, T. F., Chevalier, S., Bernabé, Y., Juanes, R. and M. Sassi. 2015. Quantitative and qualitative study of density driven CO2 mass transfer in a vertical Hele-Shaw cell. International Journal of Heat and Mass Transfer. Vol. 81, 901-914. (3) Farajzadeh, R.; Barati, A.; Delil, H. A.; Bruining, J.; Zitha, P. L. J., Mass transfer of CO2 into water and surfactant solutions, Petroleum Science and Technology 25 (12) (2007) 1493-1511.

Need to improve SWMM's subsurface flow routing algorithm for green infrastructure modeling

EPA Science Inventory

SWMM can simulate various subsurface flows, including groundwater (GW) release from a subcatchment to a node, percolation out of storage units and low impact development (LID) controls, and rainfall derived inflow and infiltration (RDII) at a node. Originally, the subsurface flow...

The Role of Subsurface Properties on Transport of Water and Trace Gases: 1D Simulations at Selected Mars Landing Sites.

NASA Astrophysics Data System (ADS)

Karatekin, O.; Gloesener, E.; Dehant, V. M. A.

2017-12-01

In this work, water ice stability and water vapour transport through porous martian subsurface are studied using a 1D diffusive model. The role of adsorption on water transfer in martian conditions is investigated as well as the range of parameters that have the largest effect on gas transport. In addition, adsorption kinetics is considered to examine its influence on the water vapor exchange between the subsurface and the atmosphere. As methane has been detected in the martian atmosphere, the subsurface model is then used to study methane diffusion in the CH4/CO2/H2O system from variable depths under the surface. The results of subsurface gas transport at selected locations/landing sites are shown and implications for present/future observations are discussed.

Reconciling the MOLA, TES, and Neutron Observations of the North Polar CO2 Mass Budget on Mars

NASA Technical Reports Server (NTRS)

Haberle, R. M.; Mattingly, B.; Titus, T. N.

2003-01-01

There are now three independent observations of the CO2 polar cap mass budget of Mars' north polar cap. The first is based elevation changes detected by the Mars Orbiter Laser Altimeter (MOLA) on the Mars Global Surveyor (MGS). The second is based on MGS Thermal Emission Spectrometer (TES) broadband observations of the solar and infrared radiation fields at the top of the atmosphere. The third is based on neutron counts measured by the neutron spectrometer (NS) on Odyssey. The TES data are based on an energy balance. The net radiative loss (gain) in a column is balanced by latent heating due condensation (sublimation) of CO2. In calculating the mass budget, the other main energy sources, atmospheric heat transport and subsurface conduction, were neglected. At the pole, atmospheric heat transport is indeed a small term. However, subsurface heat conduction can be significant because at the North Pole water ice, which has a high thermal conductivity compared to bare soil, is a dominant component of the subsurface. Thus, heat conducted down into the ice during summer will slowly bleed back out during fall and winter reducing the amount of CO2 that condenses on the pole. We have taken a first cut at quantifying this effect by fitting a curve to Paige's estimates of the conducted energy flux in his analysis of Viking IRTM data.

Effects of dissolved CO2 on Shallow Freshwater Microbial Communities simulating a CO2 Leakage Scenario

NASA Astrophysics Data System (ADS)

Gulliver, D. M.; Lowry, G. V.; Gregory, K.

2013-12-01

Geological carbon sequestration is likely to be part of a comprehensive strategy to minimize the atmospheric release of greenhouse gasses, establishing a concern of sequestered CO2 leakage into overlying potable aquifers. Leaking CO2 may affect existing biogeochemical processes and therefore water quality. There is a critical need to understand the evolution of CO2 exposed microbial communities that influence the biogeochemistry in these freshwater aquifers. The evolution of microbial ecology for different CO2 exposure concentrations was investigated using fluid-slurry samples obtained from a shallow freshwater aquifer (55 m depth, 0.5 MPa, 22 °C, Escatawpa, MS). The microbial community of well samples upstream and downstream of CO2 injection was characterized. In addition, batch vessel experiments were conducted with the upstream aquifer samples exposed to varying pCO2 from 0% to 100% under reservoir temperature and pressure for up to 56 days. The microbial community of the in situ experiment and the batch reactor experiment were analyzed with 16S rRNA clone libraries and qPCR. In both the in situ experiment and the batch reactor experiment, DNA concentration did not correlate with CO2 exposure. Both the in situ experiment and the batch reactors displayed a changing microbial community with increased CO2 exposure. The well water isolate, Curvibacter, appeared to be the most tolerant genus to high CO2 concentrations in the in situ experiments and to mid-CO2 concentrations in the batch reactors. In batch reactors with pCO2 concentrations higher than experienced in situ (pCO2 = 0.5 MPa), Pseudomonas appeared to be the most tolerant genus. Findings provide insight into a dynamic biogeochemical system that will alter with CO2 exposure. Adapted microbial populations will eventually give rise to the community that will impact the metal mobility and water quality. Knowledge of the surviving microbial populations will enable improved models for predicting the fate of CO2 following leakage and lead to better strategies for ensuring the quality of potable aquifer water.

Increased belowground C release during initial plant development of Populus deltoides x nigra grown under light and C reserve limited conditions

NASA Astrophysics Data System (ADS)

Studer, Mirjam S.; Siegwolf, Rolf T. W.; Schmidt, Michael W. I.; Abiven, Samuel

2014-05-01

Plants might be a key factor for the long-term stabilisation of carbon (C) in the soil, e.g. through enhanced physical protection of root-derived C against microbial decomposition in soil aggregates. On the other hand C released by the plants into the soil might promote the decomposition of native soil organic matter (SOM) through the stimulation of microbial activity. We measured the C budget of developing plant-soil systems (Populus deltoides x nigra, Cambisol soil) in the laboratory under controlled environmental conditions. In order to distinguish plant-derived from native C in the SOM and the soil CO2 efflux, we labelled the poplar shoots continuously with 13C-CO2 from first emergence of leaves (sprouting from stem cuttings). Throughout the experiment the CO2 fluxes (photosynthetic assimilation, dark respiratory loss, soil CO2 efflux) were measured frequently (every 30 min) and the 13C was traced in the soil CO2 efflux (1-2 times a week). After 10 weeks the plant-soil systems were destructively harvested and the distribution of the 13C distribution was analysed. The plants developed slowly (compared to previous experiments), most likely due to limitation in C reserves (long term cutting storage) and C supply (low light intensities). The amount of 13C recovered in the roots, microbial biomass and soil CO2 efflux was directly correlated with the leaf area of the different plant individuals. After 3-4 weeks of plant development we observed a high peak in the total soil CO2 efflux. During this time the relative belowground C release was increased massively over the basal rate of 17 % of net C assimilated, whereby the variability between the plant individuals was large. The smallest plants, i.e. the plants that were most resource limited, obtained the highest belowground C release accounting at the peak time for up to 57 % of net assimilated C. We hypothesize that the plants released specific compounds, which either directly (enzymatically) or indirectly (priming) enhanced the decomposition of native SOM as a survival mechanisms (e.g. mine for nutrients). The results of this study confirm linear correlations between aboveground plant traits (leaf area) and belowground C allocation into roots, microbial biomass and plant-derived respiration. However it also highlights that plant-soil systems are not permanently in a steady state. C allocation patterns can change massively when the plant is under stress, which affects other fluxes within the terrestrial C cycle, such as the microbial decomposition of SOM.

CO2 Sparging Proof of Concept Test Report, Revision 1, LCP Chemicals Site, Brunswick, Georgia

EPA Pesticide Factsheets

April 2013 report to evaluate the feasibility of CO2 sparging to remediate a sub-surface caustic brine pool (CBP) at the LCP Chemicals Superfund Site, GA. Region ID : 04, DocID: 10940639 , DocDate: 2013-04-01

Heterogeneous phase reactions of Martian volatiles with putative regolith minerals

NASA Technical Reports Server (NTRS)

Clark, B. C.; Kenley, S. L.; Obrien, D. L.; Huss, G. R.; Mack, R.; Baird, A. K.

1979-01-01

The chemical reactivity of several minerals thought to be present in Martian fines is tested with respect to gases known in the Martian atmosphere. In these experiments, liquid water is excluded from the system, environmental temperatures are maintained below 0 C, and the solar illumination spectrum is stimulated in the visible and UV using a xenon arc lamp. Reactions are detected by mass spectrometric analysis of the gas phase over solid samples. No reactions were detected for Mars nominal gas over sulfates, nitrates, chloride, nontronite clay, or magnetite. Oxidation was not observed for basaltic glass, nontronite, and magnetite. However, experiments incorporating SO2 gas an expected product of volcanism and intrusive volatile release - gave positive results. Displacement of CO2 by SO2 occurred in all four carbonates tested. These reactions are catalyzed by irradiation with the solar simulator. A calcium nitrate hydrate released NO2 in the presence of SO2. These results have implications for the cycling of atmospheric CO2, H2O, and N2 through the regolith.

Effects of nitrate on the stability of uranium in a bioreduced region of the subsurface.

PubMed

Wu, Wei-Min; Carley, Jack; Green, Stefan J; Luo, Jian; Kelly, Shelly D; Van Nostrand, Joy; Lowe, Kenneth; Mehlhorn, Tonia; Carroll, Sue; Boonchayanant, Benjaporn; Löfller, Frank E; Watson, David; Kemner, Kenneth M; Zhou, Jizhong; Kitanidis, Peter K; Kostka, Joel E; Jardine, Philip M; Criddle, Craig S

2010-07-01

The effects of nitrate on the stability of reduced, immobilized uranium were evaluated in field experiments at a U.S. Department of Energy site in Oak Ridge, TN. Nitrate (2.0 mM) was injected into a reduced region of the subsurface containing high levels of previously immobilized U(IV). The nitrate was reduced to nitrite, ammonium, and nitrogen gas; sulfide levels decreased; and Fe(II) levels increased then deceased. Uranium remobilization occurred concomitant with nitrite formation, suggesting nitrate-dependent, iron-accelerated oxidation of U(IV). Bromide tracer results indicated changes in subsurface flowpaths likely due to gas formation and/or precipitate. Desorption-adsorption of uranium by the iron-rich sediment impacted uranium mobilization and sequestration. After rereduction of the subsurface through ethanol additions, background groundwater containing high levels of nitrate was allowed to enter the reduced test zone. Aqueous uranium concentrations increased then decreased. Clone library analyses of sediment samples revealed the presence of denitrifying bacteria that can oxidize elemental sulfur, H(2)S, Fe(II), and U(IV) (e.g., Thiobacillus spp.), and a decrease in relative abundance of bacteria that can reduce Fe(III) and sulfate. XANES analyses of sediment samples confirmed changes in uranium oxidation state. Addition of ethanol restored reduced conditions and triggered a short-term increase in Fe(II) and aqueous uranium, likely due to reductive dissolution of Fe(III) oxides and release of sorbed U(VI). After two months of intermittent ethanol addition, sulfide levels increased, and aqueous uranium concentrations gradually decreased to <0.1 microM.

The latest on hydrothermal activity on Enceladus from Cassini and Laboratory work

NASA Astrophysics Data System (ADS)

Postberg, F.; Hsu, H. W.; Sekine, Y.; Shibuya, T.

2015-10-01

Various observations from the Cassini spacecraft [1,2,3], suggest the existence of subsurface water beneath the south polar region of Saturn's geologically active icy moon Enceladus. They provide information on the composition and physical conditions of water reservoirs occurring at shallow depth from which the plumes emerge [1,2,4], and about the dimensions of the south polar ocean beneath the ice crust at a depth of about 50km [3]. However, constraints on the physical and chemical conditions at the interface of the rocky core and the deep ocean are sparse. We report in situ measurements of tiny grains, so called stream particles, by Cassini's Cosmic Dust Analyser (CDA) in the Saturnian system. CDA data shows that these nano-particles are composed of silica that were initially embedded in larger μm-sized icy grains emitted from Enceladus subsurface waters and released by sputter erosion in Saturn's E ring. Comprehensive long- term laboratory experiments and model calculations were carried out to investigate the reaction conditions at the bottom of Enceladus' ocean.

Long-term in situ oxidation of biogenic uraninite in an alluvial aquifer: impact of dissolved oxygen and calcium.

PubMed

Lezama-Pacheco, Juan S; Cerrato, José M; Veeramani, Harish; Alessi, Daniel S; Suvorova, Elena; Bernier-Latmani, Rizlan; Giammar, Daniel E; Long, Philip E; Williams, Kenneth H; Bargar, John R

2015-06-16

Oxidative dissolution controls uranium release to (sub)oxic pore waters from biogenic uraninite produced by natural or engineered processes, such as bioremediation. Laboratory studies show that uraninite dissolution is profoundly influenced by dissolved oxygen (DO), carbonate, and solutes such as Ca(2+). In complex and heterogeneous subsurface environments, the concentrations of these solutes vary in time and space. Knowledge of dissolution processes and kinetics occurring over the long-term under such conditions is needed to predict subsurface uranium behavior and optimize the selection and performance of uraninite-based remediation technologies over multiyear periods. We have assessed dissolution of biogenic uraninite deployed in wells at the Rifle, CO, DOE research site over a 22 month period. Uraninite loss rates were highly sensitive to DO, with near-complete loss at >0.6 mg/L over this period but no measurable loss at lower DO. We conclude that uraninite can be stable over decadal time scales in aquifers under low DO conditions. U(VI) solid products were absent over a wide range of DO values, suggesting that dissolution proceeded through complexation and removal of oxidized surface uranium atoms by carbonate. Moreover, under the groundwater conditions present, Ca(2+) binds strongly to uraninite surfaces at structural uranium sites, impacting uranium fate.

A minimalistic microbial food web in an excavated deep subsurface clay rock.

PubMed

Bagnoud, Alexandre; de Bruijn, Ino; Andersson, Anders F; Diomidis, Nikitas; Leupin, Olivier X; Schwyn, Bernhard; Bernier-Latmani, Rizlan

2016-01-01

Clay rocks are being considered for radioactive waste disposal, but relatively little is known about the impact of microbes on the long-term safety of geological repositories. Thus, a more complete understanding of microbial community structure and function in these environments would provide further detail for the evaluation of the safety of geological disposal of radioactive waste in clay rocks. It would also provide a unique glimpse into a poorly studied deep subsurface microbial ecosystem. Previous studies concluded that microorganisms were present in pristine Opalinus Clay, but inactive. In this work, we describe the microbial community and assess the metabolic activities taking place within borehole water. Metagenomic sequencing and genome-binning of a porewater sample containing suspended clay particles revealed a remarkably simple heterotrophic microbial community, fueled by sedimentary organic carbon, mainly composed of two organisms: a Pseudomonas sp. fermenting bacterium growing on organic macromolecules and releasing organic acids and H2, and a sulfate-reducing Peptococcaceae able to oxidize organic molecules to CO(2). In Opalinus Clay, this microbial system likely thrives where pore space allows it. In a repository, this may occur where the clay rock has been locally damaged by excavation or in engineered backfills. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Simulating pathways of subsurface oil in the Faroe-Shetland Channel using an ocean general circulation model.

PubMed

Main, C E; Yool, A; Holliday, N P; Popova, E E; Jones, D O B; Ruhl, H A

2017-01-15

Little is known about the fate of subsurface hydrocarbon plumes from deep-sea oil well blowouts and their effects on processes and communities. As deepwater drilling expands in the Faroe-Shetland Channel (FSC), oil well blowouts are a possibility, and the unusual ocean circulation of this region presents challenges to understanding possible subsurface oil pathways in the event of a spill. Here, an ocean general circulation model was used with a particle tracking algorithm to assess temporal variability of the oil-plume distribution from a deep-sea oil well blowout in the FSC. The drift of particles was first tracked for one year following release. Then, ambient model temperatures were used to simulate temperature-mediated biodegradation, truncating the trajectories of particles accordingly. Release depth of the modeled subsurface plumes affected both their direction of transport and distance travelled from their release location, and there was considerable interannual variability in transport. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

Seasonal carbonate chemistry covariation with temperature, oxygen, and salinity in a fjord estuary: implications for the design of ocean acidification experiments.

PubMed

Reum, Jonathan C P; Alin, Simone R; Feely, Richard A; Newton, Jan; Warner, Mark; McElhany, Paul

2014-01-01

Carbonate chemistry variability is often poorly characterized in coastal regions and patterns of covariation with other biologically important variables such as temperature, oxygen concentration, and salinity are rarely evaluated. This absence of information hampers the design and interpretation of ocean acidification experiments that aim to characterize biological responses to future pCO2 levels relative to contemporary conditions. Here, we analyzed a large carbonate chemistry data set from Puget Sound, a fjord estuary on the U.S. west coast, and included measurements from three seasons (winter, summer, and fall). pCO2 exceeded the 2008-2011 mean atmospheric level (392 µatm) at all depths and seasons sampled except for the near-surface waters (< 10 m) in the summer. Further, undersaturated conditions with respect to the biogenic carbonate mineral aragonite were widespread (Ωar<1). We show that pCO2 values were relatively uniform throughout the water column and across regions in winter, enriched in subsurface waters in summer, and in the fall some values exceeded 2500 µatm in near-surface waters. Carbonate chemistry covaried to differing levels with temperature and oxygen depending primarily on season and secondarily on region. Salinity, which varied little (27 to 31), was weakly correlated with carbonate chemistry. We illustrate potential high-frequency changes in carbonate chemistry, temperature, and oxygen conditions experienced simultaneously by organisms in Puget Sound that undergo diel vertical migrations under present-day conditions. We used simple calculations to estimate future pCO2 and Ωar values experienced by diel vertical migrators based on an increase in atmospheric CO2. Given the potential for non-linear interactions between pCO2 and other abiotic variables on physiological and ecological processes, our results provide a basis for identifying control conditions in ocean acidification experiments for this region, but also highlight the wide range of carbonate chemistry conditions organisms may currently experience in this and similar coastal ecosystems.

Seasonal Carbonate Chemistry Covariation with Temperature, Oxygen, and Salinity in a Fjord Estuary: Implications for the Design of Ocean Acidification Experiments

PubMed Central

Reum, Jonathan C. P.; Alin, Simone R.; Feely, Richard A.; Newton, Jan; Warner, Mark; McElhany, Paul

2014-01-01

Carbonate chemistry variability is often poorly characterized in coastal regions and patterns of covariation with other biologically important variables such as temperature, oxygen concentration, and salinity are rarely evaluated. This absence of information hampers the design and interpretation of ocean acidification experiments that aim to characterize biological responses to future pCO2 levels relative to contemporary conditions. Here, we analyzed a large carbonate chemistry data set from Puget Sound, a fjord estuary on the U.S. west coast, and included measurements from three seasons (winter, summer, and fall). pCO2 exceeded the 2008–2011 mean atmospheric level (392 µatm) at all depths and seasons sampled except for the near-surface waters (< 10 m) in the summer. Further, undersaturated conditions with respect to the biogenic carbonate mineral aragonite were widespread (Ωar<1). We show that pCO2 values were relatively uniform throughout the water column and across regions in winter, enriched in subsurface waters in summer, and in the fall some values exceeded 2500 µatm in near-surface waters. Carbonate chemistry covaried to differing levels with temperature and oxygen depending primarily on season and secondarily on region. Salinity, which varied little (27 to 31), was weakly correlated with carbonate chemistry. We illustrate potential high-frequency changes in carbonate chemistry, temperature, and oxygen conditions experienced simultaneously by organisms in Puget Sound that undergo diel vertical migrations under present-day conditions. We used simple calculations to estimate future pCO2 and Ωar values experienced by diel vertical migrators based on an increase in atmospheric CO2. Given the potential for non-linear interactions between pCO2 and other abiotic variables on physiological and ecological processes, our results provide a basis for identifying control conditions in ocean acidification experiments for this region, but also highlight the wide range of carbonate chemistry conditions organisms may currently experience in this and similar coastal ecosystems. PMID:24586915

The Importance of pH, Oxygen, and Bitumen on the Oxidation and Precipitation of Fe(III)-(oxy)hydroxides during Hydraulic Fracturing of Oil/Gas Shales

NASA Astrophysics Data System (ADS)

Jew, A. D.; Dustin, M. K.; Harrison, A. L.; Joe-Wong, C. M.; Thomas, D.; Maher, K.; Brown, G. E.; Bargar, J.

2016-12-01

Due to the rapid growth of hydraulic fracturing in the United States, understanding the cause for the rapid production drop off of new wells over the initial months of production is paramount. One possibility for the production decrease is pore occlusion caused by the oxidation of Fe(II)-bearing phases resulting in Fe(III) precipitates. To understand the release and fate of Fe in the shale systems, we reacted synthesized fracture fluid at 80oC with shale from four different geological localities (Marcellus Fm., Barnett Fm., Eagle Ford Fm., and Green River Fm.). A variety of wet chemical and synchrotron-based techniques (XRF mapping and x-ray absorption spectroscopy) were used to understand Fe release and solid phase Fe speciation. Solution pH was found to be the greatest factor for Fe release. Carbonate-poor Barnett and Marcellus shale showed rapid Fe release into solution followed by a plateau or significant drop in Fe concentrations indicating mineral precipitation. Conversely, in high carbonate shales, Eagle Ford and Green River, no Fe was detected in solution indicating fast Fe oxidation and precipitation. For all shale samples, bulk Fe EXAFS data show that a significant amount of Fe in the shales is bound directly to organic carbon. Throughout the course of the experiments inorganic Fe(II) phases (primarily pyrite) reacted while Fe(II) bound to C showed no indication of reaction. On the micron scale, XRF mapping coupled with μ-XANES spectroscopy showed that at pH < 4.0, Fe(III) bearing phases precipitated as diffuse surface precipitates of ferrihydrite, goethite, and magnetite away from Fe(II) point sources. In near circum-neutral pH systems, Fe(III)-bearing phases (goethite and hematite) form large particles 10's of μm's in diameter near Fe(II) point sources. Idealized systems containing synthesized fracturing fluid, dissolved ferrous chloride, and bitumen showed that bitumen released during reaction with fracturing fluids is capable of oxidizing Fe(II) to Fe(III) at pH's 2.0 and 7.0. This indicates that bitumen can play a large role in Fe oxidation and speciation in the subsurface. This work shows that shale mineralogy has a significant impact on the morphology and phases of Fe(III) precipitates in the subsurface which in turn can significantly impact subsurface solution flow.

Integrated Modeling and Experiments to Characterize Coupled Thermo-hydro-geomechanical-chemical processes in Hydraulic Fracturing

NASA Astrophysics Data System (ADS)

Viswanathan, H. S.; Carey, J. W.; Karra, S.; Porter, M. L.; Rougier, E.; Kang, Q.; Makedonska, N.; Hyman, J.; Jimenez Martinez, J.; Frash, L.; Chen, L.

2015-12-01

Hydraulic fracturing phenomena involve fluid-solid interactions embedded within coupled thermo-hydro-mechanical-chemical (THMC) processes over scales from microns to tens of meters. Feedbacks between processes result in complex dynamics that must be unraveled if one is to predict and, in the case of unconventional resources, facilitate fracture propagation, fluid flow, and interfacial transport processes. The proposed work is part of a broader class of complex systems involving coupled fluid flow and fractures that are critical to subsurface energy issues, such as shale oil, geothermal, carbon sequestration, and nuclear waste disposal. We use unique LANL microfluidic and triaxial core flood experiments integrated with state-of-the-art numerical simulation to reveal the fundamental dynamics of fracture-fluid interactions to characterize the key coupled processes that impact hydrocarbon production. We are also comparing CO2-based fracturing and aqueous fluids to enhance production, greatly reduce waste water, while simultaneously sequestering CO2. We will show pore, core and reservoir scale simulations/experiments that investigate the contolling mechanisms that control hydrocarbon production.

Subsurface iron and arsenic removal for shallow tube well drinking water supply in rural Bangladesh.

PubMed

van Halem, D; Olivero, S; de Vet, W W J M; Verberk, J Q J C; Amy, G L; van Dijk, J C

2010-11-01

Subsurface iron and arsenic removal has the potential to be a cost-effective technology to provide safe drinking water in rural decentralized applications, using existing shallow tube wells. A community-scale test facility in Bangladesh was constructed for injection of aerated water (∼1 m(3)) into an anoxic aquifer with elevated iron (0.27 mmolL(-1)) and arsenic (0.27μmolL(-1)) concentrations. The injection (oxidation) and abstraction (adsorption) cycles were monitored at the test facility and simultaneously simulated in the laboratory with anoxic column experiments. Dimensionless retardation factors (R) were determined to represent the delayed arrival of iron or arsenic in the well compared to the original groundwater. At the test facility the iron removal efficacies increased after every injection-abstraction cycle, with retardation factors (R(Fe)) up to 17. These high removal efficacies could not be explained by the theory of adsorptive-catalytic oxidation, and therefore other ((a)biotic or transport) processes have contributed to the system's efficacy. This finding was confirmed in the anoxic column experiments, since the mechanism of adsorptive-catalytic oxidation dominated in the columns and iron removal efficacies did not increase with every cycle (stable at R(Fe)=∼8). R(As) did not increase after multiple cycles, it remained stable around 2, illustrating that the process which is responsible for the effective iron removal did not promote the co-removal of arsenic. The columns showed that subsurface arsenic removal was an adsorptive process and only the freshly oxidized adsorbed iron was available for the co-adsorption of arsenic. This indicates that arsenic adsorption during subsurface treatment is controlled by the amount of adsorbed iron that is oxidized, and not by the amount of removed iron. For operational purposes this is an important finding, since apparently the oxygen concentration of the injection water does not control the subsurface arsenic removal, but rather the injection volume. Additionally, no relation has been observed in this study between the amount of removed arsenic at different molar Fe:As ratios (28, 63, and 103) of the groundwater. It is proposed that the removal of arsenic was limited by the presence of other anions, such as phosphate, competing for the same adsorption sites. Copyright © 2010 Elsevier Ltd. All rights reserved.

Subsurface capture of carbon dioxide

DOEpatents

Blount, Gerald; Siddal, Alvin A.; Falta, Ronald W.

2014-07-22

A process and apparatus of separating CO.sub.2 gas from industrial off-gas source in which the CO.sub.2 containing off-gas is introduced deep within an injection well. The CO.sub.2 gases are dissolved in the, liquid within the injection well while non-CO.sub.2 gases, typically being insoluble in water or brine, are returned to the surface. Once the CO.sub.2 saturated liquid is present within the injection well, the injection well may be used for long-term geologic storage of CO.sub.2 or the CO.sub.2 saturated liquid can be returned to the surface for capturing a purified CO.sub.2 gas.

Laboratory Investigations in Support of Dioxide-Limestone Sequestration in the Ocean

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dan Golomb; Eugene Barry; David Ryan

2008-09-30

Research under this Project has proven that liquid carbon dioxide can be emulsified in water by using very fine particles as emulsion stabilizers. Hydrophilic particles stabilize a CO{sub 2}-in-H{sub 2}O (C/W) emulsion; hydrophobic particles stabilize a H{sub 2}O-in-CO{sub 2} (W/C) emulsion. The C/W emulsion consists of tiny CO{sub 2} droplets coated with hydrophilic particles dispersed in water. The W/C emulsion consists of tiny H{sub 2}O droplets coated with hydrophobic particles dispersed in liquid carbon dioxide. The coated droplets are called globules. The emulsions could be used for deep ocean sequestration of CO{sub 2}. Liquid CO{sub 2} is sparsely soluble inmore » water, and is less dense than seawater. If neat, liquid CO{sub 2} were injected in the deep ocean, it is likely that the dispersed CO{sub 2} droplets would buoy upward and flash into vapor before the droplets dissolve in seawater. The resulting vapor bubbles would re-emerge into the atmosphere. On the other hand, the emulsion is denser than seawater, hence the emulsion plume would sink toward greater depth from the injection point. For ocean sequestration a C/W emulsion appears to be most practical using limestone (CaCO{sub 3}) particles of a few to ten ?m diameter as stabilizing agents. A mix of one volume of liquid CO{sub 2} with two volumes of H{sub 2}O, plus 0.5 weight of pulverized limestone per weight of liquid CO{sub 2} forms a stable emulsion with density 1087 kg m{sup -3}. Ambient seawater at 500 m depth has a density of approximately 1026 kg m{sup -3}, so the emulsion plume would sink by gravity while entraining ambient seawater till density equilibrium is reached. Limestone is abundant world-wide, and is relatively cheap. Furthermore, upon disintegration of the emulsion the CaCO{sub 3} particles would partially buffer the carbonic acid that forms when CO{sub 2} dissolves in seawater, alleviating some of the concerns of discharging CO{sub 2} in the deep ocean. Laboratory experiments showed that the CaCO{sub 3} emulsion is slightly alkaline, not acidic. We tested the release of the CO{sub 2}-in-H{sub 2}O emulsion stabilized by pulverized limestone in the DOE National Energy Technology Laboratory High Pressure Water Tunnel Facility (HPWTF). Digital photographs showed the sinking globules in the HPWTF, confirming the concept of releasing the emulsion in the deep ocean. We modeled the release of an emulsion from the CO{sub 2} output of a 1000 MW coal-fired power plant at 500 m depth. The emulsion would typically sink several hundred meters before density equilibration with ambient seawater. The CO{sub 2} globules would rain out from the equilibrated plume toward the ocean bottom where they would disintegrate due to wave action and bottom friction. Conceptual release systems are described both for an open ocean release and a sloping seabed release of the emulsion.« less

A Reversed Photosynthesis-like Process for Light-Triggered CO2 Capture, Release, and Conversion.

PubMed

Wang, Dingguan; Liao, Shenglong; Zhang, Shiming; Wang, Yapei

2017-06-22

Materials for CO 2 capture have been extensively exploited for climate governance and gas separation. However, their regeneration is facing the problems of high energy cost and secondary CO 2 contamination. Herein, a reversed photosynthesis-like process is proposed, in which CO 2 is absorbed in darkness while being released under light illumination. The process is likely supplementary to natural photosynthesis of plants, in which, on the contrary, CO 2 is released during the night. Remarkably, the material used here is able to capture 9.6 wt.% CO 2 according to its active component. Repeatable CO 2 capture at room temperature and release under light irradiation ensures its convenient and cost-effective regeneration. Furthermore, CO 2 released from the system is successfully converted into a stable compound in tandem with specific catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison of Fracture Gradient Methods for the FutureGen 2.0 Carbon Storage Site, Ill., USA.

NASA Astrophysics Data System (ADS)

Appriou, D.; Spane, F.; Wurstner White, S.; Kelley, M. E.; Sullivan, E. C.; Bonneville, A.; Gilmore, T. J.

2014-12-01

As part of a first-of-its-kind carbon dioxide storage project, FutureGen Industrial Alliance is planning to inject 1.1 MMt/yr of supercritical CO2 over a 20-year period within a 1240 m deep saline aquifer (Mount Simon Sandstone) located in Morgan County, Illinois, USA. Numerous aspects of the design and operational activities of the CO2 storage site are dependent on the geomechanical properties of the targeted reservoir zone, as well as of the overlying confining zone and the underlying crystalline Precambrian basement. Detailed determination of the state-of-stress within the subsurface is of paramount importance in successfully designing well drilling/completion aspects, as well as assessing the risk of induced seismicity and the potential for creating and/or reopening pre-existing fractures; all of which help ensure the safe long-term storage of injected CO2. The quantitative determination of the subsurface fracture gradient is one of the key geomechanical parameters for the site injection design and operational limits (e.g., maximum safe injection pressure). A characterization well drilled in 2011 provides subsurface geomechanical characterization information for the FutureGen 2.0 site, and includes: 1) continuous elastic properties inferred from sonic/acoustic wireline logs 2) discrete depth geomechanical laboratory core measurements and 3) results obtained from hydraulic fracturing tests of selected borehole/depth-intervals. In this paper, the precise fracture gradients derived from borehole geomechanical test results are compared with semi-empirical, fracture gradient calculation/relationships based on elastic property wireline surveys and laboratory geomechanical core test results. Implications for using various fracture-gradients obtained from the different methods are assessed using PNNL's subsurface multiphase flow and transport simulator STOMP-CO2. The implications for operational activities at the site (based on using different fracture gradients) are also discussed.

Effect of subalpine canopy removal on snowpack, soil solution, and nutrient export, Fraser Experimental Forest, CO

USGS Publications Warehouse

Stottlemyer, R.; Troendle, C.A.

1999-01-01

Research on the effects of vegetation manipulation on snowpack, soil water, and streamwater chemistry and flux has been underway at the Fraser Experimental Forest (FEF), CO, since 1982. Greater than 95% of FEF snowmelt passes through watersheds as subsurface flow where soil processes significantly alter meltwater chemistry. To better understand the mechanisms accounting for annual variation in watershed streamwater ion concentration and flux with snowmelt, we studied subsurface water flow, its ion concentration, and flux in conterminous forested and clear cut plots. Repetitive patterns in subsurface flow and chemistry were apparent. Control plot subsurface flow chemistry had the highest ion concentrations in late winter and fall. When shallow subsurface flow occurred, its Ca2+, SO42-, and HCO3- concentrations were lower and K+ higher than deep flow. The percentage of Ca2+, NO3-, SO42-, and HCO3- flux in shallow depths was less and K+ slightly greater than the percentage of total flow. Canopy removal increased precipitation reaching the forest floor by about 40%, increased peak snowpack water equivalent (SWE) > 35%, increased the average snowpack Ca2+, NO3-, and NH4+ content, reduced the snowpack K+ content, and increased the runoff four-fold. Clear cutting doubled the percentage of subsurface flow at shallow depths, and increased K+ concentration in shallow subsurface flow and NO3- concentrations in both shallow and deep flow. The percentage change in total Ca2+, SO42-, and HCO3- flux in shallow depths was less than the change in water flux, while that of K+ and NO3- flux was greater. Relative to the control, in the clear cut the percentage of total Ca2+ flux at shallow depths increased from 5 to 12%, SO42- 5.4 to 12%, HCO3- from 5.6 to 8.7%, K+ from 6 to 35%, and NO3- from 2.7 to 17%. The increases in Ca2+ and SO42- flux were proportional to the increase in water flux, the flux of HCO3- increased proportionally less than water flux, and NO3- and K+ were proportionally greater than water flux. Increased subsurface flow accounted for most of the increase in non-limiting nutrient loss. For limiting nutrients, loss of plant uptake and increased shallow subsurface flow accounted for the greater loss. Seasonal ion concentration patterns in streamwater and subsurface flow were similar.Research on the effects of vegetation manipulation on snowpack, soil water, and streamwater chemistry and flux has been underway at the Fraser Experimental Forest (FEF), CO, since 1982. Greater than 95% of FEF snowmelt passes through watersheds as subsurface flow where soil processes significantly alter meltwater chemistry. To better understand the mechanisms accounting for annual variation in watershed streamwater ion concentration and flux with snowmelt, we studied subsurface water flow, its ion concentration, and flux in conterminous forested and clear cut plots. Repetitive patterns in subsurface flow and chemistry were apparent. Control plot subsurface flow chemistry had the highest ion concentrations in late winter and fall. When shallow subsurface flow occurred, its Ca2+, SO42-, and HCO3- concentrations were lower and K+ higher than deep flow. The percentage of Ca2+, NO3-, SO42-, and HCO3- flux in shallow depths was less and K+ slightly greater than the percentage of total flow. Canopy removal increased precipitation reaching the forest floor by about 40%, increased peak snowpack water equivalent (SWE) > 35%, increased the average snowpack Ca2+, NO3-, and NH4+ content, reduced the snowpack K+ content, and increased the runoff four-fold. Clear cutting doubled the percentage of subsurface flow at shallow depths, and increased K+ concentration in shallow subsurface flow and NO3- concentrations in both shallow and deep flow. The percentage change in total Ca2+, SO42-, and HCO3- flux in shallow depths was less than the change in water flux, while that of K+ and NO3- flux was greater. Relative to the control, in the clear cut the percentage of total Ca

Diffusivity of Carbon Dioxide in Aqueous Solutions under Geologic Carbon Sequestration Conditions.

PubMed

Perera, Pradeep N; Deng, Hang; Schuck, P James; Gilbert, Benjamin

2018-04-26

Accurate assessment of the long-term security of geologic carbon sequestration requires knowledge of the mobility of carbon dioxide in brines under pressure and temperature conditions that prevail in subsurface aquifers. Here, we report Raman spectroscopic measurements of the rate of CO 2 diffusion in water and brines as a function of pressure, salinity, and concentration of CO 2 . In pure water at 50 ± 2 °C and 90 ± 2 bar, we find the diffusion coefficient, D, to be (3.08 ± 0.03) × 10 -9 m 2 /s, a value that is consistent with a recent microfluidic study but lower than earlier PVT measurements. Under reservoir conditions, salinity affects the mobility of CO 2 significantly and D decreased by 45% for a 4 M solution of NaCl. We find significant differences of diffusivity of CO 2 in brines (0-4 M NaCl), in both the absolute values and the trend compared to the Stokes-Einstein prediction under our experimental conditions. We observe that D decreases significantly at the high CO 2 concentrations expected in subsurface aquifers (∼15% reduction at 0.55 mol/kg of CO 2 ) and provides an empirical correction to the commonly reported D values that assume a tracer concentration dependence on diffusivity.

Mofettes - Investigation of Natural CO2 Springs - Insights and Methods applied

NASA Astrophysics Data System (ADS)

Lübben, A.; Leven, C.

2014-12-01

The quantification of carbon dioxide concentrations and fluxes leaking from the subsurface into the atmosphere is highly relevant in several research fields such as climate change, CCS, volcanic activity, or earthquake monitoring. Many of the areas with elevated carbon dioxide degassing pose the problem that under the given situation a systematic investigation of the relevant processes is only possible to a limited extent (e.g. in terms of spatial extent, accessibility, hazardous conditions). The upper Neckar valley in Southwest Germany is a region of enhanced natural subsurface CO2 concentrations and mass fluxes of Tertiary volcanic origin. At the beginning of the twentieth century several companies started industrial mining of CO2. The decreasing productivity of the CO2 springs led to the complete shutdown of the industry in 1995 and the existing boreholes were sealed. However, there are evidences that the reservoir, located in the deposits of the Lower Triassic, started to refill during the last 20 years. The CO2 springs replenished and a variety of different phenomena (e.g. mofettes and perished flora and fauna) indicate the active process of large scale CO2 exhalation. This easy-to-access site serves as a perfect example for a natural analog to a leaky CCS site, including abandoned boreholes and a suitable porous rock reservoir in the subsurface. During extensive field campaigns we applied several monitoring techniques like measurements of soil gas concentrations, mass fluxes, electrical resistivity, as well as soil and atmospheric parameters. The aim was to investigate and quantify mass fluxes and the effect of variations in e.g. temperature, soil moisture on the mass flux intensity. Furthermore, we investigated the effect of the vicinity to a mofette on soil parameters like electrical conductivity and soil CO2 concentrations. In times of a changing climate due to greenhouse gases, regions featuring natural CO2 springs demand to be intensively investigated. Our results serve as a contribution to the development of site-specific monitoring networks at CCS sites, as well as a step forward to unravel the share of natural CO2 springs in the global carbon cycle.

Up-Scaling Geochemical Reaction Rates for Carbon Dioxide (CO2) in Deep Saline Aquifers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peters, Catherine A

2013-02-28

Geochemical reactions in deep subsurface environments are complicated by the consolidated nature and mineralogical complexity of sedimentary rocks. Understanding the kinetics of these reactions is critical to our ability to make long-term predictions about subsurface processes such as pH buffering, alteration in rock structure, permeability changes, and formation of secondary precipitates. In this project, we used a combination of experiments and numerical simulation to bridge the gap between our knowledge of these reactions at the lab scale and rates that are meaningful for modeling reactive transport at core scales. The focus is on acid-driven mineral dissolution, which is specifically relevantmore » in the context of CO2-water-rock interactions in geological sequestration of carbon dioxide. The project led to major findings in three areas. First, we modeled reactive transport in pore-network systems to investigate scaling effects in geochemical reaction rates. We found significant scaling effects when CO2 concentrations are high and reaction rates are fast. These findings indicate that the increased acidity associated with geological sequestration can generate conditions for which proper scaling tools are yet to be developed. Second, we used mathematical modeling to investigate the extent to which SO2, if co-injected with CO2, would acidify formation brines. We found that there exist realistic conditions in which the impact on brine acidity will be limited due to diffusion rate-limited SO2 dissolution from the CO2 phase, and the subsequent pH shift may also be limited by the lack of availability of oxidants to produce sulfuric acid. Third, for three Viking sandstones (Alberta sedimentary basin, Canada), we employed backscattered electron microscopy and energy dispersive X-ray spectroscopy to statistically characterize mineral contact with pore space. We determined that for reactive minerals in sedimentary consolidated rocks, abundance alone is not a good predictor of mineral accessible surface area, and should not be used in reactive transport modeling. Our work showed that reaction rates would be overestimated by three to five times.« less

Study on O2-supplying characteristics of Azolla in Controlled Ecological Life Support System

NASA Astrophysics Data System (ADS)

Chen, Min; Deng, Sufang; Yang, Youquang; Huang, Yibing; Liu, Zhongzhu

Azolla has high growth and propagation rate, strong photosynthetic O2-releasing ability and rich nutrient value. It is able to be used as salad-type vegetable, and can also be cultured on wet bed in multi-layer condition. Hence, it possesses a potential functioning as providing O2, fresh vegetable and absorbing CO2 for Controlled Ecological Life Support System in space. In this study, we try to make clear the O2-providing characteristics of Azolla in controlled close chamber under manned condition in order to lay a foundation for Azolla as a biological component in the next ground simulated experiment and space application. A closed test cham-ber of Controlled Ecological Life Support System and Azolla wet-culturing devices were built to measure the changes of atmospheric O2-CO2 concentration inside chamber under "Azolla-fish -men" coexisting condition. The results showed that, the amount of O2 consumption is 80.49 83.07 ml/h per kilogram fish, the amount of CO2 emissions is 70.49 73.56 ml/(kg • h); O2 consumption of trial volunteers is 19.71 L/h, the volume of respiration release CO2 18.90 L/h .Artificial light intensity of Azolla wet culture under 70009000 Lx, people respiration and Azolla photosynthesis complemented each other, the atmospheric O2-CO2 concentration inside chamber maintained equilibration. Elevated atmospheric CO2 concentrations in close chamber have obvious effects on enhancing Azolla net photosynthesis efficiency. This shows that Azolla has strong photosynthetic O2-releasing ability, which equilibrates the O2-CO2 concentration inside chamber in favor of human survival, and then verifies the prospect of Azolla in space application.

U.S. Geological Survey Geologic Carbon Sequestration Assessment

NASA Astrophysics Data System (ADS)

Warwick, P. D.; Blondes, M. S.; Brennan, S.; Corum, M.; Merrill, M. D.

2012-12-01

The Energy Independence and Security Act of 2007 authorized the U.S. Geological Survey (USGS) to conduct a national assessment of potential geological storage resources for carbon dioxide (CO2) in consultation with the U.S. Department of Energy (DOE), the U.S. Environmental Protection Agency (EPA) and State geological surveys. To conduct the assessment, the USGS developed a probability-based assessment methodology that was extensively reviewed by experts from industry, government and university organizations (Brennan et al., 2010, http://pubs.usgs.gov/of/2010/1127). The methodology is intended to be used at regional to sub-basinal scales and it identifies storage assessment units (SAUs) that are based on two depth categories below the surface (1) 3,000 to 13,000 ft (914 to 3,962 m), and (2) 13,000 ft (3,962 m) and greater. In the first category, the 3,000 ft (914 m) minimum depth of the storage reservoir ensures that CO2 is in a supercritical state to minimize the storage volume. The depth of 13,000 ft (3,962 m) represents maximum depths that are accessible with average injection pressures. The second category represents areas where a reservoir formation has potential storage at depths below 13,000 ft (3,962 m), although they are not accessible with average injection pressures; these are assessed as a separate SAU. SAUs are restricted to formation intervals that contain saline waters (total dissolved solids greater than 10,000 parts per million) to prevent contamination of protected ground water. Carbon dioxide sequestration capacity is estimated for buoyant and residual storage traps within the basins. For buoyant traps, CO2 is held in place in porous formations by top and lateral seals. For residual traps, CO2 is contained in porous formations as individual droplets held within pores by capillary forces. Preliminary geologic models have been developed to estimate CO2 storage capacity in approximately 40 major sedimentary basins within the United States. More than 200 SAUs have been identified within these basins. The results of the assessment are estimates of the technically accessible storage resources based on present-day geological and engineering technology related to CO2 injection into geologic formations; therefore the assessment is not of total in-place resources. Summary geologic descriptions of the evaluated basins and SAUs will be prepared, along with the national assessment results. During the coming year, these results will be released as USGS publications available from http://energy.usgs.gov. In support of these assessment activities, CO2 sequestration related research science is being conducted by members of the project. Results of our research will contribute to current and future CO2 storage assessments conducted by the USGS and other organizations. Research topics include: (a) geochemistry of CO2 interactions with subsurface environments; (b) subsurface petrophysical rock properties in relation to CO2 injection; (c) enhanced oil recovery and the potential for CO2 storage; (d) storage of CO2 in unconventional reservoirs (coal, shale, and basalt); (e) statistical aggregation of assessment results; and (f) potential risks of induced seismicity.

Subsurface watering resulted in reduced soil N2O and CO2 emissions and their global warming potentials than surface watering

NASA Astrophysics Data System (ADS)

Wei, Qi; Xu, Junzeng; Yang, Shihong; Liao, Linxian; Jin, Guangqiu; Li, Yawei; Hameed, Fazli

2018-01-01

Water management is an important practice with significant effect on greenhouse gases (GHG) emission from soils. Nitrous oxide (N2O) and carbon dioxide (CO2) emissions and their global warming potentials (GWPs) from subsurface watering soil (SUW) were investigated, with surface watering (SW) as a control. Results indicated that the N2O and CO2 emissions from SUW soils were somewhat different to those from SW soil, with the peak N2O and CO2 fluxes from SUW soil reduced by 28.9% and 19.4%, and appeared 72 h and 168 h later compared with SW. The fluxes of N2O and CO2 from SUW soils were lower than those from SW soil in both pulse and post-pulse periods, and the reduction was significantly (p<0.05) in pulse period. Compare to SW, the cumulative N2O and CO2 emissions and its integrative GWPs from SUW soil decreased by 21.0% (p<0.05), 15.9% and 18.0%, respectively. The contributions of N2O to GWPs were lower than those of CO2 during most of time, except in pulse emission periods, and the proportion of N2O from SUW soil was 1.4% (p>0.1) lower that from SW soil. Moreover, N2O and CO2 fluxes from both watering treatments increased exponentially with increase of soil water-filled pore space (WFPS) and temperature. Our results suggest that watering soil from subsurface could significantly reduce the integrative greenhouse effect caused by N2O and CO2 and is a promising strategy for soil greenhouse gases (GHGs) mitigation. And the pulse period, contributed most to the reduction in emissions of N2O and CO2 from soils between SW and SUW, should be a key period for mitigating GHGs emissions. Response of N2O and CO2 emissions to soil WFPS and temperature illustrated that moisture was the dominant parameters that triggering GHG pulse emissions (especially for N2O), and temperature had a greater effect on the soil microorganism activity than moisture in drier soil. Avoiding moisture and temperature are appropriate for GHG emission at the same time is essential for GHGs mitigation, because peak N2O and CO2 emission were observed only when moisture and temperature are both appropriate.

A hybrid geothermal energy conversion technology: Auxiliary heating of geothermally preheated water or CO2 - a potential solution for low-temperature resources

NASA Astrophysics Data System (ADS)

Saar, Martin; Garapati, Nagasree; Adams, Benjamin; Randolph, Jimmy; Kuehn, Thomas

2016-04-01

Safe, sustainable, and economic development of deep geothermal resources, particularly in less favourable regions, often requires employment of unconventional geothermal energy extraction and utilization methods. Often "unconventional geothermal methods" is synonymously and solely used as meaning enhanced geothermal systems, where the permeability of hot, dry rock with naturally low permeability at greater depths (4-6 km), is enhanced. Here we present an alternative unconventional geothermal energy utilization approach that uses low-temperature regions that are shallower, thereby drastically reducing drilling costs. While not a pure geothermal energy system, this hybrid approach may enable utilization of geothermal energy in many regions worldwide that can otherwise not be used for geothermal electricity generation, thereby increasing the global geothermal resource base. Moreover, in some realizations of this hybrid approach that generate carbon dioxide (CO2), the technology may be combined with carbon dioxide capture and storage (CCS) and CO2-based geothermal energy utilization, resulting in a high-efficiency (hybrid) geothermal power plant with a negative carbon footprint. Typically, low- to moderate-temperature geothermal resources are more effectively used for direct heat energy applications. However, due to high thermal losses during transport, direct use requires that the heat resource is located near the user. Alternatively, we show here that if such a low-temperature geothermal resource is combined with an additional or secondary energy resource, the power production is increased compared to the sum from two separate (geothermal and secondary fuel) power plants (DiPippo et al. 1978) and the thermal losses are minimized because the thermal energy is utilized where it is produced. Since Adams et al. (2015) found that using CO2 as a subsurface working fluid produces more net power than brine at low- to moderate-temperature geothermal resource conditions, we compare over a range of parameters the net power and efficiencies of hybrid geothermal power plants that use brine or CO2 as the subsurface working fluid, that are then heated further with a secondary energy source that is unspecified here. Parameters varied include the subsurface working fluid (brine vs. CO2), geothermal reservoir depth (2.5-4.5 km), and turbine inlet temperature (200-600°C) after auxiliary heating. The hybrid power plant is numerically modeled using an iterative coupling approach of TOUGH2-ECO2N/ECO2H (Pruess, 2004) for simulation of the subsurface reservoir and Engineering Equation Solver for well bore fluid flow and surface power plant performance. We find that hybrid power plants that are CO2-based (subsurface) systems produce more net power than the sum of the power produced by individual power plants at low turbine inlet temperatures and brine based systems produce more power at high turbine inlet temperatures. Specifically, our results indicate that geothermal hybrid plants that are CO2-based are more efficient than brine-based systems when the contribution of the geothermal resource energy is higher than 48%.

An evaluation of the residual toxicity and chemistry of a sodium hydroxide-based ballast water treatment system for freshwater ships.

PubMed

Elskus, Adria A; Ingersoll, Christopher G; Kemble, Nile E; Echols, Kathy R; Brumbaugh, William G; Henquinet, Jeffrey W; Watten, Barnaby J

2015-06-01

Nonnative organisms in the ballast water of freshwater ships must be killed to prevent the spread of invasive species. The ideal ballast water treatment system (BWTS) would kill 100% of ballast water organisms with minimal residual toxicity to organisms in receiving waters. In the present study, the residual toxicity and chemistry of a BWTS was evaluated. Sodium hydroxide was added to elevate pH to >11.5 to kill ballast water organisms, then reduced to pH <9 by sparging with wet-scrubbed diesel exhaust (the source of CO2 ). Cladocerans (Ceriodaphnia dubia), amphipods (Hyalella azteca), and fathead minnows (Pimephales promelas) were exposed for 2 d to BWTS water under an air atmosphere (pH drifted to ≥9) or a 2.5% CO2 atmosphere (pH 7.5-8.2), then transferred to control water for 5 d to assess potential delayed toxicity. Chemical concentrations in the BWTS water met vessel discharge guidelines with the exception of concentrations of copper. There was little to no residual toxicity to cladocerans or fish, but the BWTS water was toxic to amphipods. Maintaining a neutral pH and diluting BWTS water by 50% eliminated toxicity to the amphipods. The toxicity of BWTS water would likely be minimal because of rapid dilution in the receiving water, with subsurface release likely preventing pH rise. This BWTS has the potential to become a viable method for treating ballast water released into freshwater systems. © 2015 SETAC.

FY12 ARRA-NRAP Report – Studies to Support Risk Assessment of Geologic Carbon Sequestration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cantrell, Kirk J.; Shao, Hongbo; Thompson, C. J.

2011-09-27

This report summarizes results of research conducted during FY2012 to support the assessment of environmental risks associated with geologic carbon dioxide (CO2) sequestration and storage. Several research focus areas are ongoing as part of this project. This includes the quantification of the leachability of metals and organic compounds from representative CO2 storage reservoir and caprock materials, the fate of metals and organic compounds after release, and the development of a method to measure pH in situ under supercritical CO2 (scCO2) conditions. Metal leachability experiments were completed on 6 different rock samples in brine in equilibrium with scCO2 at representative geologicmore » reservoir conditions. In general, the leaching of RCRA metals and other metals of concern was found to be limited and not likely to be a significant issue (at least, for the rocks tested). Metals leaching experiments were also completed on 1 rock sample with scCO2 containing oxygen at concentrations of 0, 1, 5, and 10% to simulate injection of CO2 originating from the oxy-fuel combustion process. Significant differences in the leaching behavior of certain metals were observed when oxygen is present in the CO2. These differences resulted from oxidation of sulfides, release of sulfate, ferric iron and other metals, and subsequent precipitation of iron oxides and some sulfates such as barite. Experiments to evaluate the potential for mobilization of organic compounds from representative reservoir materials and cap rock and their fate in porous media (quartz sand) have been conducted. Results with Fruitland coal and Gothic shale indicate that lighter organic compounds were more susceptible to mobilization by scCO2 compared to heavier compounds. Alkanes demonstrated very low extractability by scCO2. No significant differences were observed between the extractability of organic compounds by dry or water saturated scCO2. Reaction equilibrium appears to have been reached by 96 hours. When the scCO2 was released from the reactor, less than 60% of the injected lighter compounds (benzene, toluene) were transported through dry sand column by the CO2, while more than 90% of the heavier organics were trapped in the sand column. For wet sand columns, most (80% to 100%) of the organic compounds injected into the sand column passed through, except for naphthalene which was substantial removed from the CO2 within the column. A spectrophotometric method was developed to measure pH in brines in contact with scCO2. This method provides an alternative to fragile glass pH electrodes and thermodynamic modeling approaches for estimating pH. The method was tested in simulated reservoir fluids (CO2–NaCl–H2O) at different temperatures, pressures, and ionic strength, and the results were compared with other experimental studies and geochemical models. Measured pH values were generally in agreement with the models, but inconsistencies were present between some of the models.« less

Nitrogen fertilization raises CO2 efflux from inorganic carbon: A global assessment.

PubMed

Zamanian, Kazem; Zarebanadkouki, Mohsen; Kuzyakov, Yakov

2018-07-01

Nitrogen (N) fertilization is an indispensable agricultural practice worldwide, serving the survival of half of the global population. Nitrogen transformation (e.g., nitrification) in soil as well as plant N uptake releases protons and increases soil acidification. Neutralizing this acidity in carbonate-containing soils (7.49 × 10 9  ha; ca. 54% of the global land surface area) leads to a CO 2 release corresponding to 0.21 kg C per kg of applied N. We here for the first time raise this problem of acidification of carbonate-containing soils and assess the global CO 2 release from pedogenic and geogenic carbonates in the upper 1 m soil depth. Based on a global N-fertilization map and the distribution of soils containing CaCO 3 , we calculated the CO 2 amount released annually from the acidification of such soils to be 7.48 × 10 12  g C/year. This level of continuous CO 2 release will remain constant at least until soils are fertilized by N. Moreover, we estimated that about 273 × 10 12  g CO 2 -C are released annually in the same process of CaCO 3 neutralization but involving liming of acid soils. These two CO 2 sources correspond to 3% of global CO 2 emissions by fossil fuel combustion or 30% of CO 2 by land-use changes. Importantly, the duration of CO 2 release after land-use changes usually lasts only 1-3 decades before a new C equilibrium is reached in soil. In contrast, the CO 2 released by CaCO 3 acidification cannot reach equilibrium, as long as N fertilizer is applied until it becomes completely neutralized. As the CaCO 3 amounts in soils, if present, are nearly unlimited, their complete dissolution and CO 2 release will take centuries or even millennia. This emphasizes the necessity of preventing soil acidification in N-fertilized soils as an effective strategy to inhibit millennia of CO 2 efflux to the atmosphere. Hence, N fertilization should be strictly calculated based on plant-demand, and overfertilization should be avoided not only because N is a source of local and regional eutrophication, but also because of the continuous CO 2 release by global acidification. © 2018 John Wiley & Sons Ltd.

Equilibrium and Kinetic Models for Colloid Release Under Transient Solution Chemistry Conditions

NASA Astrophysics Data System (ADS)

Bradford, S. A.; Torkzaban, S.; Leij, F. J.; Simunek, J.

2014-12-01

Colloid retention and release is well known to depend on a wide variety of physical, chemical, and microbiological factors that may vary temporally in the subsurface environment. We present equilibrium, kinetic, combined equilibrium and kinetic, and two-site kinetic models of colloid release during transient physicochemical conditions. Our mathematical modeling approach relates colloid release under transient conditions to changes in the fraction of the solid surface area that contributes to retention. The developed models were subsequently applied to experimental colloid release datasets to investigate the influence of variations in ionic strength (IS), pH, cation exchange, colloid size, and water velocity on release. Various combinations of equilibrium and/or kinetic release models were needed to describe the experimental data depending on the transient conditions and colloid type. Release of E. coli D21g was promoted by a decrease in solution IS and an increase in pH, similar to expected trends for a reduction in the secondary minimum and nanoscale chemical heterogeneity, respectively. The retention and release of 20 nm carboxyl modified latex nanoparticles (NPs) were demonstrated to be more sensitive to the presence of Ca2+ than D21g. Specifically, retention of NPs was greater than D21g in the presence of 2 mM CaCl2 solution, and release of NPs only occurred after exchange of Ca2+ by Na+ and then a reduction in the solution IS. These findings highlight the limitations of conventional interaction energy calculations to describe colloid retention and release, and point to the need to consider Born repulsion and nanoscale heterogeneity. Temporal changes in the water velocity did not have a large influence on the release of D21g. This insensitivity was likely due to factors that reduce the applied hydrodynamic torque and/or increase the resisting adhesive torque. Collectively, experimental and modeling results indicate that episodic colloid transport in the subsurface is expected because of transient conditions.

Hydrogen peroxide release and acid-base status in exhaled breath condensate at rest and after maximal exercise in young, healthy subjects.

PubMed

Marek, E; Platen, P; Volke, J; Mückenhoff, K; Marek, W

2009-12-07

Exhaled breath condensate (EBC) contains among a large number of mediators hydrogen peroxide (H2O2) as a marker of airway inflammation and oxidative stress. Similarly EBC pH also changes in respiratory diseases. It was the aim of our investigation to prove if hydrogen peroxide release and changes in pH of EBC changes with exercise. EBC was collected from 100 litres exhaled air along with samples of arterialized blood of 16 healthy subjects (9 males, 7 females, age 23 +/- 1 years). EBC hydrogen peroxide was analyzed with EcoCheck amperometer (FILT, Berlin). The rate of H(2)O(2) release was calculated from the concentration and collection time. pH and PCO(2) in blood and in EBC were measured with the Radiometer blood gas analyzer, EBC was equilibrated with a gas mixture (5% CO(2) in O(2)). The bicarbonate concentration was calculated according to the law of mass action for CO(2) and HCO(3)(-) (pK = 6.1). H(2)O(2) concentration in EBC was 190 +/- 109 nmol/l, and H (2)O(2) release at rest was 31.0 +/- 18.3 pmol/min. At maximal exercise, the H(2)O(2) concentration in EBC increased to 250 +/- 120 nmol/l, and H(2)O(2) release significantly increased at maximal exercise to 84.4 +/- 39.9 pmol/min (P<0.01). At rest pH of the CO(2) equilibrated EBC was at 6.08 +/- 0.23 and the [HCO(3)(-)] was 1.03 +/- 0.40 mmol/l. At maximum exercise, pH 6.18 +/- 0.17 and [HCO(3)(-)] 1.23 +/- 0.30 mmol/l remained almost unaltered. The rate of H(2)O(2) release in EBC increased during exhausting exercise (external load: 300 Watt) by a factor of 2, whereas the pH and the bicarbonate concentration of the EBC, equilibrated with 5% CO(2) at 37 degrees C were not significantly altered. It has to be proven by further experiments whether there is a linear relationship between the rates of H(2)O(2) release in EBC in graded submaximal exercise.

Subsurface Growth of CoSi2 by Deposition of Co on Si-Capped CoSi2 Seed Regions

NASA Technical Reports Server (NTRS)

Fathauer, R. W.; George, T.; Pike, W. T.

1991-01-01

At a growth temperature of 800 C, Co deposited on Si(111) diffuses through a Si cap and exhibits oriented growth on buried CoSi2 grains, a process referred to as endotaxy. This occurs preferentially to surface nucleation of CoSi2 provided the thickness of the Si cap is less than a critical value between 100 and 200 nm for a deposition rate of 0.01 nm/s. Steady-state endotaxy is modeled under the assumption that the process is controlled by Co diffusion.

Negative CO2 emissions via subsurface mineral carbonation in fractured peridotite

NASA Astrophysics Data System (ADS)

Kelemen, P. B.; Matter, J.

2014-12-01

Uptake of CO2 from surface water via mineral carbonation in peridotite can be engineered to achieve negative CO2 emissions. Reaction with peridotite, e.g., CO2 + olivine (A), serpentine (B) and brucite (C), forms inert, non-toxic, solid carbonates such as magnesite. Experimental studies show that A can be 80% complete in a few hours with 30 micron powders and elevated P(CO2) [1,2,3]. B is slower, but in natural systems the rate of B+C is significant [4]. Methods for capture of dilute CO2 via mineral carbonation [4,5,6,7] are not well known, though CO2 storage via mineral carbonation has been discussed for decades [8,9]. Where crushed peridotite is available, as in mine tailings, increased air or water flow could enhance CO2 uptake at a reasonable cost [4,5]. Here we focus on enhancing subsurface CO2 uptake from surface water flowing in fractured peridotite, in systems driven by thermal convection such as geothermal power plants. Return of depleted water to the surface would draw down CO2 from the air [6,7]. CO2 uptake from water, rate limited by flow in input and output wells, could exceed 1000 tons CO2/yr [7]. If well costs minus power sales were 0.1M to 1M and each system lasts 10 years this costs < 10 to 100 per ton CO2. As for other CCS methods, upscaling requires infrastructure resembling the oil industry. Uptake of 1 Gt CO2/yr at 1000 t/well/yr requires 1M wells, comparable to the number of producing oil and gas wells in the USA. Subsurface CO2 uptake could first be applied in coastal, sub-seafloor peridotite with onshore drilling. Sub-seafloor peridotite is extensive off Oman, New Caledonia and Papua New Guinea, with smaller amounts off Spain, Morocco, USA, etc. This would be a regional contribution, used in parallel with other methods elsewhere. To achieve larger scale is conceivable. There is a giant mass of seafloor peridotite along slow-spreading mid-ocean ridges. Could robotic drills enhance CO2 uptake at a reasonable cost, while fabric chimneys transport CO2-depleted water to the sea surface? Does anyone know James Cameron's phone number? [1] O'Connor et al DOE Report 04 [2] Chizmeshya et al DOE Report 07 [3] Gadikota et al Phys Chem Chem Phys 14 [4] Wilson et al IJGHGC 14 [5] Schuiling & Krijgsman Climate Change 06 [6] Kelemen & Matter PNAS 08 [7] Kelemen et al AREPS 11 [8] Seifritz Nature 90 [9] Lackner et al Energy 95

Hydrogeochemical alteration of groundwater due to a CO2 injection test into a shallow aquifer in Northeast Germany

NASA Astrophysics Data System (ADS)

Dethlefsen, Frank; Peter, Anita; Hornbruch, Götz; Lamert, Hendrik; Garbe-Schönberg, Dieter; Beyer, Matthias; Dietrich, Peter; Dahmke, Andreas

2014-05-01

The accidental release of CO2 into potable aquifers, for instance as a consequence of a leakage out of a CO2 store site, can endanger drinking water resources due to the induced geochemical processes. A 10-day CO2 injection experiment into a shallow aquifer was carried out in Wittstock (Northeast Germany) in order to investigate the geochemical impact of a CO2 influx into such an aquifer and to test different monitoring methods. Information regarding the site investigation, the injection procedure monitoring setup, and first geochemical monitoring results are described in [1]. Apart from the utilization of the test results to evaluate monitoring approaches [2], further findings are presented on the evaluation of the geophysical monitoring [3], and the monitoring of stable carbon isotopes [4]. This part of the study focuses of the hydrogeochemical alteration of groundwater due to the CO2 injection test. As a consequence of the CO2 injection, major cations were released, i.e. concentrations increased, whereas major anion concentrations - beside bicarbonate - decreased, probably due to increased anion sorption capacity at variably charged exchange sites of minerals. Trace element concentrations increased as well significantly, whereas the relative concentration increase was far larger than the relative concentration increase of major cations. Furthermore, geochemical reactions show significant spatial heterogeneity, i.e. some elements such as Cr, Cu, Pb either increased in concentration or remained at stable concentrations with increasing TIC at different wells. Statistical analyses of regression coefficients confirm the different spatial reaction patterns at different wells. Concentration time series at single wells give evidence, that the trace element release is pH dependent, i.e. trace elements such as Zn, Ni, Co are released at pH of around 6.2-6.6, whereas other trace elements like As, Cd, Cu are released at pH of 5.6-6.4. [1] Peter, A., et al., Investigation of the geochemical impact of CO2; on shallow groundwater: design and implementation of a CO2; injection test in Northeast Germany. Environmental Earth Sciences, 2012. 67(2): p. 335-349. [2] Dethlefsen, F., et al., Monitoring approaches for detecting and evaluating CO2 and formation water leakages into near-surface aquifers. Energy Procedia, 2013. 37(0): p. 4886-4893. [3] Lamert, H., et al., Feasibility of geoelectrical monitoring and multiphase modeling for process understanding of gaseous CO2; injection into a shallow aquifer. Environmental Earth Sciences, 2012. 67(2): p. 447-462. [4] Schulz, A., et al., Monitoring of a simulated CO2 leakage in a shallow aquifer using stable carbon isotopes. Environmental Science & Technology, 2012. 46(20): p. 11243-11250.

Growth and Survivability of Microorganisms at Martian Temperatures and Pressures

NASA Astrophysics Data System (ADS)

Mickol, Rebecca Lynne

The discovery of methane in the martian atmosphere via numerous ground- and space-based sources has prompted the study of methanogens as models for life on Mars. Methanogens are microorganisms within the domain Archaea, many of which utilize carbon dioxide (CO2) and hydrogen to produce methane. The non-photosynthetic nature of methanogens indicates that they could exist in sub-surface environments, protected from harmful UV and ionizing radiation on the surface of Mars. These organisms also do not require organics, which are sparse on the planet. Additionally, the wide variety of environments we find life in on Earth, as well as evidence for liquid brines on the surface of Mars, suggest that habitable environments may still exist on the planet. However, there are a variety of conditions that any extant life on Mars would need to endure, including wide variations in temperature over one sol, a low-pressure atmosphere, and a limited availability of liquid water, among others. This dissertation encompasses various experiments that examined the ability of four species of methanogens (Methanosarcina barkeri, Methanobacterium formicicum, Methanococcus maripaludis, and Methanothermobacter wolfeii) to survive and/or grow under 1) low-pressure conditions and 2) freeze/thaw cycles. Low pressure studies include both survival and active growth experiments conducted between 7 mbar (the average surface pressure on Mars) and 143 mbar. Freeze/thaw experiments utilized short- and long-term cycles varying in temperature between the organisms' growth temperatures (22 °C, M. maripaludis; 37 °C, M. barkeri and M. formicicum; 55 °C, M. wolfeii ) and -80 °C, encompassing Mars-relevant temperature changes. As a comparison to methanogen growth and survivability, additional experiments were conducted using a non-spore-forming bacterium, Serratia liquefaciens , previously shown capable of growth at 7 mbar, 0 °C and within an anoxic CO2 atmosphere. The experiments described here assessed the survivability of S. liquefaciens exposed to martian UV irradiation within liquid brines and ices. The experiments discussed here demonstrate the ability of Earth microorganisms to withstand certain extreme conditions on Mars and suggest that the planet may contain relatively habitable microenvironments within the near subsurface.

Monitoring the bio-stimulation of hydrocarbon-contaminated soils by measurements of soil electrical properties, and CO2 content and its 13C/12C isotopic signature

NASA Astrophysics Data System (ADS)

Noel, C.; Gourry, J.; Ignatiadis, I.; Colombano, S.; Dictor, M.; Guimbaud, C.; Chartier, M.; Dumestre, A.; Dehez, S.; Naudet, V.

2013-12-01

Hydrocarbon contaminated soils represent an environmental issue as it impacts on ecosystems and aquifers. Where significant subsurface heterogeneity exists, conventional intrusive investigations and groundwater sampling can be insufficient to obtain a robust monitoring of hydrocarbon contaminants, as the information they provide is restricted to vertical profiles at discrete locations, with no information between sampling points. In order to obtain wider information in space volume on subsurface modifications, complementary methods can be used like geophysics. Among geophysical methods, geoelectrical techniques such as electrical resistivity (ER) and induced polarization (IP) seem the more promising, especially to study the effects of biodegradation processes. Laboratory and field geoelectrical experiments to characterize soils contaminated by oil products have shown that mature hydrocarbon-contaminated soils are characterized by enhanced electrical conductivity although hydrocarbons are electrically resistive. This high bulk conductivity is due to bacterial impacts on geological media, resulting in changes in the chemical and physical properties and thus, to the geophysical properties of the ground. Moreover, microbial activity induced CO2 production and isotopic deviation of carbon. Indeed, produced CO2 will reflect the pollutant isotopic signature. Thus, the ratio δ13C(CO2) will come closer to δ13C(hydrocarbon). BIOPHY, project supported by the French National Research Agency (ANR), proposes to use electrical methods and gas analyses to develop an operational and non-destructive method for monitoring in situ biodegradation of hydrocarbons in order to optimize soil treatment. Demonstration field is located in the South of Paris (France), where liquid fuels (gasoline and diesel) leaked from some tanks in 1997. In order to stimulate biodegradation, a trench has been dug to supply oxygen to the water table and thus stimulate aerobic metabolic bioprocesses. ER and IP surveys are performed regularly to monitor the stimulated biodegradation and progress of remediation until soil cleanup. Microbial activity is characterized by CO2 production increase and δ13C isotopic deviation, in the produced CO2 measured by infrared laser spectroscopy, and by an evolution of electrical conductivity and IP responses in correlation with microbiological and chemical analyses.

Production of reactive oxygen species from abraded silicates. Implications for the reactivity of the Martian soil

NASA Astrophysics Data System (ADS)

Bak, Ebbe N.; Zafirov, Kaloyan; Merrison, Jonathan P.; Jensen, Svend J. Knak; Nørnberg, Per; Gunnlaugsson, Haraldur P.; Finster, Kai

2017-09-01

The results of the Labeled Release and the Gas Exchange experiments conducted on Mars by the Viking Landers show that compounds in the Martian soil can cause oxidation of organics and a release of oxygen in the presence of water. Several sources have been proposed for the oxidizing compounds, but none has been validated in situ and the cause of the observed oxidation has not been resolved. In this study, laboratory simulations of saltation were conducted to examine if and under which conditions wind abrasion of silicates, a process that is common on the Martian surface, can give rise to oxidants in the form of hydrogen peroxide (H2O2) and hydroxyl radicals (ṡOH). We found that silicate samples abraded in simulated Martian atmospheres gave rise to a significant production of H2O2 and ṡOH upon contact with water. Our experiments demonstrated that abraded silicates could lead to a production of H2O2 facilitated by atmospheric O2 and inhibited by carbon dioxide. Furthermore, during simulated saltation the silicate particles became triboelectrically charged and at pressures similar to the Martian surface pressure we observed glow discharges. Electrical discharges can cause dissociation of CO2 and through subsequent reactions lead to a production of H2O2. These results indicate that the reactions linked to electrical discharges are the dominant source of H2O2 during saltation of silicates in a simulated Martian atmosphere, given the low pressure and the relatively high concentration of CO2. Our experiments provide evidence that wind driven abrasion could enhance the reactivity of the Martian soil and thereby could have contributed to the oxidation of organic compounds and the O2 release observed in the Labeled Release and the Gas Exchange experiments. Furthermore, the release of H2O2 and ṡOH from abraded silicates could have a negative effect on the persistence of organic compounds in the Martian soil and the habitability of the Martian surface.

Field demonstration of CO2 leakage detection in potable aquifers with a pulselike CO2-release test.

PubMed

Yang, Changbing; Hovorka, Susan D; Delgado-Alonso, Jesus; Mickler, Patrick J; Treviño, Ramón H; Phillips, Straun

2014-12-02

This study presents two field pulselike CO2-release tests to demonstrate CO2 leakage detection in a shallow aquifer by monitoring groundwater pH, alkalinity, and dissolved inorganic carbon (DIC) using the periodic groundwater sampling method and a fiber-optic CO2 sensor for real-time in situ monitoring of dissolved CO2 in groundwater. Measurements of groundwater pH, alkalinity, DIC, and dissolved CO2 clearly deviated from their background values, showing responses to CO2 leakage. Dissolved CO2 observed in the tests was highly sensitive in comparison to groundwater pH, DIC, and alkalinity. Comparison of the pulselike CO2-release tests to other field tests suggests that pulselike CO2-release tests can provide reliable assessment of geochemical parameters indicative of CO2 leakage. Measurements by the fiber-optic CO2 sensor, showing obvious leakage signals, demonstrated the potential of real-time in situ monitoring of dissolved CO2 for leakage detection at a geologic carbon sequestration (GCS) site. Results of a two-dimensional reactive transport model reproduced the geochemical measurements and confirmed that the decrease in groundwater pH and the increases in DIC and dissolved CO2 observed in the pulselike CO2-release tests were caused by dissolution of CO2 whereas alkalinity was likely affected by carbonate dissolution.

Electrochemical capture and release of carbon dioxide

DOE PAGES

Rheinhardt, Joseph H.; Singh, Poonam; Tarakeshwar, Pilarisetty; ...

2017-01-18

Understanding the chemistry of carbon dioxide is key to affecting changes in atmospheric concentrations. One area of intense interest is CO 2 capture in chemically reversible cycles relevant to carbon capture technologies. Most CO 2 capture methods involve thermal cycles in which a nucleophilic agent captures CO 2 from impure gas streams (e.g., flue gas), followed by a thermal process in which pure CO 2 is released. Several reviews have detailed progress in these approaches. A less explored strategy uses electrochemical cycles to capture CO 2 and release it in pure form. These cycles typically rely on electrochemical generation ofmore » nucleophiles that attack CO 2 at the electrophilic carbon atom, forming a CO 2 adduct. Then, CO 2 is released in pure form via a subsequent electrochemical step. In this Perspective, we describe electrochemical cycles for CO 2 capture and release, emphasizing electrogenerated nucleophiles. As a result, we also discuss some advantages and disadvantages inherent in this general approach.« less

Modern water/rock reactions in Oman hyperalkaline peridotite aquifers and implications for microbial habitability

NASA Astrophysics Data System (ADS)

Miller, Hannah M.; Matter, Jürg M.; Kelemen, Peter; Ellison, Eric T.; Conrad, Mark E.; Fierer, Noah; Ruchala, Tyler; Tominaga, Masako; Templeton, Alexis S.

2016-04-01

The Samail ophiolite in Oman is undergoing modern hydration and carbonation of peridotite and may host a deep subsurface biosphere. Previous investigations of hyperalkaline fluids in Oman have focused on fluids released at surface seeps, which quickly lose their reducing character and precipitate carbonates upon contact with the O2/CO2-rich atmosphere. In this work, geochemical analysis of rocks and fluids from the subsurface provides new insights into the operative reactions in serpentinizing aquifers. Serpentinite rock and hyperalkaline fluids (pH > 10), which exhibit millimolar concentrations of Ca2+, H2 and CH4, as well as variable sulfate and nitrate, were accessed from wells situated in mantle peridotite near Ibra and studied to investigate their aqueous geochemistry, gas concentrations, isotopic signatures, mineralogy, Fe speciation and microbial community composition. The bulk mineralogy of drill cuttings is dominated by olivine, pyroxene, brucite, serpentine and magnetite. At depth, Fe-bearing brucite is commonly intermixed with serpentine, whereas near the surface, olivine and brucite are lost and increased magnetite and serpentine is detected. Micro-Raman spectroscopy reveals at least two distinct generations of serpentine present in drill cuttings recovered from several depths from two wells. Fe K-edge X-ray absorption near-edge spectroscopy (XANES) analysis of the lizardite shows a strong tetrahedral Fe coordination, suggesting a mixture of both Fe(II) and Fe(III) in the serpentine. Magnetite veins are also closely associated with this second generation serpentine, and 2-10 μm magnetite grains overprint all minerals in the drill cuttings. Thus we propose that the dissolved H2 that accumulates in the subsurface hyperalkaline fluids was evolved through low temperature oxidation and hydration of relict olivine, as well as destabilization of pre-existing brucite present in the partially serpentinized dunites and harzburgites. In particular, we hypothesize that Fe-bearing brucite is currently reacting with dissolved silica in the aquifer fluids to generate late-stage magnetite, additional serpentine and dissolved H2. Dissolved CH4 in the fluids exhibits the most isotopically heavy carbon in CH4 reported in the literature thus far. The CH4 may have formed through abiotic reduction of dissolved CO2 or through biogenic pathways under extreme carbon limitation. The methane isotopic composition may have also been modified by significant methane oxidation. 16S rRNA sequencing of DNA recovered from filtered hyperalkaline well fluids reveals an abundance of Meiothermus, Thermodesulfovibrionaceae (sulfate-reducers) and Clostridia (fermenters). The fluids also contain candidate phyla OP1 and OD1, as well as Methanobacterium (methanogen) and Methylococcus sp. (methanotroph). The composition of these microbial communities suggests that low-temperature hydrogen and methane generation, coupled with the presence of electron acceptors such as nitrate and sulfate, sustains subsurface microbial life within the Oman ophiolite.

Proof-of-concept study on the suitability of 13C-urea as a marker substance for assessment of in vivo behaviour of oral colon-targeted dosage forms

PubMed Central

Schellekens, RCA; Olsder, GG; Langenberg, SMCH; Boer, T; Woerdenbag, HJ; Frijlink, HW; Kosterink, JGW; Stellaard, F

2009-01-01

Background and purpose: 13C-urea may be a suitable marker to assess the in vivo fate of colon-targeted dosage forms given by mouth. We postulated that release in the colon (urease-rich segment) of 13C-urea from colon-targeted capsules would lead to fermentation of 13C-urea by bacterial ureases into 13CO2. Subsequent absorption into the blood and circulation would lead to detectable 13C (as 13CO2) in breath. If, however, release of 13C-urea occurred in the small intestine (urease-poor segment), we expected detectable 13C (as 13C-urea) in blood but no breath 13C (as 13CO2). The differential kinetics of 13C-urea could thus potentially describe both release kinetics and indicate the gastrointestinal segment of release. Experimental approach: The in vivo study consisted of three experiments, during which the same group of four volunteers participated. Key results: The kinetic model was internally valid. The appearance of 13C-in breath CO2 (Ffermented) and the appearance of 13C in blood as 13C-urea (Fnot fermented) show a high inverse correlation (Pearson's r=−0.981, P= 0.06). The total recovery of 13C (Ffermented+Fnot fermented) averaged 99%, indicating complete recovery of the administered 13C via breath and blood. 13CO2 exhalation was observed in all subjects. This indicates that 13C-urea was available in urease-rich segments, such as the caecum or colon. Conclusions and implications: In this proof-of-concept study, 13C-urea was able to provide information on both the release kinetics of a colon-targeted oral dosage form and the gastrointestinal segment where it was released. PMID:19732063

Enhanced U(VI) release from autunite mineral by aerobic Arthrobacter sp. in the presence of aqueous bicarbonate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Katsenovich, Yelena P.; Carvajal, Denny A.; Wellman, Dawn M.

2012-05-01

The bacterial effect on U(VI) release from the autunite mineral (Ca[(UO2)(PO4)]2•3H2O) was investigated to provide a more comprehensive understanding of the important microbiological processes affecting autunite stability within subsurface bicarbonate-bearing environments. Experiments were performed in a culture of the Arthrobacter oxydans G975 strain, herein referred to as G975, a soil bacterium previously isolated from Hanford Site soil. 91 mg of autunite powder and 50 mL of phosphorous-limiting sterile media were amended with bicarbonate (ranging between 1 and 10 mM) in glass reactor bottles and inoculated with the G975 strain after the dissolution of autunite was at steady state. SEM observationsmore » indicated that G975 formed a biofilm on the autunite surface and penetrated the mineral cleavages. The mineral surface colonization by bacteria tended to increase concomitantly with bicarbonate concentrations. Additionally, a sterile culture-ware with inserts was used in non-contact dissolution experiments where autunite and bacteria cells were kept separately. The data suggest that G975 bacteria is able to enhance the release of U(VI) from autunite without direct contact with the mineral. In the presence of bicarbonate, the damage to bacterial cells caused by U(VI) toxicity was reduced, yielding similar values for total organic carbon (TOC) degradation and cell density compared to U(VI)-free controls. The presence of active bacterial cells greatly enhanced the release of U(VI) from autunite in bicarbonate-amended media.« less

Relationship between soil cobalt and vitamin B12 levels in the liver of livestock in Saudi Arabia: role of competing elements in soils.

PubMed

Huwait, Etimad A; Kumosani, Taha A; Moselhy, Said S; Mosaoa, Rami M; Yaghmoor, Soonham S

2015-09-01

This study aimed to analyze the agricultural soils from different regions in Saudi Arabia for cobalt and related metals as Cu(2+), Ni(2+), Cr(3+), Zn(2+) and Pb(2+). Liver and muscle tissues of livestock grazing on the selected areas were analyzed for the content of Co and vitamin B12. Our results indicated that the levels of Co in surface soil (0-15 cm) were higher than in sub-surface soil (>15 cm-45 cm). In contrast, Pb and Zn were higher in sub-surface soil than in surface soil. A significant positive correlation existed between the levels of Co and vitamin B12 in the liver of livestock. However, Co was not detected in muscle tissues while vitamin B12 was present at very low levels in comparison with the levels found in the liver. The results indicated that Zn(2+), Pb(2+) compete with Co in soil, which eventually affected the levels of vitamin B12 in liver. It was recommended that survey of heavy metals in grazing fields of cattle should consider inclusion of multiple elements that compete with the bioavailability of essential elements in plants and animals for the prevention of deficiency of essential elements such as Co.

Shock-induced CO2 loss from CaCO3: Implications for early planetary atmospheres

NASA Technical Reports Server (NTRS)

Lange, M. A.; Ahrens, T. J.

1984-01-01

Recovered samples from shock recovery experiments on single crystal calcite were subjected to thermogravimetric analysis to determine the amount of post-shock CO2, the decarbonization interval and the activation energy, for the removal of remaining CO2 in shock-loaded calcite. Comparison of post-shock CO2 with that initially present determines shock-induced CO2 loss as a function of shock pressure. Incipient to complete CO2 loss occurs over a pressure range of approximately 10 to approximately 70 GPa. Optical and scanning electron microscopy reveal structural changes, which are related to the shock-loading. The occurrence of dark, diffuse areas, which can be resolved as highly vesicular areas as observed with a scanning electron microscope are interpreted as representing quenched partial melts, into which shock-released CO2 was injected. The experimental results are used to constrain models of shock-produced, primary CO2 atmospheres on the accreting terrestrial planets.

Modeling of Single and Dual Reservoir Porous Media Compressed Gas (Air and CO2) Storage Systems

NASA Astrophysics Data System (ADS)

Oldenburg, C. M.; Liu, H.; Borgia, A.; Pan, L.

2017-12-01

Intermittent renewable energy sources are causing increasing demand for energy storage. The deep subsurface offers promising opportunities for energy storage because it can safely contain high-pressure gases. Porous media compressed air energy storage (PM-CAES) is one approach, although the only facilities in operation are in caverns (C-CAES) rather than porous media. Just like in C-CAES, PM-CAES operates generally by injecting working gas (air) through well(s) into the reservoir compressing the cushion gas (existing air in the reservoir). During energy recovery, high-pressure air from the reservoir is mixed with fuel in a combustion turbine to produce electricity, thereby reducing compression costs. Unlike in C-CAES, the storage of energy in PM-CAES occurs variably across pressure gradients in the formation, while the solid grains of the matrix can release/store heat. Because air is the working gas, PM-CAES has fairly low thermal efficiency and low energy storage density. To improve the energy storage density, we have conceived and modeled a closed-loop two-reservoir compressed CO2 energy storage system. One reservoir is the low-pressure reservoir, and the other is the high-pressure reservoir. CO2 is cycled back and forth between reservoirs depending on whether energy needs to be stored or recovered. We have carried out thermodynamic and parametric analyses of the performance of an idealized two-reservoir CO2 energy storage system under supercritical and transcritical conditions for CO2 using a steady-state model. Results show that the transcritical compressed CO2 energy storage system has higher round-trip efficiency and exergy efficiency, and larger energy storage density than the supercritical compressed CO2 energy storage. However, the configuration of supercritical compressed CO2 energy storage is simpler, and the energy storage densities of the two systems are both higher than that of PM-CAES, which is advantageous in terms of storage volume for a given power rating.

Low pCO2 under sea-ice melt in the Canada Basin of the western Arctic Ocean

NASA Astrophysics Data System (ADS)

Kosugi, Naohiro; Sasano, Daisuke; Ishii, Masao; Nishino, Shigeto; Uchida, Hiroshi; Yoshikawa-Inoue, Hisayuki

2017-12-01

In September 2013, we observed an expanse of surface water with low CO2 partial pressure (pCO2sea) (< 200 µatm) in the Chukchi Sea of the western Arctic Ocean. The large undersaturation of CO2 in this region was the result of massive primary production after the sea-ice retreat in June and July. In the surface of the Canada Basin, salinity was low (< 27) and pCO2sea was closer to the air-sea CO2 equilibrium (˜ 360 µatm). From the relationships between salinity and total alkalinity, we confirmed that the low salinity in the Canada Basin was due to the larger fraction of meltwater input (˜ 0.16) rather than the riverine discharge (˜ 0.1). Such an increase in pCO2sea was not so clear in the coastal region near Point Barrow, where the fraction of riverine discharge was larger than that of sea-ice melt. We also identified low pCO2sea (< 250 µatm) in the depth of 30-50 m under the halocline of the Canada Basin. This subsurface low pCO2sea was attributed to the advection of Pacific-origin water, in which dissolved inorganic carbon is relatively low, through the Chukchi Sea where net primary production is high. Oxygen supersaturation (> 20 µmol kg-1) in the subsurface low pCO2sea layer in the Canada Basin indicated significant net primary production undersea and/or in preformed condition. If these low pCO2sea layers surface by wind mixing, they will act as additional CO2 sinks; however, this is unlikely because intensification of stratification by sea-ice melt inhibits mixing across the halocline.

The Effects of Varying Crustal Carbonate Composition on Assimilation and CO2 Degassing at Arc Volcanoes

NASA Astrophysics Data System (ADS)

Carter, L. B.; Holmes, A. K.; Dasgupta, R.; Tumiati, S.

2015-12-01

Magma-crustal carbonate interaction and subsequent decarbonation can provide an additional source of CO2 release to the exogenic system superimposed on mantle-derived CO2. Carbonate assimilation at present day volcanoes is often modeled by limestone consumption experiments [1-4]. Eruptive products, however, do not clearly display the characteristic ultracalcic melt compositions produced during limestone-magma interaction [4]. Yet estimated CO2outflux [5] and composition of volcanics in many volcanic systems may allow ~3-17% limestone- or dolostone-assimilated melt contribution. Crystallization may retain ultracalcic melts in pyroxenite cumulates. To extend our completed study on limestone assimilation, here we explore the effect of varying composition from calcite to dolomite on chemical and thermal decarbonation efficiency of crustal carbonates. Piston cylinder experiments at 0.5 GPa and 900-1200 °C demonstrate that residual mineralogy during interaction with magma shifts from CaTs cpx and anorthite/scapolite in the presence of calcite to Di cpx and Fo-rich olivine with dolomite. Silica-undersaturated melts double in magnesium content, while maintaining high (>30 wt.%) CaO values. At high-T, partial thermal breakdown of dolomite into periclase and CO2 is minimal (<5%) suggesting that in the presence of magma, CO2 is primarily released due to assimilation. Assimilated melts at identical P-T conditions depict similarly high volatile contents (10-20 wt.% by EMPA deficit at 0.5 GPa, 1150 °C with hydrous basalt) with calcite or dolomite. Analysis of the coexisting fluid phase indicates the majority of water is dissolved in the melt, while CO2 released from the carbonate is preferentially partitioned into the vapor. This suggests that although assimilated melts have a higher CO2 solubility, most of the CO2can easily degas from the vapor phase at arc volcanoes, possibly more so at volcanic plumbing systems traversing dolomite [8]. [1]Conte et al 2009 EuJMin (21) 763-782; [2]Iacono-Marziano et al 2008 CMP (155) 719-738; [3]Mollo et al 2010 Lithos (114) 503-514; [4]Carter and Dasgupta 2015 EPSL (427) 202-214; [5]Burton et al 2013 RevMinGeochem (75) 323-254; [6]Balassone et al 2013 Lithos (160-161) 84-97; [7]Di Rocco et al. 2012 JPet (53) 2307-2332; [8]Del Moro et al 2001 JVGR (112) 15-24.

Cultivating the Deep Subsurface Microbiome

NASA Astrophysics Data System (ADS)

Casar, C. P.; Osburn, M. R.; Flynn, T. M.; Masterson, A.; Kruger, B.

2017-12-01

Subterranean ecosystems are poorly understood because many microbes detected in metagenomic surveys are only distantly related to characterized isolates. Cultivating microorganisms from the deep subsurface is challenging due to its inaccessibility and potential for contamination. The Deep Mine Microbial Observatory (DeMMO) in Lead, SD however, offers access to deep microbial life via pristine fracture fluids in bedrock to a depth of 1478 m. The metabolic landscape of DeMMO was previously characterized via thermodynamic modeling coupled with genomic data, illustrating the potential for microbial inhabitants of DeMMO to utilize mineral substrates as energy sources. Here, we employ field and lab based cultivation approaches with pure minerals to link phylogeny to metabolism at DeMMO. Fracture fluids were directed through reactors filled with Fe3O4, Fe2O3, FeS2, MnO2, and FeCO3 at two sites (610 m and 1478 m) for 2 months prior to harvesting for subsequent analyses. We examined mineralogical, geochemical, and microbiological composition of the reactors via DNA sequencing, microscopy, lipid biomarker characterization, and bulk C and N isotope ratios to determine the influence of mineralogy on biofilm community development. Pre-characterized mineral chips were imaged via SEM to assay microbial growth; preliminary results suggest MnO2, Fe3O4, and Fe2O3 were most conducive to colonization. Solid materials from reactors were used as inoculum for batch cultivation experiments. Media designed to mimic fracture fluid chemistry was supplemented with mineral substrates targeting metal reducers. DNA sequences and microscopy of iron oxide-rich biofilms and fracture fluids suggest iron oxidation is a major energy source at redox transition zones where anaerobic fluids meet more oxidizing conditions. We utilized these biofilms and fluids as inoculum in gradient cultivation experiments targeting microaerophilic iron oxidizers. Cultivation of microbes endemic to DeMMO, a system locally dominated by unclassified and candidate phyla, has the potential to yield novel subsurface organisms with unique physiologies. We intend to further utilize subsurface isolates to probe the effects of geochemical perturbations on biosignatures in future studies, thus broadening our understanding of subterranean ecosystems.

U-tube based near-surface environmental monitoring in the Shenhua carbon dioxide capture and storage (CCS) project.

PubMed

Li, Qi; Song, Ranran; Shi, Hui; Ma, Jianli; Liu, Xuehao; Li, Xiaochun

2018-04-01

The CO 2 injected into deep formations during implementation of carbon dioxide (CO 2 ) capture and storage (CCS) technology may leak and migrate into shallow aquifers or ground surfaces through a variety of pathways over a long period. The leaked CO 2 can threaten shallow environments as well as human health. Therefore, almost all monitoring programs for CCS projects around the world contain near-surface monitoring. This paper presents a U-tube based near-surface monitoring technology focusing on its first application in the Shenhua CCS demonstration project, located in the Ordos Basin, Inner Mongolia, China. First, background information on the site monitoring program of the Shenhua CCS demonstration project was provided. Then, the principle of fluid sampling and the monitoring methods were summarized for the U-tube sampler system, and the monitoring data were analyzed in detail. The U-tube based monitoring results showed that the U-tube sampler system is accurate, flexible, and representative of the subsurface fluid sampling process. The monitoring indicators for the subsurface water and soil gas at the Shenhua CCS site indicate good stratification characteristics. The concentration level of each monitoring indicator decreases with increasing depth. Finally, the significance of this near-surface environmental monitoring technology for CO 2 leakage assessments was preliminarily confirmed at the Shenhua CCS site. The application potential of the U-tube based monitoring technology was also demonstrated during the subsurface environmental monitoring of other CCS projects.

Effect of different fertilization measures on soil CO2 emissions of spring corn in Northeast China

NASA Astrophysics Data System (ADS)

Xu, Shicai; Qiao, Shaoqing

2018-04-01

To research the sustainability of efficient utilization approaches and modes of nitrogen in spring corns. Taking different fertilization measures to research the influence on soil respiration and microbial biomass carbon and nitrogen; the experiment takes the spring corns and black soil of Harbin in Northeast China as research objects. It researches the influence of 4 different fertilization measures by using field long-term located experiment on soil respiration of the spring corns and analyzes the yield. The four measures are as follows: farmer's fertilization practice FP; Tl mode of decreasing 20% of nitrogenous fertilizer on the basis of FP; T2 mode of 20% of Tl nitrogenous fertilizer replaced by organic fertilizer and other 20% replaced by slow-release nitrogen fertilizer; T3 mode of adding 2t/hm2 of corn stalk carbon on the basis of T2. There are significant differences of CO2 emission flux in spring corn soil with four fertilization measures (P<0.05). The rank of CO2 emission flux is: T3>Tl>T2>FP and the yield rank of spring corns is: T3>T2>Tl>FP. (1) The rational nitrogen-decrease fertilization measure has no obvious influence on spring corn yield and the replacement of organic fertilizer and slow-release nitrogen fertilizer and the addition of active carbon can improve the spring corn yield. (2) Utilization of organic fertilizer can accelerate the emission of CO2 from the soil. (3) Addition of biological carbon can promote the emission of CO2 from soil during the growing period of spring corns.

Constraining Path-Dependent Processes During Basalt-CO2 Interactions with Observations From Flow-Through and Batch Experiments

NASA Astrophysics Data System (ADS)

Thomas, D.; Garing, C.; Zahasky, C.; Harrison, A. L.; Bird, D. K.; Benson, S. M.; Oelkers, E. H.; Maher, K.

2017-12-01

Predicting the timing and magnitude of CO2 storage in basaltic rocks relies partly on quantifying the dependence of reactivity on flow path and mineral distribution. Flow-through experiments that use intact cores are advantageous because the spatial heterogeneity of pore space and reactive phases is preserved. Combining aqueous geochemical analyses and petrologic characterization with non-destructive imaging techniques (e.g. micro-computed tomography) constrains the relationship between irreversible reactions, pore connectivity and accessible surface area. Our work enhances these capabilities by dynamically imaging flow through vesicular basalts with Positron Emission Tomography (PET) scanning. PET highlights the path a fluid takes by detecting photons produced during radioactive decay of an injected radiotracer (FDG). We have performed single-phase, CO2-saturated flow-through experiments with basaltic core from Iceland at CO2 sequestration conditions (50 °C; 76-90 bar Ptot). Constant flow rate and continuous pressure measurements at the inlet and outlet of the core constrain permeability. We monitor geochemical evolution through cation and anion analysis of outlet fluid sampled periodically. Before and after reaction, we perform PET scans and characterize the core using micro-CT. The PET scans indicate a discrete, localized flow path that appears to be a micro-crack connecting vesicles, suggesting that vesicle-lining minerals are immediately accessible and important reactants. Rapid increases in aqueous cation concentration, pH and HCO3- indicate that the rock reacts nearly immediately after CO2 injection. After 24 hours the solute release decreases, which may reflect a transition to reaction with phases with slower kinetic dissolution rates (e.g. zeolites and glasses to feldspar), a decrease in available reactive surface area or precipitation. We have performed batch experiments using crushed material of the same rock to elucidate the effect of flow path geometry and mineral accessibility on geochemical evolution. Interestingly, surface area-normalized dissolution rates as evinced by SiO2 release in all experiments approach similar values ( 10-15 mol/cm2/s). Our experiments show how imaging techniques are helpful in interpreting path-dependent processes in open systems.

How CO2 Leakage May Impact the Role of Geologic Carbon Storage in Climate Mitigation

NASA Astrophysics Data System (ADS)

Peters, C. A.; Deng, H.; Bielicki, J. M.; Fitts, J. P.; Oppenheimer, M.

2014-12-01

Among CCUS technologies (Carbon Capture Utilization and Sequestration), geological storage of CO2 has a large potential to mitigate greenhouse gas emissions, but confidence in its deployment is often clouded by the possibility and cost of leakage. In this study, we took the Michigan sedimentary basin as an example to investigate the monetized risks associated with leakage, using the Risk Interference of Subsurface CO2 Storage (RISCS) model. The model accounts for spatial heterogeneity and variability of hydraulic properties of the subsurface system and permeability of potential leaking wells. In terms of costs, the model quantifies the financial consequences of CO2 escaping back to the atmosphere as well as the costs incurred if CO2 or brine leaks into overlying formations and interferes with other subsurface activities or resources. The monetized leakage risks derived from the RISCS model were then used to modify existing cost curves by shifting them upwards and changing their curvatures. The modified cost curves were used in the integrated assessment model - GCAM (Global Change Assessment Model), which provides policy-relevant results to help inform the potential role of CCUS in future energy systems when carbon mitigation targets and incentives are in place. The results showed that the extent of leakage risks has a significant effect on the extent of CCUS deployment. Under more stringent carbon mitigation policies such as a high carbon tax, higher leakage risks can be afforded and incorporating leakage risks will have a smaller impact on CCUS deployment. Alternatively, if the leakage risks were accounted for by charging a fixed premium, similar to how the risk of nuclear waste disposal is treated, the contribution of CCUS in mitigating climate change varies, depending on the value of the premium.

Sugarcane vinasse CO2 gasification and release of ash-forming matters in CO2 and N2 atmospheres.

PubMed

Dirbeba, Meheretu Jaleta; Brink, Anders; DeMartini, Nikolai; Lindberg, Daniel; Hupa, Mikko

2016-10-01

Gasification of sugarcane vinasse in CO2 and the release of ash-forming matters in CO2 and N2 atmospheres were investigated using a differential scanning calorimetry and thermogravimetric analyzer (DSC-TGA) at temperatures between 600 and 800°C. The results showed that pyrolysis is the main mechanism for the release of the organics from vinasse. Release of ash-forming matters in the vinasse is the main cause for vinasse char weight losses in the TGA above 700°C. The losses are higher in N2 than in CO2, and increase considerably with temperature. CO2 gasification also consumes the carbon in the vinasse chars while suppressing alkali release. Alkali release was also significant due to volatilization of KCl and reduction of alkali sulfate and carbonate by carbon. The DSC measured thermal events during heating up in N2 atmosphere that correspond to predicted melting temperatures of alkali salts in the char. Copyright © 2016 Elsevier Ltd. All rights reserved.

Imaging CO2 reservoirs using muons borehole detectors

NASA Astrophysics Data System (ADS)

Bonneville, A.; Bonal, N.; Lintereur, A.; Mellors, R. J.; Paulsson, B. N. P.; Rowe, C. A.; Varner, G. S.; Kouzes, R.; Flygare, J.; Mostafanezhad, I.; Yamaoka, J. A. K.; Guardincerri, E.; Chapline, G.

2016-12-01

Monitoring of the post-injection fate of CO2 in subsurface reservoirs is of utmost importance. Generally, monitoring options are active methods, such as 4D seismic reflection or pressure measurements in monitoring wells. We present a method of 4D density tomography of subsurface CO2 reservoirs using cosmic-ray muon detectors deployed in a borehole. Although muon flux rapidly decreases with depth, preliminary analyses indicate that the muon technique is sufficiently sensitive to effectively map density variations caused by fluid displacement at depths consistent with proposed CO2reservoirs. The intensity of the muon flux is, to first order, inversely proportional to the density times the path length, with resolution increasing with measurement time. The primary technical challenge preventing deployment of this technology in subsurface locations is the lack of miniaturized muon-tracking detectors both capable of fitting in standard boreholes and that will be able to resist the harsh underground conditions (temperature, pressure, corrosion) for long periods of time. Such a detector with these capabilities has been developed through a collaboration supported by the U.S. Department of Energy. A prototype has been tested in underground laboratories during 2016. In particular, we will present results from a series of tests performed in a tunnel comparing efficiencies, and angular and position resolution to measurements collected at the same locations by large instruments developed by Los Alamos and Sandia National Laboratories. We will also present the results of simulations of muon detection for various CO2 reservoir situations and muon detector configurations. Finally, to improve imaging of 3D subsurface structures, a combination of seismic data, gravity data, and muons can be used. Because seismic waves, gravity anomalies, and muons are all sensitive to density, the combination of two or three of these measurements promises to be a powerful way to improve spatial resolution and reduce uncertainty. With sufficient crossing paths, the muon data can resolve spatial density anomalies, rather than simply a path-integrated flux variance. Several approaches for combining these three measurements will be presented and discussed.

Activated Persulfate Treatment of 1,4-Dioxane in the Presence of Chlorinated Solvent Co-contaminants

NASA Astrophysics Data System (ADS)

Boving, T. T.; Eberle, D. E. H.; Ball, R.

2014-12-01

1,4-dioxane is an emerging groundwater contaminant and a likely human carcinogen. Due to its history as a stabilizer in chlorinated solvents, 1,4-dioxane is often found as a co-contaminant at solvent releases sites such as landfills, solvent recycling facilities, vapor decreasing operations, and fire-training areas. Historically, 1,4-dioxane was not routinely analyzed for at solvent release sites. The lack of analyses and the limitations of the analyses that were performed (i.e. high reporting limits) means that the scale of 1,4-dioxane subsurface contamination is still emerging. With the number of known 1,4-dioxane sites increasing, the need for cost effective 1,4-dioxane remediation technologies is rising as well. Remediation strategies that are capable of treating both 1,4-dioxane as well as chlorinated co-contaminants are of particular importance, especially when treating mixed-waste source zones. In the present study, we examined the fate of 1,4-dioxane during the targeted remediation of aqueous phase volatile organic compounds (VOC) using an activated persulfate based ISCO method (OxyZone®). Bench scale laboratory experiments are used to evaluate the treatability of 1,4-dioxane both as a single compound and in the presence of trichloroethene (TCE) and 1,1,1-trichloroethane (1,1,1-TCA). Possible dependencies on oxidant concentration and reaction kinetics were studied. Preliminary results are promising and show that OxyZone® is persistent and long lived, with oxidation of 1,4-dioxane continuing more than 12 days after initial dosage, even at dilute oxidant concentrations. The oxidative destruction of 1,4-dioxane, TCE and 1,1,1-TCA in single compound batch systems followed pseudo first order reaction kinetics. The rate of oxidation for each contaminant increased linearly with increasing persulfate concentration over the range of oxidant concentrations tested. The rate of oxidative destruction, from most easily degraded to least was: TCE > 1,4-Dioxane > 1,1,1-TCA. Experiments examining the destruction of 1,4-dioxane in the presence of TCE and 1,1,1-TCA are ongoing. The final results of this study will be presented.

TOUGH2Biot - A simulator for coupled thermal-hydrodynamic-mechanical processes in subsurface flow systems: Application to CO2 geological storage and geothermal development

NASA Astrophysics Data System (ADS)

Lei, Hongwu; Xu, Tianfu; Jin, Guangrong

2015-04-01

Coupled thermal-hydrodynamic-mechanical processes have become increasingly important in studying the issues affecting subsurface flow systems, such as CO2 sequestration in deep saline aquifers and geothermal development. In this study, a mechanical module based on the extended Biot consolidation model was developed and incorporated into the well-established thermal-hydrodynamic simulator TOUGH2, resulting in an integrated numerical THM simulation program TOUGH2Biot. A finite element method was employed to discretize space for rock mechanical calculation and the Mohr-Coulomb failure criterion was used to determine if the rock undergoes shear-slip failure. Mechanics is partly coupled with the thermal-hydrodynamic processes and gives feedback to flow through stress-dependent porosity and permeability. TOUGH2Biot was verified against analytical solutions for the 1D Terzaghi consolidation and cooling-induced subsidence. TOUGH2Biot was applied to evaluate the thermal, hydrodynamic, and mechanical responses of CO2 geological sequestration at the Ordos CCS Demonstration Project, China and geothermal exploitation at the Geysers geothermal field, California. The results demonstrate that TOUGH2Biot is capable of analyzing change in pressure and temperature, displacement, stress, and potential shear-slip failure caused by large scale underground man-made activity in subsurface flow systems. TOUGH2Biot can also be easily extended for complex coupled process problems in fractured media and be conveniently updated to parallel versions on different platforms to take advantage of high-performance computing.

Experimentally Shock-loaded Anhydrite: Unit-Cell Dimensions, Microstrain and Domain Size from X-Ray Diffraction

NASA Technical Reports Server (NTRS)

Skala, R.; Hoerz, F.

2003-01-01

Cretaceous Tertiary (K/T) boundary is traditionally associated with one of the most dramatic mass extinctions in the Earth history. A number of killing mechanisms have been suggested to contribute to the widespread extinctions of Cretaceous biota at this boundary, including severe, global deterioration of the atmosphere and hydrosphere from the shock-induced release of CO2 and SO(x) from carbonate- and sulfate-bearing target rocks, respectively. Recently carried out calculations revealed that the global warming caused by CO2 release was considerably less important than the cooling due to SO(x) gases release during the Chicxulub impact event. Considering apparent potential importance of the response of sulfates to the shock metamorphism, relative lack of the data on shock behavior of sulfates as well as some general difficulties encountered during thermodynamic modeling of the shock-induced CO2 loss from carbonates we subjected anhydrite to a series of shock experiments designed for complete recovery of the shocked material. We report here on the detail X-ray diffraction analysis of seven samples that were subjected to experimental shock-loading from 10 to 65 GPa.

SPRUCE Porewater Chemistry Data for Experimental Plots Beginning in 2013

DOE Data Explorer

Griffiths, N. A. [Center, Oak Ridge National Laboratory, U.S. Department of Energy, Oak Ridge, Tennessee, U.S.A.; Sebestyen, S. D. [Center, Oak Ridge National Laboratory, U.S. Department of Energy, Oak Ridge, Tennessee, U.S.A.

2016-01-01

This data set reports the chemistry of porewater in the SPRUCE plots located in the S1 bog. Sample collection and analyses started in August of 2013 and will continue for the duration of the experiment. Results will be added to this data set and released to the public periodically as quality assurance and publication of results are accomplished. These data are the pre- and post-treatment data from the warming and elevated CO2 treatments associated with the SPRUCE experiment. There are 10 experimental plots in SPRUCE: 5 temperature treatments (+0, +2.25, +4.5, +6.75, +9°C) at ambient CO2, and the same 5 temperature treatments at elevated CO2 (+500 ppm). There are 7 additional ambient plots without experimental enclosures, and thus a total of 17 plots.

Carbon dioxide enhanced oil recovery performance according to the literature

USGS Publications Warehouse

Olea, Ricardo A.

2017-07-17

IntroductionThe need to increase the efficiency of oil recovery and environmental concerns are bringing to prominence the use of carbon dioxide (CO2) as a tertiary recovery agent. Assessment of the impact of flooding with CO2 all eligible reservoirs in the United States not yet undergoing enhanced oil recovery (EOR) requires making the best possible use of the experience gained in 40 years of applications. Review of the publicly available literature has located relevant CO2-EOR information for 53 units (fields, reservoirs, pilot areas) in the United States and 17 abroad.As the world simultaneously faces an increasing concentration of CO2 in the atmosphere and a higher demand for fossil fuels, the CO2-EOR process continues to gain popularity for its efficiency as a tertiary recovery agent and for the potential for having some CO2 trapped in the subsurface as an unintended consequence of the enhanced production (Advanced Resources International and Melzer Consulting, 2009). More extensive application of CO2-EOR worldwide, however, is not making it significantly easier to predict the exact outcome of the CO2 flooding in new reservoirs. The standard approach to examine and manage risks is to analyze the intended target by conducting laboratory work, running simulation models, and, finally, gaining field experience with a pilot test. This approach, though, is not always possible. For example, assessment of the potential of CO2-EOR at the national level in a vast country such as the United States requires making forecasts based on information already available.Although many studies are proprietary, the published literature has provided reviews of CO2-EOR projects. Yet, there is always interest in updating reports and analyzing the information under new perspectives. Brock and Bryan (1989) described results obtained during the earlier days of CO2-EOR from 1972 to 1987. Most of the recovery predictions, however, were based on intended injections of 30 percent the size of the reservoir’s hydrocarbon pore volume (HCPV), and the predictions in most cases badly missed the actual recoveries because of the embryonic state of tertiary recovery in general and CO2 flooding in particular at the time. Brock and Bryan (1989), for example, reported for the Weber Sandstone in the Rangely oil field in Colorado, an expected recovery of 7.5 percent of the original oil in place (OOIP) after injecting a volume of CO2 equivalent to 30 percent of the HCPV, but Clark (2012) reported that after injecting a volume of CO2 equivalent to 46 percent of the HCPV, the actual recovery was 4.8 percent of the OOIP. Decades later, the numbers by Brock and Bryan (1989) continue to be cited as part of expanded reviews, such as the one by Kuuskraa and Koperna (2006). Other comprehensive reviews including recovery factors are those of Christensen and others (2001) and Lake and Walsh (2008). The Oil and Gas Journal (O&GJ) periodically reports on active CO2-EOR operations worldwide, but those releases do not include recovery factors. The monograph by Jarrell and others (2002) remains the most technically comprehensive publication on CO2 flooding, but it does not cover recovery factors either.This chapter is a review of the literature found in a search for information about CO2-EOR. It has been prepared as part of a project by the U.S. Geological Survey (USGS) to assess the incremental oil production that would be technically feasible by CO2 flooding of all suitable oil reservoirs in the country not yet undergoing tertiary recovery.

Detection of Evolved Carbon Dioxide in the Rocknest Eolian Bedform by the Sample Analysis at Mars(SAM) Instrument at the Mars Curiosity Landing Site

NASA Technical Reports Server (NTRS)

Sutter, B.; Archer, D.; McAdam, A.; Franz, H.; Ming, D. W.; Eigenbrode, J. L.; Glavin, D. P.; Mahaffy, P.; Stern, J.; Navarro-Gonzalez, R.

2013-01-01

The Sample Analysis at Mars (SAM) instrument detected four releases of carbon dioxide (CO2) that ranged from 100 to 700 C from the Rocknest eolian bedform material (Fig. 1). Candidate sources of CO2 include adsorbed CO2, carbonate(s), combusted organics that are either derived from terrestrial contamination and/or of martian origin, occluded or trapped CO2, and other sources that have yet to be determined. The Phoenix Lander s Thermal Evolved Gas Analyzer (TEGA) detected two CO2 releases (400-600, 700-840 C) [1,2]. The low temperature release was attributed to Fe- and/or Mg carbonates [1,2], per-chlorate interactions with carbonates [3], nanophase carbonates [4] and/or combusted organics [1]. The high temperature CO2 release was attributed to a calcium bearing carbonate [1,2]. No evidence of a high temperature CO2 release similar to the Phoenix material was detected in the Rocknest materials by SAM. The objectives of this work are to evaluate the temperature and total contribution of each Rocknest CO2 release and their possible sources. Four CO2 releases from the Rocknest material were detected by SAM. Potential sources of CO2 are adsorbed CO2, (peak 1) and Fe/Mg carbonates (peak 4). Only a fraction of peaks 2 and 3 (0.01 C wt.%) may be partially attributed to combustion of organic contamination. Meteoritic organics mixed in the Rocknest bedform could be present, but the peak 2 and 3 C concentration (approx.0.21 C wt. %) is likely too high to be attributed solely to meteoritic organic C. Other inorganic sources of C such as interactions of perchlorates and carbonates and sources yet to be identified will be evaluated to account for CO2 released from the thermal decomposition of Rocknest material.

CO2 study shows effects on scrub oak environment

NASA Technical Reports Server (NTRS)

2000-01-01

CO2 study site manager and plant physiologist Graham Hymus (left) examines scrub oak foliage while project engineer David Johnson (right) looks on. The life sciences study is showing that rising levels of carbon dioxide in our atmosphere, caused by the burning of fossil fuels, could spur plant growth globally. The site of KSC's study is a natural scrub oak area near the Vehicle Assembly Building. Twelve-foot areas of scrub oak have been enclosed in 16 open-top test chambers into which CO2 has been blown. Five scientists from NASA and the Smithsonian Environmental Research Center in Edgewater, Md., work at the site to monitor experiments and keep the site running. Scientists hope to continue the study another five to 10 years. More information on this study can be found in Release No. 57- 00.

Effect of Climate Extremes, Seasonal Change, and Agronomic Practices on Measured Evapotranspiration and CO2 Exchange in Sacramento-San Joaquin River Delta Alfalfa Fields

NASA Astrophysics Data System (ADS)

Clay, J.; Kent, E. R.; Leinfelder-Miles, M.; Paw U, K. T.; Little, C.; Lambert, J. J.

2017-12-01

Evapotranspiration and CO2 exchange was measured in five alfalfa fields in the Sacramento-San Joaquin River Delta region from 2016 to 2017 using eddy covariance and surface renewal methods. Seasonal changes of evapotranspiration and CO2 fluxes were compared between 2016, a drought year, and 2017, a high rainfall year. Additionally, changes in evapotranspiration and CO2 flux were investigated across various agronomic considerations, such as irrigation methods (border-check flood and sub-surface), stand life, and herbicide programs. Components of the energy balance, including net radiation, latent heat, ground heat flux, and sensible heat, were evaluated considering correlations to wind speed measured by three sonic anemometers, irrigation frequency, and crop cutting cycle. Comparisons between two different types of radiometers were also carried out. Under drought conditions, we observed higher amounts of evapotranspiration in a field having a stand life of less than two years of age compared to older stands, and in a sub-surface irrigated field compared to flood irrigated fields.

User's Guide for Evaluating Subsurface Vapor Intrusion into Buildings

EPA Pesticide Factsheets

This revised version of the User's Guide corresponds with the release of Version 3.1 of the Johnson and Ettinger (1991) model (J E) spreadsheets for estimating subsurface vapor intrusion into buildings.

MONTHLY HIGHLIGHTS (SUBSURFACE PROTECTION AND REMEDIATION DIVISION)

EPA Science Inventory

The Subsurface Protection and Remediation Division (SPRD) produces monthly highlights describing research accomplishments, involvement in current technical assistance activities, and staff participation in scientific meetings and conferences. Announcements of the release and avai...

Estimation of hydrocarbon biodegradation rates in gasoline-contaminated sediment from measured respiration rates

USGS Publications Warehouse

Baker, R.J.; Baehr, A.L.; Lahvis, M.A.

2000-01-01

An open microcosm method for quantifying microbial respiration and estimating biodegradation rates of hydrocarbons in gasoline-contaminated sediment samples has been developed and validated. Stainless-steel bioreactors are filled with soil or sediment samples, and the vapor-phase composition (concentrations of oxygen (O2), nitrogen (N2), carbon dioxide (CO2), and selected hydrocarbons) is monitored over time. Replacement gas is added as the vapor sample is taken, and selection of the replacement gas composition facilitates real-time decision-making regarding environmental conditions within the bioreactor. This capability allows for maintenance of field conditions over time, which is not possible in closed microcosms. Reaction rates of CO2 and O2 are calculated from the vapor-phase composition time series. Rates of hydrocarbon biodegradation are either measured directly from the hydrocarbon mass balance, or estimated from CO2 and O2 reaction rates and assumed reaction stoichiometries. Open microcosm experiments using sediments spiked with toluene and p-xylene were conducted to validate the stoichiometric assumptions. Respiration rates calculated from O2 consumption and from CO2 production provide estimates of toluene and p- xylene degradation rates within about ??50% of measured values when complete mineralization stoichiometry is assumed. Measured values ranged from 851.1 to 965.1 g m-3 year-1 for toluene, and 407.2-942.3 g m-3 year-1 for p- xylene. Contaminated sediment samples from a gasoline-spill site were used in a second set of microcosm experiments. Here, reaction rates of O2 and CO2 were measured and used to estimate hydrocarbon respiration rates. Total hydrocarbon reaction rates ranged from 49.0 g m-3 year-1 in uncontaminated (background) to 1040.4 g m-3 year-1 for highly contaminated sediment, based on CO2 production data. These rate estimates were similar to those obtained independently from in situ CO2 vertical gradient and flux determinations at the field site. In these experiments, aerobic conditions were maintained in the microcosms by using air as the replacement gas, thus preserving the ambient aerobic environment of the subsurface near the capillary zone. This would not be possible with closed microcosms.

Response of surface CH4 and CO2 fluxes to whole ecosystem warming and elevated CO2 in a boreal black spruce peatland, northern Minnesota

NASA Astrophysics Data System (ADS)

Hsieh, I. F.; Gill, A. L.; Finzi, A.

2017-12-01

Potential increase in peatland C losses by environmental change has been presented by impacting the balance of CO2 and CH4 sequestration and release. While temperature warming may accelerate the temperature-sensitive processes and release CO2 and CH4 from peat C stores, factors associated with warming and that associated with elevated CO2 concentration may alter the intrinsic characteristics of CO2 and CH4 emission from peatland. By leveraging Spruce and Peatland Responses Under Changing Environments (SPRUCE) experiment, we measured peat surface CO2 and CH4 fluxes and their i13C signatures across a gradient of warming temperatures in a boreal black spruce peat bog in 2015 and 2016 growing seasons. Elevated CO2 (eCO2) treatment was added to the warming experiment in June, 2016. Our results show both CH4 and CO2 flux increased with warming temperature in the two-year measurement period. Total emission for both gases were higher in 2016 with whole ecosystem warming than that in 2015 with deep peat heat warming. The 2016 increase in CO2 emission was significantly larger in the hummock microtopographic position compared to hollows. The opposite was true for CH4 fluxes, where the increase was strongest in the hollows. In fact, CH4 flux from hummocks declined in 2016 compared to 2015, suggesting lower overall rates of CH4 production and/or greater rates of methanotrophy. The increase (less depleted) in i13C -CH4 signatures suggest acetoclastic methanogensis increased its contribution to total CH4 production across the growing season and in response to experimental warming, while hydrogenotrophic methanogenesis dominated total CH4 production. On the contrary, results of i13C-CO2 show no significant change in the contribution of different sources to total CO2 emission through time or across warming temperature. On the other hand, i13C-CO2 signatures under CO2 fumigation in 2016 was significantly depleted since the eCO2 initiation, indicating a rapid increase in plant productivity and the subsequent belowground transfer of photosynthate. Our results emphasize the susceptibleness of northern peat bog to changes in the environment by illustrating measureable influences of whole ecosystem warming and elevated CO2 on greenhouse gases emission.

Reoxidation of estuarine sediments during simulated resuspension events: Effects on nutrient and trace metal mobilisation

NASA Astrophysics Data System (ADS)

Vidal-Durà, Andrea; Burke, Ian T.; Stewart, Douglas I.; Mortimer, Robert J. G.

2018-07-01

Estuarine environments are considered to be nutrient buffer systems as they regulate the delivery of nutrients from rivers to the ocean. In the Humber Estuary (UK) seawater and freshwater mixing during tidal cycles leads to the mobilisation of oxic surface sediments (0-1 cm). However, less frequent seasonal events can also mobilise anoxic subsurface (5-10 cm) sediments, which may have further implications for the estuarine geochemistry. A series of batch experiments were carried out on surface and subsurface sediments taken from along the salinity gradient of the Humber Estuary. The aim was to investigate the geochemical processes driving major element (N, Fe, S, and Mn) redox cycling and trace metal behaviour during simulated resuspension events. The magnitude of major nutrient and metal release was significantly greater during the resuspension of outer estuarine sediments rather than from inner estuarine sediments. When comparing resuspension of surface versus subsurface sediment, only the outer estuary experiments showed significant differences in major nutrient behaviour with sediment depth. In general, any ammonium, manganese and trace metals (Cu and Zn) released during the resuspension experiments were rapidly removed from solution as new sorption sites (i.e. Fe/Mn oxyhydroxides) formed. Therefore Humber estuary sediments showed a scavenging capacity for these dissolved species and hence may act as an ultimate sink for these elements. Due to the larger aerial extent of the outer estuary intertidal mudflats in comparison with the inner estuary area, the mobilisation of the outer estuary sediments (more reducing and richer in sulphides and iron) may have a greater impact on the transport and cycling of nutrients and trace metals. Climate change-associated sea level rise combined with an increasing frequency of major storm events in temperate zones, which are more likely to mobilise deeper sediment regions, will impact the nutrient and metal inputs to the coastal waters, and therefore enhance the likelihood of eutrophication in this environment.

Effect of bacteria and dissolved organics on mineral dissolution kinetics:

NASA Astrophysics Data System (ADS)

Pokrovsky, Oleg; Shirokova, Liudmila; Benezeth, Pascale; Zabelina, Svetlana

2010-05-01

Quantification of the effect of microorganisms and associated organic ligands on mineral dissolution rate is one among the last remaining challenges in modeling of water-rock interactions under earth surface and subsurface environments. This is especially true for deep underground settings within the context of CO2 capture, sequestration and storage. First, elevated CO2 pressures create numerous experimental difficulties for performing robust flow-through experiments at a given saturation state. Second, reactivity of main rock-forming minerals in abiotic systems at pCO2 >> 1 atm and circumneutral pH is still poorly constrained. And third, most of microbial habitats of the subsurface biosphere are not suitable for routine culturing in the laboratory, many of them are anaerobic and even strictly anaerobic, and many bacteria and archae cultures can live only in the consortium of microorganisms which is very hard to maintain at a controlled and stable biomass concentration. For experimental modeling of bio-mineral interactions in the laboratory, two other main conceptual challenges exist. Typical concentration of dissolved organic carbon that serves as a main nutrient for heterotrophic bacteria in underground waters rarely exceeds 3-5 mg/L. Typical concentration of DOC in nutrient media used for bacteria culturing is between 100 and 10,000 mg/L. Therefore, performing mineral-bacteria interactions in the laboratory under environmentally-sound conditions requires significant dilution of the nutrient media or the use of flow-through reactors. Concerning the effect of organic ligands and bacterial excudates on rock-forming mineral dissolution, at the present time, mostly empirical (phenomenological) approach can be used. Indeed, the pioneering studies of Stumm and co-workers have established a firm basis for modeling the catalyzing and inhibiting effects of ligands on metal oxide dissolution rate. This approach, very efficient for studying the interaction of organic and inorganic ligands with trivalent metal oxides, is based on applying multiple spectroscopic techniques allowing to reveal the chemical structure of adsorbed complexes. However, due to i) low surface area of most rock-forming minerals (carbonates, non-clay silicates), ii) difficulties of applying surface spectroscopic techniques at elevated pressures, and iii) very complex nature of bacterial exometabolites, it is not possible at the present time, to use rigorous surface complexation approach for rationalizing ligand- and bacteria-affected mineral dissolution under sub-surface CO2 storage environment. In this work, we present examples of overcoming these difficulties via concerted study of olivine, wollastonite and calcite interaction with heterotrophic bacteria and methanogenic archaes.

Uranium (VI) transport in saturated heterogeneous media: Influence of kaolinite and humic acid.

PubMed

Chen, Chong; Zhao, Kang; Shang, Jianying; Liu, Chongxuan; Wang, Jin; Yan, Zhifeng; Liu, Kesi; Wu, Wenliang

2018-05-07

Natural aquifers typically exhibit a variety of structural heterogeneities. However, the effect of mineral colloids and natural organic matter on the transport behavior of uranium (U) in saturated heterogeneous media are not totally understood. In this study, heterogeneous column experiments were conducted, and the constructed columns contained a fast-flow domain (FFD) and a slow-flow domain (SFD). The effect of kaolinite, humic acid (HA), and kaolinite/HA mixture on U(VI) retention and release in saturated heterogeneous media was examined. Media heterogeneity significantly influenced U fate and transport behavior in saturated subsurface environment. The presence of kaolinite, HA, and kaolinite/HA enhanced the mobility of U in heterogeneous media, and the mobility of U was the highest in the presence of kaolinite/HA and the lowest in the presence of kaolinite. In the presence of kaolinite, there was no difference in the amount of U released from the FFD and SFD. However, in the presence of HA and kaolinite/HA, a higher amount of U was released from the FFD. The findings in this study showed that medium structure and mineral colloids, as well as natural organic matter in the aqueous phase had significant effects on U transport and fate in subsurface environment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Ultrasonic laboratory measurements of the seismic velocity changes due to CO2 injection

NASA Astrophysics Data System (ADS)

Park, K. G.; Choi, H.; Park, Y. C.; Hwang, S.

2009-04-01

Monitoring the behavior and movement of carbon dioxide (CO2) in the subsurface is a quite important in sequestration of CO2 in geological formation because such information provides a basis for demonstrating the safety of CO2 sequestration. Recent several applications in many commercial and pilot scale projects and researches show that 4D surface or borehole seismic methods are among the most promising techniques for this purpose. However, such information interpreted from the seismic velocity changes can be quite subjective and qualitative without petrophysical characterization for the effect of CO2 saturation on the seismic changes since seismic wave velocity depends on various factors and parameters like mineralogical composition, hydrogeological factors, in-situ conditions. In this respect, we have developed an ultrasonic laboratory measurement system and have carried out measurements for a porous sandstone sample to characterize the effects of CO2 injection to seismic velocity and amplitude. Measurements are done by ultrasonic piezoelectric transducer mounted on both ends of cylindrical core sample under various pressure, temperature, and saturation conditions. According to our fundamental experiments, injected CO2 introduces the decrease of seismic velocity and amplitude. We identified that the velocity decreases about 6% or more until fully saturated by CO2, but the attenuation of seismic amplitude is more drastically than the velocity decrease. We also identified that Vs/Vp or elastic modulus is more sensitive to CO2 saturation. We note that this means seismic amplitude and elastic modulus change can be an alternative target anomaly of seismic techniques in CO2 sequestration monitoring. Thus, we expect that we can estimate more quantitative petrophysical relationships between the changes of seismic attributes and CO2 concentration, which can provide basic relation for the quantitative assessment of CO2 sequestration by further researches.

PCL foamed scaffolds loaded with 5-fluorouracil anti-cancer drug prepared by an eco-friendly route.

PubMed

Salerno, Aurelio; Domingo, Concepción; Saurina, Javier

2017-06-01

This study describes a new preparation method, which combines freeze drying and supercritical CO 2 foaming approaches, for the preparation of drug delivery scaffolds of polycaprolactone loaded with 5-fluorouracil, an anti-cancer drug, with low solubility in scCO 2 . It is a principal objective of this work to design a scCO 2 strategy to reduce 5-Fu solubility limitations in its homogeneous distribution into a PCL scaffold through the design of an innovative processing method. The design of this process is considered valuable for the development of clean technology in pharmacy and medicine, since most of the active agents have a null solubility in scCO 2 ·Supercritical CO 2 is used as a blowing agent to induce polymer foaming by means of the low temperature pressure quench process. The resulting samples have been prepared under different operational conditions focused on enhancing the performance of the release process. In this case, design of experiments (DOE) was considered for a more comprehensive and systematic optimization of the product. In particular, drug amount, equals to 4.8 or 9.1wt%, process temperature, of 45 or 50°C and depressurization rate, equals to 0.1MPas -1 or 2MPas -1 were selected as the factors to be investigated by a three-factor at two-level full factorial design. Samples were characterized to establish porosity data, drug loading percentage and, especially, release profile chromatographically monitored. Results from DOE have concluded which are the best samples providing a sustained drug release for several days, which may be of great interest to develop materials for tissue engineering and sustained release applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Experimental high strain-rate deformation products of carbonate-silicate rocks: Comparison with terrestrial impact materials

NASA Astrophysics Data System (ADS)

van der Bogert, C. H.; Schultz, P. H.; Spray, J. G.

2008-09-01

Introduction. The response of carbonate to impact processes has thus far been investigated using a combination of thermodynamic modelling, shock experiments, and impact experiments. Localized shear deformation was suggested to play an important role in the failure of carbonate during some shock experiments [1,2], and was invoked to explain significant degassing of carbonates during oblique impact experiments [3]. The results of the impact experiments are at odds with experiments [4] that show back-reaction of CO2 with CaO and MgO could significantly reduce CO2 degassing during impact events. We performed a frictional-welding experiment in order to investigate the effects of high strain-rate deformation on carbonate-silicate target materials, exclusive of shock deformation effects, and to investigate the differing results of other experiments. Samples and Techniques. A frictional melting experiment was performed using dolomitic marble and quartzite samples to simulate conditions during an impact into carbonate-silicate target rocks. The experiment followed the method of Spray (1995) [5]. The 1.5 cm3 samples were mounted onto separate steel cylinders with epoxy. Using a Blacks FWH-3 axial friction-welding rig, the samples were brought into contact at room temperature and under dry conditions with ~5 MPa applied pressure. Contact was maintained for two seconds at 750 rpm for a sustained strain-rate of 102 to 103 s-1. Results. Vapor or fine dust escaped from the interface during the experiment. Immediately after sample separation, the interfaces were incandescent. Once cooled, opaque white material adhered to both the quartzite and dolomitic marble samples. Quartzite sample. Material was injected into cracks that formed in the quartzite sample. Cooling and crystallization of the friction products resulted in the formation of submicron-sized minerals such as periclase and Ca- and Ca,Mg-silicates (Fig. 1) including merwinite and åkermanite. While periclase was observed as an individual mineral species, no pure lime was observed to be present. In the quartzite sample, CaO is present only as a component of the Ca- and Ca,Mg-silicates. In the fine-grained shear zone materials, however, elemental mapping and EMP analyses reveal an overall segregation of MgO and CaO [6], suggesting that CaO is mostly present in Casilicates and Ca,Mg-silicates with low MgO contents. Dolomitic marble sample. The dolomitic marble section exhibited thinner, shorter fractures than the quartzite sample. Mechanical twinning was induced by the deformation. The adhered friction products were very fine-grained material with larger, untwinned calcite (Fig. 2), and dendritic carbonates with a composition similar to huntite. Most of the secondary calcite had rounded margins, which suggested that they were molten during the experiment. The dendritic huntite-like carbonate, with a CO2 content higher than of these secondary carbonate grains (Fig. 3). However, calcite was the dominant secondary mineral. The finegrained portion of the shear zone material contained pervasive vesicles. The vesicles immediately adjacent to the secondary calcite grains were smaller than those adjacent to the dolomitic marble. This suggests that incorporation of CO2 near the calcite grains facilitated their growth. Discussion. The textures and compositions of the experimental products indicate that the dolomitic marble decarbonated in response to the high temperatures generated during experimental deformation. Simultaneously, the liberated CaO recombined with CO2 to form molten calcite in the shear zone. This effect, in part, is due to the lower decarbonation temperature for dolomite versus calcite [c.f., 7], which allows calcite to survive at higher temperatures than dolomite. In addition, the confining pressure during the experiment was high enough to allow calcite to be present as a liquid [c.f., 8]. Both the calcite and dendritic carbonate are likely products of back-reaction of CaO and MgO with CO2. However, both CaO and MgO were also incorporated into secondary silicates, which reduced the total amount available to back-react with CO2. It appears that all CaO released from the dolomitic marble formed secondary minerals (carbonates and silicates), because it is not present as pure CaO. The MgO released from the dolomitic marble primarily formed secondary silicates, periclase, and minor secondary carbonate. As a result, the secondary carbonates cannot be a sink for all the CO2 gas released from the dolomitic marble, unless a much higher proportion of the huntite-like phase was present. Thus, there was a net release of CO2 gas from the original dolomitic marble. A portion of this CO2 remained trapped in vesicles, but CO2 gas also escaped from the shear zone. This is consistent with compositional measurements of the shear zone that suggest a release of at least 5 wt% CO2 relative to the original dolomitic marble. Comparison with terrestrial craters. Many of the descriptions of deformation features in carbonates at terrestrial craters, such as mechanical twinning and bent fractures [9-11], are similar to those seen in our experimental products. Carbonates that survive impact seem to accommodate both shock and shear deformation primarily through mechanical fracturing and twinning. Impact melts at craters in carbonate-rich targets have been found to contain both silicic and carbonatitic melts [e.g., 12], with mineral phases that are indicative of high temperature reactions between carbonate and silicate rocks [e.g., 9]. Our experiments also showed these characteristics, however, the mineral phases produced were slightly different and we have not observed silicate glass in our experimental products. The segregation of MgO from CaO has been observed, for example, at Haughton [12] and Popigai [13], and was also seen in our experimental products [6]. Implications. The products of high strain-rate deformation experiments with carbonate-silicate rocks are similar in many aspects to impact products at terrestrial craters in mixed carbonate-silicate targets. The experiments show that decarbonation of carbonate targets and high temperature reactions between carbonate and silicates in the target rocks are not exclusive effects of shock deformation. Shear deformation alone can generate temperature and pressure conditions necessary to decarbonate dolomitic marble and generate calcitic melts. Thus, high strain-rate deformation is a potentially major contributor to the total impact-related energy deposited into the target, especially for oblique impacts. Shear deformation occuring during and after shock deformation could, in fact, enhance the release of CO2 as a gas, by creating pathways that allow gases to escape from target materials. Understanding the relative importance and interaction of each CO2 releasing or trapping mechanism is important for the determination of the environmental significance of impacts in targets containing carbonates. References. [1] Lange M. A. and Ahrens T. J. (1986) EPSL 77, 409-418. [2] Tyburczy J. A. and Ahrens T. J. (1986) JGR 91, 4730-4744. [3] Schultz P. H. (1996) GSA Abstracts, A384. [4] Agrinier P., et al. (2001) GCA 65, 2615-2632. [5] Spray J. G. (1995) Geology 23, 1119-1122. [6] van der Bogert C. H., et al. (2007) LPI Contribution No. 1360, 123-124. [7] Martinez I., et al. (1995) JGR 100, 15456-15476. [8] Ivanov B. A. and Deutsch A. (2002) Phys. Earth Planet. Int. 129, 131-143. [9] Martinez I., et al. (1994) EPSL 121, 559-574. [10] Redeker H.-J. and Stöffler D. (1988) Meteoritics 23, 185-196. [11] Skála R. and Jakes P. (1999). In Large Meteorite Impacts and Planetary Evolution II (eds. B. O. Dressler and V. L. Sharpton), pp. 205-214. [12] Osinski G. R. and Spray J. G. (2001) EPSL 194, 17-29. [13] Kenkmann T., et al. (1999) LPS XXX, Abstract #1561.

Monitoring of environmental influences on seismic velocity at the geological storage site for CO2 in Ketzin (Germany) with ambient seismic noise

NASA Astrophysics Data System (ADS)

Gassenmeier, M.; Sens-Schönfelder, C.; Delatre, M.; Korn, M.

2015-01-01

Regarding the exploitation of natural resources, storage of waste or subsurface construction, there is an increasing need to obtain comprehensive knowledge about the subsurface and its temporal changes. We investigate the possibility of a passive monitoring using ambient seismic noise, which is cheap and continuous compared to active seismics. We work with data acquired with a seismic network in Ketzin (Germany) where 67 271 tons of CO2 were injected from 2008 June until 2013 August into a saline aquifer at a depth of about 650 m. Monitoring the expansion of the CO2 plume is essential for the characterization of the reservoir as well as the detection of potential leakage. By cross-correlating about 4 yr of passive seismic data in a frequency range of 0.05-4.5 Hz we found periodic velocity variations with a period of approximately 1 yr that cannot be caused by the CO2 injection. The prominent direction of the noise wavefield indicates a wind farm as the dominant source providing the temporally stable noise field. This spacial stability excludes variations of the noise source distribution as a cause of spurious velocity variations. Based on an amplitude decrease associated with time windows towards later parts of the coda, we show that the variations must be generated in the shallow subsurface. A comparison to groundwater level data reveals a direct correlation between depth of the groundwater level and the seismic velocity. The influence of ground frost on the seismic velocities is documented by a sharp increase of velocity when the maximum daily temperature stays below 0 °C. Although the observed periodic changes and the changes due to ground frost affect only the shallow subsurface, they mask potential signals of material changes from the reservoir depths.

Method for production of hydrocarbons from hydrates

DOEpatents

McGuire, Patrick L.

1984-01-01

A method of recovering natural gas entrapped in frozen subsurface gas hydrate formations in arctic regions. A hot supersaturated solution of CaCl.sub.2 or CaBr.sub.2, or a mixture thereof, is pumped under pressure down a wellbore and into a subsurface hydrate formation so as to hydrostatically fracture the formation. The CaCl.sub.2 /CaBr.sub.2 solution dissolves the solid hydrates and thereby releases the gas entrapped therein. Additionally, the solution contains a polymeric viscosifier, which operates to maintain in suspension finely divided crystalline CaCl.sub.2 /CaBr.sub.2 that precipitates from the supersaturated solution as it is cooled during injection into the formation.

Developing a trend prediction model of subsurface damage for fixed-abrasive grinding of optics by cup wheels.

PubMed

Dong, Zhichao; Cheng, Haobo

2016-11-10

Fixed-abrasive grinding by cup wheels plays an important role in the production of precision optics. During cup wheel grinding, we strive for a large removal rate while maintaining fine integrity on the surface and subsurface layers (academically recognized as surface roughness and subsurface damage, respectively). This study develops a theoretical model used to predict the trend of subsurface damage of optics (with respect to various grinding parameters) in fixed-abrasive grinding by cup wheels. It is derived from the maximum undeformed chip thickness model, and it successfully correlates the pivotal parameters of cup wheel grinding with the subsurface damage depth. The efficiency of this model is then demonstrated by a set of experiments performed on a cup wheel grinding machine. In these experiments, the characteristics of subsurface damage are inspected by a wedge-polishing plus microscopic inspection method, revealing that the subsurface damage induced in cup wheel grinding is composed of craterlike morphologies and slender cracks, with depth ranging from ∼6.2 to ∼13.2  μm under the specified grinding parameters. With the help of the proposed model, an optimized grinding strategy is suggested for realizing fine subsurface integrity as well as high removal rate, which can alleviate the workload of subsequent lapping and polishing.

Effect of electrochemical corrosion on the subsurface microstructure evolution of a CoCrMo alloy in albumin containing environment

NASA Astrophysics Data System (ADS)

Wang, Zhongwei; Yan, Yu; Su, Yanjing; Qiao, Lijie

2017-06-01

The subsurface microstructures of metallic implants play a key role in bio-tribocorrosion. Due to wear or change of local environment, the implant surface can have inhomogeneous electrochemical corrosion properties. In this work, the effect of electrochemical corrosion conditions on the subsurface microstructure evolution of CoCrMo alloys for artificial joints was investigated. Transmission electron microscope (TEM) was employed to observe the subsurface microstructures of worn areas at different applied potentials in a simulated physiological solution. The results showed that applied potentials could affect the severity of the subsurface deformation not only by changing the surface passivation but also affecting the adsorption of protein on the alloy surface.

HANDBOOK: GROUNDWATER - METHODOLOGY - VOL. 2

EPA Science Inventory

The subsurface environment of ground water is characterized by a complex interplay of physical, geochemical and biological forces that govern the release, transport and fate of a variety of chemical substances. There are literally as many varied hydrogeologic settings as there ar...

Atmospheric modeling of Mars CH4 subsurface clathrates releases mimicking SAM and 2003 Earth-based detections

NASA Astrophysics Data System (ADS)

Pla-Garcia, Jorge

2017-10-01

The aim of this work is to establish the amount of mixing during all martian seasons to test whether CH4 releases inside or outside of Gale crater are consistent with MSL-SAM observations. Several modeling scenarios were configured, including instantaneous and steady releases, both inside and outside the crater. A simulation to mimic the 2003 Earth-based detections (Mumma et al. 2009 or M09) was also performed. In the instantaneous release inside Gale experiments, Ls270 was shown to be the faster mixing season when air within and outside the crater was well mixed: all tracer mass inside the crater is diluted after just 8 hours. The mixing of near surface crater air with the external environment in the rest of the year is potentially rapid but slower than Ls270. In the instantaneous release outside Gale (NW) experiment, in just 12 hours the CH4 that makes it to the MSL landing location is diluted by six orders of magnitude. The timescale of mixing in the model is on the order of 1 sol regardless of season. The duration of the CH4 peak observed by SAM is 100 sols. Therefore there is a steady release inside the crater, or there is a large magnitude steady release outside the crater. In the steady release Gale experiments, CH4 flux rate from ground is 1.8 kg m-2 s-1 (Gloesener et al. 2017) and it is not predictive. In these experiments, ~200 times lower CH4 values detected by SAM are modeled around MSL location. There are CH4 concentration variations of orders of magnitude depending on the hour, so timing of SAM measurements is important. With a larger (but further away) outside crater release area compared to inside, similar CH4 values around MSL are modeled, so distance to source is important. In the steady experiments mimicking M09 detection release area, only 12 times lower CH4 values detected by SAM are modeled around MSL. The highest value in the M09 modeled scenario (0.6 ppbv) is reached in Ls270. This value is the highest of all modeled experiments. With our initial conditions, SAM should not be able to detect CH4, but if we multiply flux by 12, increase the release area or move it closer to MSL (or all of above), it may be possible to get CH4 values that SAM could detect regardless where it comes from.

Large CO 2 and CH 4 emissions from polygonal tundra during spring thaw in northern Alaska: Spring Pulse Emission

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raz-Yaseef, Naama; Torn, Margaret S.; Wu, Yuxin

The few prethaw observations of tundra carbon fluxes suggest that there may be large spring releases, but little Is lmown about the scale and underlying mechanisms of this phenomenon. To address these questions, we combined ecosystem eddy flux measurements from two towers near Barrow, Alaska, with mechanistic soil-core thawing experiment During a 2week period prior to snowmelt In 2014, large fluxes were measured, reducing net summer uptake of CO2 by 46% and adding 6% to cumulative CH4 emissions. Emission pulses were linked to unique rain-on-snow events enhancing soli cracking. Controlled laboratory experiment revealed that as surface Ice thaws, an immediate,more » large pulse of trapped gases Is emitted. These results suggest that the Arctic C02 and CH4 spring pulse is a delayed release of biogenic gas production from the previous fall and that the pulse can be large enough to offset a significant fraction of the moderate Arctic tundra carbon sink.« less

Using the Viking biology experimental results to obtain chemical information about Martian regolith

NASA Technical Reports Server (NTRS)

Plumb, Robert C.

1992-01-01

Although initially formulated as biology experiments, most of the results produced by the Viking Labeled Release (LR), Gas Exchange (GEX), and Pyrolytic Release (PR) experiments have been reproduced by chemical means. The experiments do not need more study as 'biological' phenomena, but they do deserve much more careful consideration from a chemical viewpoint. They are the only 'wet-chemical' experiments that scientists have performed on another planet, but they have not found very general use as sources of scientific information. There is a large set of potentially useful chemical observations, e.g., the three resolvable and precisely measured kinetic components of the release of C-14-labeled gases, the thermal sensitivity and magnitudes of the oxidation reaction(s) of the LR experiments, the kinetics and magnitude of the O2 and CO2 release of the GEX experiments, the thermal sensitivity of the GEX results, the differences between the thermal sensitivity of the GEX and the thermal sensitivity of the LR responses, and the kinetics and magnitudes of the LR successive injection reabsorption effect. It should be possible to test many chemical aspects of hypothetical martian phenomena in experiments using the biology experimental configurations and derive much valuable information by comparisons with the Viking observations.

Does encapsulation protect embryos from the effects of ocean acidification? The example of Crepidula fornicata.

PubMed

Noisette, Fanny; Comtet, Thierry; Legrand, Erwann; Bordeyne, François; Davoult, Dominique; Martin, Sophie

2014-01-01

Early life history stages of marine organisms are generally thought to be more sensitive to environmental stress than adults. Although most marine invertebrates are broadcast spawners, some species are brooders and/or protect their embryos in egg or capsules. Brooding and encapsulation strategies are typically assumed to confer greater safety and protection to embryos, although little is known about the physico-chemical conditions within egg capsules. In the context of ocean acidification, the protective role of encapsulation remains to be investigated. To address this issue, we conducted experiments on the gastropod Crepidula fornicata. This species broods its embryos within capsules located under the female and veliger larvae are released directly into the water column. C. fornicata adults were reared at the current level of CO2 partial pressure (pCO2) (390 μatm) and at elevated levels (750 and 1400 μatm) before and after fertilization and until larval release, such that larval development occurred entirely at a given pCO2. The pCO2 effects on shell morphology, the frequency of abnormalities and mineralization level were investigated on released larvae. Shell length decreased by 6% and shell surface area by 11% at elevated pCO2 (1400 μatm). The percentage of abnormalities was 1.5- to 4-fold higher at 750 μatm and 1400 μatm pCO2, respectively, than at 390 μatm. The intensity of birefringence, used as a proxy for the mineralization level of the larval shell, also decreased with increasing pCO2. These negative results are likely explained by increased intracapsular acidosis due to elevated pCO2 in extracapsular seawater. The encapsulation of C. fornicata embryos did not protect them against the deleterious effects of a predicted pCO2 increase. Nevertheless, C. fornicata larvae seemed less affected than other mollusk species. Further studies are needed to identify the critical points of the life cycle in this species in light of future ocean acidification.

HTO and OBT activity concentrations in soil at the historical atmospheric HT release site (Chalk River Laboratories).

PubMed

Kim, S B; Bredlaw, M; Korolevych, V Y

2012-01-01

Tritium is routinely released by the Chalk River Laboratories (CRL) nuclear facilities. Three International HT release experiments have been conducted at the CRL site in the past. The site has not been disturbed since the last historical atmospheric testing in 1994 and presents an opportunity to assess the retention of tritium in soil. This study is devoted to the measurement of HTO and OBT activity concentration profiles in the subsurface 25 cm of soil. In terms of soil HTO, there is no evidence from the past HT release experiments that HTO was retained. The HTO activity concentration in the soil pore water appears similar to concentrations found in background areas in Ontario. In contrast, OBT activity concentrations in soil at the same site were significantly higher than HTO activity concentrations in soil. Elevated OBT appears to reside in the top layer of the soil (0-5 cm). In addition, OBT activity concentrations in the top soil layer did not fluctuate much with season, again, quite in contrast with soil HTO. This result suggests that OBT activity concentrations retained the signature of the historical tritium releases. Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.

In vitro evaluation of anticancer nanomedicines based on doxorubicin and amphiphilic Y-shaped copolymers

PubMed Central

Li, Di; Ding, Jian Xun; Tang, Zhao Hui; Sun, Hai; Zhuang, Xiu Li; Xu, Jing Zhe; Chen, Xue Si

2012-01-01

Four monomethoxy poly(ethylene glycol)-poly(L-lactide-co-glycolide)2 (mPEG-P( LA-co-GA)2) copolymers were synthesized by ring-opening polymerization of L-lactide and glycolide with double hydroxyl functionalized mPEG (mPEG-(OH)2) as macroinitiator and stannous octoate as catalyst. The copolymers self-assembled into nanoscale micellar/vesicular aggregations in phosphate buffer at pH 7.4. Doxorubicin (DOX), an anthracycline anticancer drug, was loaded into the micellar/vesicular nanoparticles, yielding micellar/vesicular nanomedicines. The in vitro release behaviors could be adjusted by content of hydrophobic polyester and pH of the release medium. In vitro cell experiments showed that the intracellular DOX release could be adjusted by content of P(LA-co-GA), and the nanomedicines displayed effective proliferation inhibition against Henrietta Lacks’s cells with different culture times. Hemolysis tests indicated that the copolymers were hemocompatible, and the presence of copolymers could reduce the hemolysis ratio of DOX significantly. These results suggested that the novel anticancer nanomedicines based on DOX and amphiphilic Y-shaped copolymers were attractive candidates as tumor tissular and intracellular targeting drug delivery systems in vivo, with enhanced stability during circulation and accelerated drug release at the target sites. PMID:22701317

Adsorption and co-precipitation behavior of arsenate, chromate, selenate and boric acid with synthetic allophane-like materials.

PubMed

Opiso, Einstine; Sato, Tsutomu; Yoneda, Tetsuro

2009-10-15

Pollution caused by boric acid and toxic anions such as As(V), Cr(VI) and Se(VI) is hazardous to human health and environment. The sorption characteristics of these environmentally significant ionic species on allophane-like nanoparticles were investigated in order to determine whether allophane can reduce their mobility in the subsurface environment at circum-neutral pH condition. Solutions containing 100 or 150 mmol of AlCl(3)x6H(2)O were mixed to 100 mmol of Na(4)SiO(4) and the pH were adjusted to 6.4+/-0.3. The mineral suspensions were shaken for 1h and incubated at 80 degrees C for 5 days. Appropriate amounts of As, B, Cr and Se solutions were added separately during and after allophane precipitation. The results showed that As(V) and boric acid can be irreversibly fixed during co-precipitation in addition to surface adsorption. However, Cr(VI) and Se(VI) retention during and after allophane precipitation is mainly controlled by surface adsorption. The structurally fixed As(V) and boric acid were more resistant to release than those bound on the surface. The sorption characteristics of oxyanions and boric acid were also influenced by the final Si/Al molar ratio of allophane in which Al-rich allophane tend to have higher uptake capacity. The overall results of this study have demonstrated the role of allophane-like nanoparticles and the effect of its Si/Al ratio on As, B, Cr and Se transport processes in the subsurface environment.

Smoke and fire characteristics for cerrado and deforestation burns in Brazil - BASE-B experiment

NASA Technical Reports Server (NTRS)

Ward, D. E.; Susott, R. A.; Kauffman, J. B.; Babbitt, R. E.; Cummings, D. L.; Dias, B.; Holben, B. N.; Kaufman, Y. J.; Rasmussen, R. A.; Setzer, A. W.

1992-01-01

Five test fires were performed during August and September 1990 in the cerrado (savannalike region) in central Brazil (three fires) and tropical moist forest (two fires) in the eastern Amazon. This paper details the gases released, the ratios of the gases to each other and to particulate matter, fuel loads, and the fraction consumed (combustion factors), and the fire behavior associated with biomass consumption. Models are presented for evaluating emission factors for CH4, CO2, CO, H2, and particles less than 2.5 micron diam (PM2.5) as a function of combustion efficiency. The ratio of carbon released as CO2 (combustion efficiency) for the cerrado fires averaged 0.94 and for the deforestation fires it decreased from 0.88 for the flaming phase to less than 0.80 during the smoldering phase of combustion. For tropical ecosystems, emissions of most products of incomplete combustion are projected to be lower than previous estimates for savanna ecosystems and somewhat higher for fires used for deforestation purposes.

Volatile Emissions from Hot Spring Basin, Yellowstone National Park, USA

NASA Astrophysics Data System (ADS)

Werner, C.; Hurwitz, S.; Bergfeld, D.; Evans, W. C.; Lowenstern, J. B.; Jaworowski, C.; Heasler, H.

2007-12-01

The flux and composition of magmatic volatiles were characterized for Hot Spring Basin (HSB), Yellowstone National Park, in August 2006. Diffuse fluxes of CO2 (228 sites) from thermal soil were elevated, with a population distribution similar to that of other acid-sulfate areas in Yellowstone. Thus the estimated diffuse emission rate at HSB is proportionately larger than other areas due to its large area, and could be as high as 1000 td-1 CO2. The diffuse flux of H2S was only above detection limits at 20 of the 31 sites measured. The estimated diffuse H2S emission rate was ~ 4 td-1. Good correlation exists between the log of CO2 flux and shallow soil temperatures, indicating linked steam and gas upflow in the subsurface. The correlation between CO2 and H2S fluxes is weak, and the CO2 / H2S diffuse flux ratio was higher than in fumarolic ratios of CO2 to H2S. This suggests that various reactions, e.g., native sulfur deposition, act to remove H2S from the original gas stream in the diffuse low- temperature environment. Dissolved sulfate flux through Shallow Creek, which drains part of HSB, was ~ 4 td-1. Comparing dissolved sulfate flux to estimates of primary emission of H2S based on fumarolic gas geochemistry gives first order estimates of the sulfur consumed in surficial or subsurface mineral deposition. Total C and S outputs from HSB are comparable to other active volcanic systems.

The Inherent Tracer Fingerprint of Captured CO2

NASA Astrophysics Data System (ADS)

Flude, Stephanie; Gyore, Domokos; Stuart, Finlay; Boyce, Adrian; Haszeldine, Stuart; Chalaturnyk, Rick; Gilfillan, Stuart

2017-04-01

Inherent tracers, the isotopic and trace gas composition of captured CO2 streams, are potentially powerful tracers for use in CCS technology [1,2]. Despite this potential, the inherent tracer fingerprint in captured CO2 streams has yet to be robustly investigated and documented [3]. Here, we will present the first high quality systematic measurements of the carbon and oxygen isotopic and noble gas fingerprints measured in anthropogenic CO2 captured from combustion power stations and fertiliser plants, using amine capture, oxyfuel and gasification processes, and derived from coal, biomass and natural gas feedstocks. We will show that δ13C values are mostly controlled by the feedstock composition, as expected. The majority of the CO2 samples exhibit δ18O values similar to atmospheric O2 although captured CO2 samples from biomass and gas feedstocks at one location in the UK are significantly higher. Our measured noble gas concentrations in captured CO2 are generally as expected [2], typically being two orders of magnitude lower in concentration than in atmospheric air. Relative noble gas elemental abundances are variable and often show an opposite trend to that of a water in contact with the atmosphere. Expected enrichments in radiogenic noble gases (4He and 40Ar) for fossil fuel derived CO2 were not always observed due to dilution with atmospheric noble gases during the CO2 generation and capture process. Many noble gas isotope ratios indicate that isotopic fractionation takes place during the CO2 generation and capture processes, resulting in isotope ratios similar to fractionated air. We conclude that phase changes associated with CO2 transport and sampling may induce noble gas elemental and isotopic fractionation, due to different noble gas solubilities between high (liquid or supercritical) and low (gaseous) density CO2. Data from the Australian CO2CRC Otway test site show that δ13C of CO2 will change once injected into the storage reservoir, but that this change is small and can be quantitatively modelled in order to determine the proportion of CO2 that has dissolved into the formation waters. Furthermore, noble gas data from the Otway storage reservoir post-injection, shows evidence of noble gas stripping of formation water and contamination with Kr and Xe related to an earlier injection experiment. Importantly, He data from SaskPower's Aquistore illustrates that injected CO2 will inherit distinctive crustal radiogenic noble gas fingerprints from the subsurface once injected into an undisturbed geological storage reservoir, meaning this could be used to identify unplanned migration of the CO2 to the surface and shallow subsurface [4]. References [1] Mayer et al., (2015) IJGGC, Vol. 37, 46-60 http://dx.doi.org/10.1016/j.ijggc.2015.02.021 [2] Gilfillan et al., (2014) Energy Procedia, Vol. 63, 4123-4133 http://dx.doi.org/10.1016/j.egypro.2014.11.443 [3] Flude et al., (2016) Environ. Sci. Technol., 50 (15), pp 7939-7955 DOI: 10.1021/acs.est.6b01548 [4] Gilfillan et al., (2011) IJGGC, Vol. 5 (6) 1507-1516 http://dx.doi.org/10.1016/j.ijggc.2011.08.008

Iron-Rich Carbonates as the Potential Source of Evolved CO2 Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater

NASA Technical Reports Server (NTRS)

Sutter, B.; Heil, E.; Rampe, E. B.; Morris, R. V.; Ming, D. W.; Archer, P. D.; Eigenbrode, J. L.; Franz, H. B.; Glavin, D. P.; McAdam, A. C.;

Metal release from sandstones under experimentally and numerically simulated CO2 leakage conditions.

PubMed

Kirsch, Katie; Navarre-Sitchler, Alexis K; Wunsch, Assaf; McCray, John E

2014-01-01

Leakage of CO2 from a deep storage formation into an overlying potable aquifer may adversely impact water quality and human health. Understanding CO2-water-rock interactions is therefore an important step toward the safe implementation of geologic carbon sequestration. This study targeted the geochemical response of siliclastic rock, specifically three sandstones of the Mesaverde Group in northwestern Colorado. To test the hypothesis that carbonate minerals, even when present in very low levels, would be the primary source of metals released into a CO2-impacted aquifer, two batch experiments were conducted. Samples were reacted for 27 days with water and CO2 at partial pressures of 0.01 and 1 bar, representing natural background levels and levels expected in an aquifer impacted by a small leakage, respectively. Concentrations of major (e.g., Ca, Mg) and trace (e.g., As, Ba, Cd, Fe, Mn, Pb, Sr, U) elements increased rapidly after CO2 was introduced into the system, but did not exceed primary Maximum Contaminant Levels set by the U.S. Environmental Protection Agency. Results of sequential extraction suggest that carbonate minerals, although volumetrically insignificant in the sandstone samples, are the dominant source of mobile metals. This interpretation is supported by a simple geochemical model, which could simulate observed changes in fluid composition through CO2-induced calcite and dolomite dissolution.

Biogeochemical control points in a water-limited critical zone

NASA Astrophysics Data System (ADS)

Chorover, J.; Brooks, P. D.; Gallery, R. E.; McIntosh, J. C.; Olshansky, Y.; Rasmussen, C.

2017-12-01

The routing of water and carbon through complex terrain is postulated to control structure evolution in the sub-humid critical zone of the southwestern US. By combining measurements of land-atmosphere exchange, ecohydrologic partitioning, and subsurface biogeochemistry, we seek to quantify how a heterogeneous (in time and space) distribution of "reactants" impacts both short-term (sub-)catchment response (e.g., pore and surface water chemical dynamics) and long-term landscape evolution (e.g., soil geochemistry/morphology and regolith weathering depth) in watersheds underlain by rhyolite and schist. Instrumented pedons in convergent, planar, and divergent landscape positions show distinct depth-dependent responses to precipitation events. Wetting front propagation, dissolved carbon flux and associated biogeochemical responses (e.g., pulses of CO2 production, O2 depletion, solute release) vary with topography, revealing the influence of lateral subsidies of water and carbon. The impacts of these episodes on the evolution of porous media heterogeneity is being investigated by statistical analysis of pore water chemistry, chemical/spectroscopic studies of solid phase organo-mineral products, sensor-derived water characteristic curves, and quantification of co-located microbial community activity/composition. Our results highlight the interacting effects of critical zone structure and convergent hydrologic flows in the evolution of biogeochemical control points.

Assessment of brine migration risks along vertical pathways due to CO2 injection

NASA Astrophysics Data System (ADS)

Kissinger, Alexander; Class, Holger

2015-04-01

Global climate change, shortage of resources and the growing usage of renewable energy sources has lead to a growing demand for the utilization of subsurface systems. Among these competing uses are Carbon Capture and Storage (CCS), geothermal energy, nuclear waste disposal, 'renewable' methane or hydrogen storage as well as the ongoing production of fossil resources like oil, gas and coal. Additionally, these technologies may also create conflicts with essential public interests such as water supply. For example, the injection of CO2 into the subsurface causes an increase in pressure reaching far beyond the actual radius of influence of the CO2 plume, potentially leading to large amounts of displaced salt water. In this work we focus on the large scale impacts of CO2 storage on brine migration but the methodology and the obtained results may also apply to other fields like waste water disposal, where large amounts of fluid are injected into the subsurface. In contrast to modeling on the reservoir scale the spatial scale required for this work is much larger in both vertical and lateral direction, as the regional hydrogeology has to be considered. Structures such as fault zones, hydrogeological windows in the Rupelian clay or salt domes are considered as potential pathways for displaced fluids into shallow systems and their influence has to be taken into account. We put the focus of our investigations on the latter type of scenario, since there is still a poor understanding of the role that salt diapirs would play in CO2 storage projects. As there is hardly any field data available on this scale, we compare different levels of model complexity in order to identify the relevant processes for brine displacement and simplify the modeling process wherever possible, for example brine injection vs. CO2 injection, simplified geometries vs. the complex formation geometry and the role of salt induced density differences on flow. Further we investigate the impact of the displaced brine due to CO2 injection and compare it to the natural fluid exchange between shallow and deep aquifers in order to asses possible damage.

Tipping Point for Expansion of Layered Aluminosilicates in Weakly Polar Solvents: Supercritical CO2.

PubMed

Schaef, Herbert T; Loganathan, Narasimhan; Bowers, Geoffrey M; Kirkpatrick, R James; Yazaydin, A Ozgur; Burton, Sarah D; Hoyt, David W; Thanthiriwatte, K Sahan; Dixon, David A; McGrail, B Peter; Rosso, Kevin M; Ilton, Eugene S; Loring, John S

2017-10-25

Layered aluminosilicates play a dominant role in the mechanical and gas storage properties of the subsurface, are used in diverse industrial applications, and serve as model materials for understanding solvent-ion-support systems. Although expansion in the presence of H 2 O is well-known to be systematically correlated with the hydration free energy of the interlayer cation, particularly in environments dominated by nonpolar solvents (i.e., CO 2 ), uptake into the interlayer is not well-understood. Using novel high-pressure capabilities, we investigated the interaction of dry supercritical CO 2 with Na-, NH 4 -, and Cs-saturated montmorillonite, comparing results with predictions from molecular dynamics simulations. Despite the known trend in H 2 O and that cation solvation energies in CO 2 suggest a stronger interaction with Na, both the NH 4 - and Cs-clays readily absorbed CO 2 and expanded, while the Na-clay did not. The apparent inertness of the Na-clay was not due to kinetics, as experiments seeking a stable expanded state showed that none exists. Molecular dynamics simulations revealed a large endothermicity to CO 2 intercalation in the Na-clay but little or no energy barrier for the NH 4 - and Cs-clays. Indeed, the combination of experiment and theory clearly demonstrate that CO 2 intercalation of Na-montmorillonite clays is prohibited in the absence of H 2 O. Consequently, we have shown for the first time that in the presence of a low dielectric constant, gas swelling depends more on the strength of the interaction between the interlayer cation and aluminosilicate sheets and less on that with solvent. The finding suggests a distinct regime in layered aluminosilicate swelling behavior triggered by low solvent polarizability, with important implications in geomechanics, storage, and retention of volatile gases, and across industrial uses in gelling, decoloring, heterogeneous catalysis, and semipermeable reactive barriers.

Potential for Nitrogen Fixation and Nitrification in the Granite-Hosted Subsurface at Henderson Mine, CO

PubMed Central

Swanner, Elizabeth D.; Templeton, Alexis S.

2011-01-01

The existence of life in the deep terrestrial subsurface is established, yet few studies have investigated the origin of nitrogen that supports deep life. Previously, 16S rRNA gene surveys cataloged a diverse microbial community in subsurface fluids draining from boreholes 3000 feet deep at Henderson Mine, CO, USA (Sahl et al., 2008). The prior characterization of the fluid chemistry and microbial community forms the basis for the further investigation here of the source of NH4+. The reported fluid chemistry included N2, NH4+ (5–112 μM), NO2− (27–48 μM), and NO3− (17–72 μM). In this study, the correlation between low NH4+ concentrations in dominantly meteoric fluids and higher NH4+ in rock-reacted fluids is used to hypothesize that NH4+ is sourced from NH4+-bearing biotite. However, biotite samples from the host rocks and ore-body minerals were analyzed by Fourier transform infrared (FTIR) microscopy and none-contained NH4+. However, the nitrogenase-encoding gene nifH was successfully amplified from DNA of the fluid sample with high NH4+, suggesting that subsurface microbes have the capability to fix N2. If so, unregulated nitrogen fixation may account for the relatively high NH4+ concentrations in the fluids. Additionally, the amoA and nxrB genes for archaeal ammonium monooxygenase and nitrite oxidoreductase, respectively, were amplified from the high NH4+ fluid DNA, while bacterial amoA genes were not. Putative nitrifying organisms are closely related to ammonium-oxidizing Crenarchaeota and nitrite-oxidizing Nitrospira detected in other subsurface sites based upon 16S rRNA sequence analysis. Thermodynamic calculations underscore the importance of NH4+ as an energy source in a subsurface nitrification pathway. These results suggest that the subsurface microbial community at Henderson is adapted to the low nutrient and energy environment by their capability of fixing nitrogen, and that fixed nitrogen may support subsurface biomass via nitrification. PMID:22190904

Analytical solutions to dissolved contaminant plume evolution with source depletion during carbon dioxide storage.

PubMed

Yang, Yong; Liu, Yongzhong; Yu, Bo; Ding, Tian

2016-06-01

Volatile contaminants may migrate with carbon dioxide (CO2) injection or leakage in subsurface formations, which leads to the risk of the CO2 storage and the ecological environment. This study aims to develop an analytical model that could predict the contaminant migration process induced by CO2 storage. The analytical model with two moving boundaries is obtained through the simplification of the fully coupled model for the CO2-aqueous phase -stagnant phase displacement system. The analytical solutions are confirmed and assessed through the comparison with the numerical simulations of the fully coupled model. Then, some key variables in the analytical solutions, including the critical time, the locations of the dual moving boundaries and the advance velocity, are discussed to present the characteristics of contaminant migration in the multi-phase displacement system. The results show that these key variables are determined by four dimensionless numbers, Pe, RD, Sh and RF, which represent the effects of the convection, the dispersion, the interphase mass transfer and the retention factor of contaminant, respectively. The proposed analytical solutions could be used for tracking the migration of the injected CO2 and the contaminants in subsurface formations, and also provide an analytical tool for other solute transport in multi-phase displacement system. Copyright © 2016 Elsevier B.V. All rights reserved.

Interaural level differences do not suffice for restoring spatial release from masking in simulated cochlear implant listening.

PubMed

Ihlefeld, Antje; Litovsky, Ruth Y

2012-01-01

Spatial release from masking refers to a benefit for speech understanding. It occurs when a target talker and a masker talker are spatially separated. In those cases, speech intelligibility for target speech is typically higher than when both talkers are at the same location. In cochlear implant listeners, spatial release from masking is much reduced or absent compared with normal hearing listeners. Perhaps this reduced spatial release occurs because cochlear implant listeners cannot effectively attend to spatial cues. Three experiments examined factors that may interfere with deploying spatial attention to a target talker masked by another talker. To simulate cochlear implant listening, stimuli were vocoded with two unique features. First, we used 50-Hz low-pass filtered speech envelopes and noise carriers, strongly reducing the possibility of temporal pitch cues; second, co-modulation was imposed on target and masker utterances to enhance perceptual fusion between the two sources. Stimuli were presented over headphones. Experiments 1 and 2 presented high-fidelity spatial cues with unprocessed and vocoded speech. Experiment 3 maintained faithful long-term average interaural level differences but presented scrambled interaural time differences with vocoded speech. Results show a robust spatial release from masking in Experiments 1 and 2, and a greatly reduced spatial release in Experiment 3. Faithful long-term average interaural level differences were insufficient for producing spatial release from masking. This suggests that appropriate interaural time differences are necessary for restoring spatial release from masking, at least for a situation where there are few viable alternative segregation cues.

Preliminary Results of Simulations and Field Investigations of the Performance of the WISDOM GPR of the ExoMars Rover

NASA Astrophysics Data System (ADS)

Ciarletti, V.; Corbel, C.; Cais, P.; Pltettemeier, D.; Hamran, S. E.; Oyan, M.; Clifford, S.; Reineix, A.

2009-04-01

WISDOM (Water Ice and Subsurface Deposit Observations on Mars) is a ground penetrat-ing radar (GPR) that was selected as one of three survey instruments on the ExoMars Rover Pasteur Payload. Its purpose is to characterize the nature of the shallow subsurface (including geological structure, electromagnetic properties, and potential hydrological state) and identify the most promising locations for investigation and sampling by the Rover's onboard drill - providing information down to a depth of 2 or 3 meters with a vertical resolution of a few centimeters (performance characteristics that will vary, depending on the local permittivity and conductivity of the subsurface). WISDOM is a polarimetric, step-frequency GPR operating over the frequency range of 0.5 - 3 GHz. The polarimetric capability of WISDOM is particularly useful for identifying and characterizing oriented structures like faults, fractures and stratigraphic interface roughness. To achieve this objective, special care has been dedicated to the design of the antenna system, which consists of a pair of Vivaldi antenna to conduct both co- and cross-polar measurements. WISDOM will perform its scientific investigations at each of the sites visited by the Rover and during the intervening traverses. During a traverse between two successive experiment cycles of the mission (drilling and sample analysis), WISDOM soundings will be performed to provide a coarse survey of the structure and nature of the underground and its large-scale variations. This information is required to understand the overall geological context and the properties of the subsurface. When a particular location has been selected for potential investigation by the drill, WISDOM will obtain subsurface profiles on a 2D grid, in order to synthesize a 3D map of subsurface soil characteristics and spatial variabil-ity. Full polarimetric soundings will be performed at 10 cm intervals along each parallel grid line, which will have a line-to-line spacing of 100cm. The typical grid-size for this 3D characterization is 5 m x 5 m. FDTD electromagntic simulations have been run on realistic Martian subsurface models to investigate the likely performances of the instrument once on Mars. In additiona, experi-mental field data was acquired during a 2008 mission to Svalabard, where the performance of the instrument in a permafrost environment was demonstrated. The results of that inves-tigation showed that WISDOM is capable of obtaining accurate data to depths in excess of 2-3 meters in ice-rich environments - successfully soundings through sediment layers, ice, and even into the underlying moraine, with sufficient spatial resolution to identify fine-scale layering within the intervening ice. Further results of these investigations will be presented at the meeting.

Atmospheric modeling of Mars CH4 subsurface clathrates releases mimicking SAM and 2003 Earth-based detections

NASA Astrophysics Data System (ADS)

Pla-García, J.; Rafkin, S. C.

2017-12-01

The aim of this work is to establish the amount of mixing during all martian seasons to test whether CH4 releases inside or outside of Gale crater are consistent with MSL-SAM observations. Several modeling scenarios were configured, including instantaneous and steady releases, both inside and outside the crater. A simulation to mimic the 2003 Earth-based detections (Mumma et al. 2009 or M09) was also performed. In the instantaneous release inside Gale experiments, Ls270 was shown to be the faster mixing season when air within and outside the crater was well mixed: all tracer mass inside the crater is diluted after just 8 hours. The mixing of near surface crater air with the external environment in the rest of the year is potentially rapid but slower than Ls270.In the instantaneous release outside Gale (NW) experiment, in just 12 hours the CH4 that makes it to the MSL landing location is diluted by six orders of magnitude. The timescale of mixing in MRAMS experiments is on the order of 1 sol regardless of season. The duration of the CH4 peak observed by SAM is 100 sols. Therefore there is a steady release inside the crater, or there is a very large magnitude steady release outside the crater. In the steady release Gale experiments, CH4 flux rate from ground is 1.8 kg m-2 s-1 (derived from Gloesener et al. 2017 clathrates fluxes) and it is not predictive. In these experiments, 200 times lower CH4 values detected by SAM are modeled around MSL location. There are CH4 concentration variations of orders of magnitude depending on the hour, so timing of SAM measurements is important. With a larger (but further away) outside crater release area compared to inside, similar CH4 values around MSL are modeled, so distance to source is important. In the steady experiments mimicking M09 detection release area, only 12 times lower CH4 values detected by SAM are modeled around MSL. The highest value in the M09 modeled scenario (0.6 ppbv) is reached in Ls270. This value is the highest of all modeled experiments. With our initial conditions (flux rates, release area size and distance to MSL), SAM should not be able (or very difficult) to detect CH4, but if we multiply flux by 12, increase the release area or move it closer to MSL (or all of above), it may be possible to get CH4 values that SAM could detect regardless where it comes from: inside, outside (close to) or far away from Gale.

An Idea for an Active Seismic Experiment on Mars in 2008

NASA Technical Reports Server (NTRS)

Lognonne, Ph.; Banerdt, B.; Giardini, D.; Costard, F.

2001-01-01

The detection of liquid water is of prime interest and should have deep implications in the understanding of the Martian hydrological cycle and also in exobiology. In the frame of the 2007 joint CNES-NASA mission to Mars, a set of 4 NETLANDERS developed by an European consortium is expected to be launched in June 2007. We propose to use a second spacecraft going or landing to Mars to release near one of the Netlander a series of artificial metallic meteorites, in order to perform an active seismic experiment providing a seismic profile of the crust and subsurface.

Investigating ebullition in a sand column using dissolved gas analysis and reactive transport modeling

USGS Publications Warehouse

Amos, Richard T.; Mayer, K. Ulrich

2006-01-01

Ebullition of gas bubbles through saturated sediments can enhance the migration of gases through the subsurface, affect the rate of biogeochemical processes, and potentially enhance the emission of important greenhouse gases to the atmosphere. To better understand the parameters controlling ebullition, methanogenic conditions were produced in a column experiment and ebullition through the column was monitored and quantified through dissolved gas analysis and reactive transport modeling. Dissolved gas analysis showed rapid transport of CH4 vertically through the column at rates several times faster than the bromide tracer and the more soluble gas CO2, indicating that ebullition was the main transport mechanism for CH4. An empirically derived formulation describing ebullition was integrated into the reactive transport code MIN3P allowing this process to be investigated on the REV scale in a complex geochemical framework. The simulations provided insights into the parameters controlling ebullition and show that, over the duration of the experiment, 36% of the CH4 and 19% of the CO2 produced were transported to the top of the column through ebullition.

Carbon Flux Signal Detection for the ASCENDS mission

NASA Astrophysics Data System (ADS)

Hammerling, D.; Michalak, A. M.; Kawa, S. R.; Doney, S. C.; Schaefer, K. M.

2012-12-01

Emerging satellite observations of carbon dioxide (CO2) offer novel and distinctive opportunities for quantifying the carbon cycle, which is an important scientific and societal challenge with anthropogenic CO2 emissions and accumulation rates in the atmosphere still on the rise. One mission in the planning stage is the Active Sensing of CO2 Emissions over Nights, Days, and Seasons (ASCENDS) mission, which is a laser CO2 sensing mission with an anticipated launch date around 2022. Notable features of this mission include the ability to sample at night and at high latitudes, which passive missions cannot do because of their reliance on reflected sunlight. In this work we present findings from signal detection studies, i.e. experiments that investigate if perturbations in carbon fluxes can be detected in the ASCENDS observations of atmospheric CO2 concentrations. The experiments employ a realistic synthetic-data setup using the PCTM/GEOS-5/CASA GFED CO2 flux and transport model in combination with CALIPSO and MODIS measurements. The signal detection approach applied uses a geostatistical mapping methodology that can leverage the information content of nearby observations, thereby potentially facilitating enhanced signal detection. The specific perturbation scenarios investigated are: carbon release from the melting of permafrost in the high Northern latitudes, the shifting of fossil fuel emissions from Europe to P.R. China, and natural variability in the CO2 fluxes in the Southern Ocean. Results indicate that the permafrost carbon release is comparatively easy to detect, while the Southern Ocean change is more challenging. The ability to detect a shift in fossil fuel emissions strongly depends on its magnitude: a 50% decrease in Europe is easily detectible, while a 20% decrease is only marginally so. A key conclusion is that the optimal signal detection strategy is intrinsically linked to how the carbon flux perturbations translate into atmospheric CO2 concentrations, which varies significantly among the investigated scenarios.

Carbon Cycling and pH regulation on the Scotian Shelf, NW Atlantic

NASA Astrophysics Data System (ADS)

Thomas, Helmuth

2015-04-01

This presentation intends to describe the biogeochemical context for ocean acidification studies on the Scotian Shelf. The seasonality of the dominant processes, regulating surface ocean CO2 conditions, including pH, will be assessed as well as cross-shelf transports of CO2, acidity and nutrient, the latter ones exerting the "subsurface control" of CO2 air-sea fluxes and surface pH. Methods summary: The seasonal variability of inorganic carbon in the surface waters of the Scotian Shelf region of the Canadian northwestern Atlantic Ocean was assessed using hourly measurements of the partial pressure of CO2 (pCO2), and hydrographic variables obtained by an autonomous moored instrument (44.3°N and 63.3°W). These measurements were complemented by seasonal shipboard sampling of dissolved inorganic carbon (DIC), total alkalinity (TA), and pCO2, at the mooring site, and over the larger spatial scale. The Scotian Shelf is a 700 km long section of the continental shelf off Nova Scotia. Bounded by the Laurentian Channel to the northeast, and by the Northeast Channel and the Gulf of Maine to the southwest, it varies in width from 120 to 240 km covering roughly 120,000 km2 with an average depth of 90 m . Convective mixin in winter time and coastal upwelling and the associated favorable wind conditions on the Scotian Shelf have long been recognized. Strong winds of speeds greater than 10 m s-1, blowing to the northeast, and persisting for several days force relatively cold, saline, water toward the surface, displacing the warmer, fresher water offshore. Upwelling events have frequently been observed in the region in winter, and modeling studies have reproduced these observed events. Furthermore, these events may play a role in initiating and sustaining the spring phytoplankton bloom by displacing nutrient-depleted surface water and bring nutrient-rich waters up to the surface. Biological processes were found to be the dominant control on mixed-layer DIC, with the delivery of carbon-rich subsurface waters also playing an important role. The region acts as a net source of CO2 to the atmosphere at the annual scale, with a reversal of this trend occurring only during the diatom dominated spring phytoplankton bloom, when a pronounced undersaturation of the surface waters is reached for a short period. During that time, the pH is at its annual maximum (pH≈8.15), while the Aragonite saturation state reaches its minimum just before the onset of the spring bloom in late March. After of the spring bloom period, the competing effects of temperature and biology influence surface pCO2 in roughly equal magnitude. During that time carbon fixation is driven by the smaller phytoplankton size classes, which can grow in warmer, nutrient poor conditions. In the Scotian Shelf region the summertime population these numerically abundant small cells accounts for approximately 10-20% of annual carbon uptake. The regional mean surface water pH is roughly 7.8 in April and increases to greater than 8.0 in September; subsurface pH is approximately 7.6 throughout the region and indicates a seasonal decrease due to the respiration of organic matter at depth. The surface aragonite saturation state increases from less than 2.0 to values as high as 3.2 between April and September; the region as a whole exhibits relatively low saturation states, however values approaching 1.0 were only observed in the Cabot Strait at depths below roughly 100m. Subsurface onshore gradients of CO2 and nutrient species yield onshore carbon, nutrient and hydrogen ion (H+) fluxes in subsurface waters, which in turn regulate surface pH and fuel the CO2 outgassing from the Scotian Shelf.

CO2 and CH4 Surface Flux, Soil Profile Concentrations, and Stable Isotope Composition, Barrow, Alaska, 2012-2013

DOE Data Explorer

Curtis, J.B.; Vaughn, L.S.; Torn, M.S.; Conrad, M.S.; Chafe, O.; Bill, M.

2015-12-31

In August-October 2012 and June-October 2013, co-located measurements were made of surface CH4 and CO2 flux, soil pore space concentrations and stable isotope compositions of CH4 and CO2, and subsurface temperature and soil moisture. Measurements were made in intensive study site 1 areas A, B, and C, and from the site 0 and AB transects, from high-centered, flat-centered, and low-centered polygons, from the center, edge, and trough of each polygon.

SOLID OXYGEN SOURCE FOR BIOREMEDIATION IN SUBSURFACE SOILS

EPA Science Inventory

Sodium percarbonate was encapsulated in poly(vinylidene chloride) to determine its potential as a slow-release oxygen source for biodegradation of contaminan ts in subsurface soils. In laboratory studies under aqueous conditions, the encapsulated sodium percarbonate was estimate...

The Frio Brine Pilot Experiment Managing CO2 Sequestration in a Brine Formation

NASA Astrophysics Data System (ADS)

Sakurai, S.

2005-12-01

Funded by the U.S. Department of Energy National Energy Technology Laboratory, the Frio Brine Pilot Experiment was begun in 2002. The increase in greenhouse gas emissions, such as carbon dioxide (CO2), is thought to be a major cause of climate change. Sequestration of CO2 in saline aquifers below and separate from fresh water is considered a promising method of reducing CO2 emissions. The objectives of the experiment are to (1) demonstrate CO2 can be injected into a brine formation safely; (2) measure subsurface distribution of injected CO2; (3) test the validity of conceptual, hydrologic, and geochemical models, and (4) develop experience necessary for larger scale CO2 injection experiments. The Bureau of Economic Geology (BEG) is the leading institution on the project and is collaborating with many national laboratories and private institutes. BEG reviewed many saline formations in the US to identify candidates for CO2 storage. The Frio Formation was selected as a target that could serve a large part of the Gulf Coast and site was selected for a brine storage pilot experiment in the South Liberty field, Dayton, Texas. Most wells were drilled in the 1950's, and the fluvial sandstone of the upper Frio Formation in the Oligocene is our target, at a depth of 5,000 ft. An existing well was used as the observation well. A new injection well was drilled 100 ft away, and 30 ft downdip from the observation well. Conventional cores were cut, and analysis indicated 32 to 35 percent porosity and 2,500 md permeability. Detailed core description was valuable as better characterization resulted in design improvements. A bed bisecting the interval originally thought to be a significant barrier to flow is a sandy siltstone having a permeability of about 100 md. As a result, the upper part of the sandstone was perforated. Because of changes in porosity, permeability, and the perforation zone, input for the simulation model was updated and the model was rerun to estimate timing of CO2 breakthrough and saturation changes. A pulsed neutron tool was selected as the primary wireline log for monitoring saturation changes, because of high formation water salinity, along with high porosity. Baseline logs were recorded as preinjection values. We started injection of CO2 on October 4, 2004, and injected 1,600 tons of CO2 for 10 days. Breakthrough of CO2 to the observation well was observed on the third day by geochemical measurement of recovered fluids, including gas analysis and decreased pH value. Multiple capture logs were run to monitor saturation changes. The first log run after CO2 breakthrough on the fourth day showed a significant decrease in sigma was recorded within the upper part of the porous section (6 ft) correlative with the injection interval. Postinjection logs were compared with baseline logs to determine CO2 distribution as CO2 migrated away from the injection point. The dipole acoustic tool was used to estimate saturation changes to improve geophysical data interpretation using VSP and crosswell tomography. Compared with the baseline log, wireline sonic log made 3 months later showed a weak and slower arrival of compressional wave over the perforated interval. Results from crosswell tomography data also showed changes in compressional velocity. Successful measurement of plume evolution documents an effective method to monitor CO2 in reservoirs and document migration.

Preparation and characterization of cross-linked excipient of coprocessed xanthan gum-acacia gum as matrix for sustained release tablets

NASA Astrophysics Data System (ADS)

Surini, Silvia; Wati, Dina Risma; Syahdi, Rezi Riadhi

2018-02-01

Sustained release tablet is solid dosage form which is designed to release drugs slowly in the body. This research was intended to prepare and characterize the cross-linked excipients of co-processed xanthan gum-acacia gum (CL-Co-XGGA) as matrices for sustained release tablets with gliclazide as a model drug. CL-Co-XGGA excipients were cross-linked materials of co-processed excipients of xanthan gum-acacia gum (Co-XGGA) using sodium trimetaphosphate. Co-processed excipients of xanthan gum-acacia gum were prepared in the ratio of each excipient 1:2, 1:1 and 2:1. Co-XGGA and CL-Co-XGGA excipients were characterized physically, chemically and functionally. Then, the sustained release (SR) tablets were formulated by wet granulation method using CL-Co-XGGA excipients as matrices. Also, the dissolution study of the gliclazide SR tablets was carried out in phosphate buffer medium pH 7,4 containing sodium lauryl sulphate 0.2% for 12 hours. The results showed that the degree of substitution (DS) of CL-Co-XGGA 1:2, 1:1, 2:1 excipients were respectively 0.067, 0.082 and 0.08. Besides that, the excipients gel strengths were 14.03, 17.27 and 20,70 gF, respectively. The cross-linked excipients had improved flow properties and swelling capability compared to the Co-XGGA excipients. The results of the gliclazide SR tablets evaluations showed that all tablets were passed all tablet requirements. Moreover, the gliclazide release from SR tablets F1 - F6 revealed the sustained release profile, which was following zero order kinetics (F1, F2, F3, F6) and Higuchi kinetics (F4 and F5). It could be concluded that the obtained CL-Co-XGGA excipients might be used as matrices for sustained release tablets and could retard drug release up to 8 until 32 hours.

Introducing a decomposition rate modifier in the Rothamsted Carbon Model to predict soil organic carbon stocks in saline soils.

PubMed

Setia, Raj; Smith, Pete; Marschner, Petra; Baldock, Jeff; Chittleborough, David; Smith, Jo

2011-08-01

Soil organic carbon (SOC) models such as the Rothamsted Carbon Model (RothC) have been used to estimate SOC dynamics in soils over different time scales but, until recently, their ability to accurately predict SOC stocks/carbon dioxide (CO(2)) emissions from salt-affected soils has not been assessed. Given the large extent of salt-affected soils (19% of the 20.8 billion ha of arable land on Earth), this may lead to miss-estimation of CO(2) release. Using soils from two salt-affected regions (one in Punjab, India and one in South Australia), an incubation study was carried out measuring CO(2) release over 120 days. The soils varied both in salinity (measured as electrical conductivity (EC) and calculated as osmotic potential using EC and water content) and sodicity (measured as sodium adsorption ratio, SAR). For soils from both regions, the osmotic potential had a significant positive relationship with CO(2)-C release, but no significant relationship was found between SAR and CO(2)-C release. The monthly cumulative CO(2)-C was simulated using RothC. RothC was modified to take into account reductions in plant inputs due to salinity. A subset of non-salt-affected soils was used to derive an equation for a "lab-effect" modifier to account for changes in decomposition under lab conditions and this modifier was significantly related with pH. Using a subset of salt-affected soils, a decomposition rate modifier (as a function of osmotic potential) was developed to match measured and modelled CO(2)-C release after correcting for the lab effect. Using this decomposition rate modifier, we found an agreement (R(2) = 0.92) between modelled and independently measured data for a set of soils from the incubation experiment. RothC, modified by including reduced plant inputs due to salinity and the salinity decomposition rate modifier, was used to predict SOC stocks of soils in a field in South Australia. The predictions clearly showed that SOC stocks are reduced in saline soils. Therefore both the decomposition rate modifier and plant input modifier should be taken into account when accounting for SOC turnover in saline soils. Since modeling has previously not accounted for the impact of salinity, our results suggest that previous predictions may have overestimated SOC stocks.

Microbially Induced Carbonate Precipitation: a Novel Grout for Permeability Control in Subsurface Engineering Works

NASA Astrophysics Data System (ADS)

Minto, J. M.; Hingerl, F.; Lunn, R. J.; Benson, S. M.

2016-12-01

ContextWe utilise the urea hydrolysing capability of soil bacteria Sporosarcina pasteurii to precipitate CaCO3 in a process termed Microbially Induced Carbonate Precipitation (MICP). MICP injection fluid properties are low particle size and low viscosity giving excellent grout penetrability. The CaCO3 grout has been shown to be effective at reducing permeability in porous and fractured media. MICP has consequently been proposed as an alternative to more traditional cement and chemical grouts, particularly in the fields of radioactive waste disposal and geological sequestration of CO2. This study investigates the role of fluid flow/CaCO3 feedback during precipitation and accelerated dissolution to better understand the longevity of an MICP grout under low pH environmental conditions such as found in a carbon sequestration reservoir. MethodsExperiments were conducted on a single Berea sandstone core in a high pressure core holder to characterise permeability, porosity and multiphase flow behaviour at sequestration reservoir temperature and pressure. Characterisation was carried out before MICP, after MICP, and after accelerated dissolution with hydrochloric acid. At each step the entire core was scanned in a medical x-ray CT scanner to spatially resolve (with a resolution of 0.5x0.5x1mm) the changes in porosity and saturation with CaCO3 precipitation and dissolution. Finally, the dried core was scanned with μ-CT at 30μm (full core) and 10μm (sub-volume) resolutions to investigate structural changes to the Berea at near pore scale. ResultsSix MICP treatment cycles over two days reduced core permeability from 886 mDarcy to 40 mDarcy with a greater reduction in porosity at the inlet. Dissolution with acid restored much of the porosity, but did not restore permeability to the same extent. Preferential flow paths formed during the dissolution step were visible in the first 4mm of the 100mm core, but did not extend further into the core. DiscussionThis study provides evidence that MICP can potentially produce a long lasting seal, even in challenging subsurface environments, provided that a thick enough layer of CaCO3 can be precipitated with a low initial permeability. Challenges remain for ensuring that such a barrier can be created in the subsurface and are the subject of further investigation.

Detection of Noble Gas Radionuclides from an Underground Nuclear Explosion During a CTBT On-Site Inspection

NASA Astrophysics Data System (ADS)

Carrigan, Charles R.; Sun, Yunwei

2014-03-01

The development of a technically sound approach to detecting the subsurface release of noble gas radionuclides is a critical component of the on-site inspection (OSI) protocol under the Comprehensive Nuclear Test Ban Treaty. In this context, we are investigating a variety of technical challenges that have a significant bearing on policy development and technical guidance regarding the detection of noble gases and the creation of a technically justifiable OSI concept of operation. The work focuses on optimizing the ability to capture radioactive noble gases subject to the constraints of possible OSI scenarios. This focus results from recognizing the difficulty of detecting gas releases in geologic environments—a lesson we learned previously from the non-proliferation experiment (NPE). Most of our evaluations of a sampling or transport issue necessarily involve computer simulations. This is partly due to the lack of OSI-relevant field data, such as that provided by the NPE, and partly a result of the ability of computer-based models to test a range of geologic and atmospheric scenarios far beyond what could ever be studied by field experiments, making this approach very highly cost effective. We review some highlights of the transport and sampling issues we have investigated and complete the discussion of these issues with a description of a preliminary design for subsurface sampling that addresses some of the sampling challenges discussed here.

Effect of layer thickness on the thermal release from Be-D co-deposited layers

NASA Astrophysics Data System (ADS)

Baldwin, M. J.; Doerner, R. P.

2014-08-01

The results of previous work (Baldwin et al 2013 J. Nucl. Mater. 438 S967-70 and Baldwin et al 2014 Nucl. Fusion 54 073005) are extended to explore the influence of layer thickness on the thermal D2 release from co-deposited Be-(0.05)D layers produced at ˜323 K. Bake desorption of layers of thickness 0.2-0.7 µm are explored with a view to examine the influence of layer thickness on the efficacy of the proposed ITER bake procedure, to be carried out at the fixed temperatures of 513 K on the first wall and 623 K in the divertor. The results of experiment and modelling with the TMAP-7 hydrogen transport code, show that thicker Be-D co-deposited layers are relatively more difficult to desorb (time-wise) than thinner layers with the same concentrations of intrinsic traps and retained hydrogen isotope fraction.

Biogeochemical characteristics of mesoscale eddies in the generation zone off Valparaíso, Chile

NASA Astrophysics Data System (ADS)

Villegas, Valerie; Cornejo, Marcela; Molina, Verónica; Silva, Nelson; Hormazábal, Samuel

2016-04-01

The coastal area off Valparaiso is characterized by an intense mesoscale activity associated with eddies, which transport highly productive-coastal waters to the oligotrophic areas of the Subtropical Gyre. Among these, the Intrathermocline Anticyclonic Eddies (ITE's) which are forming in the eastern South Pacific, transport low oxygen- and high nutrients- subsurface water of Equatorial Subsurface Water (ESSW). These eddies have been well characterized in terms of generation rate, direction, speed and water transport. However, biogeochemical conditions in their origin and its temporal variability are not well assessed. The present study aims to determine the variability, spatially and temporally, of the biogeochemical properties in the water column at the eddies generation zone, off Punta Ángeles, Valparaíso (33° S). For this, a monthly time series was conducted between January and August 2016 where a cross-shore transect with six-stations was deployed (from coast to 16 nm). Each station was sampled with CTD-OF, while only in station 5 (1300 m depth) was sampled in 16 depth for biogeochemical variables: nutrients (NO3-, NO2-, PO4-3, Si(OH)4), greenhouse gases (CO2, CH4 and N2O), chlorophyll a, stable isotopes in particulate organic material (13C, 15N), content of organic carbon and nitrogen in POM. The spatial and temporal distribution shows the presence of subsurface cores (100 - 300 m) with water with high salinity (> 34.7 psu) and low oxygen content (< 0.5 mLṡL-1), associated with mesoscale subsurface structures. The largest vertical and horizontal extension of these structures was observed in January 2015. These subsurface structures showed a significant deficit of reactive nitrogen (N* < -10 μM), nitrite accumulation (> 0.6 μM) and the highest supersaturations of CO2 (110 - 344%) and N2O (107 - 407%). Along with this, the eddies generation zone presented a temporal variability of air-sea gases fluxes with the highest in the austral summer and autumn (from 67.64 to 9.12 mmolṡm-2ṡd-1, from 3.00 to 0.94 μmolṡm-2ṡd-1, and from 19.62 to 5.77 μmolṡm-2ṡd-1, for CO2, CH4 and N2O, respectively), while between June and August, the ocean-atmosphere flows were close to equilibrium (from 0.09 to -1.93 mmolṡm-2ṡd-1, from 0.40 to 0.03 μmolṡm-2ṡd-1, and from 0,29 to -0.02 μmolṡm-2ṡd-1, for CO2, CH4 and N2O, respectively). Acknowledgment: This work is part of the PIA 037.474 Project (PUCV) and the Instituto Milenio de Oceanografía (IMO-Chile).

Thermal and Evolved Gas Analysis of "Nanophase" Carbonates: Implications for Thermal and Evolved Gas Analysis on Mars Missions

NASA Technical Reports Server (NTRS)

Lauer, Howard V., Jr.; Archer, P. D., Jr.; Sutter, B.; Niles, P. B.; Ming, Douglas W.

2012-01-01

Data collected by the Mars Phoenix Lander's Thermal and Evolved Gas Analyzer (TEGA) suggested the presence of calcium-rich carbonates as indicated by a high temperature CO2 release while a low temperature (approx.400-680 C) CO2 release suggested possible Mg- and/or Fe-carbonates [1,2]. Interpretations of the data collected by Mars remote instruments is done by comparing the mission data to a database on the thermal properties of well-characterized Martian analog materials collected under reduced and Earth ambient pressures [3,4]. We are proposing that "nano-phase" carbonates may also be contributing to the low temperature CO2 release. The objectives of this paper is to (1) characterize the thermal and evolved gas proper-ties of carbonates of varying particle size, (2) evaluate the CO2 releases from CO2 treated CaO samples and (3) examine the secondary CO2 release from reheated calcite of varying particle size.

Patch test reactivity to a cobalt-chromium-molybdenum alloy and stainless steel in metal-allergic patients in correlation to the metal ion release.

PubMed

Summer, Burkhard; Fink, Ulrich; Zeller, Richard; Rueff, Franziska; Maier, Sonja; Roider, Gabriele; Thomas, Peter

2007-07-01

Nickel, chromium, and cobalt released from stainless steel and CoCrMo alloys have been postulated to trigger hypersensitivity reactions. The objective of this study was to assess the ion release from a CoCrMo alloy and stainless steel in vitro and the cutaneous reactivity to it by patch test. 52 metal-allergic patients and 48 non-allergic controls were patch tested to stainless steel and CoCrMo discs. In addition, using atomic absorption spectrometry, the release of nickel, cobalt, and chromium from both materials was assessed upon 2-day exposure to distilled water, artificial sweat (AS), and cell culture medium. There was low nickel ion release from stainless steel (0.3-0.46 microg/cm(2)/2 days) and CoCrMo discs (up to 0.33 microg/cm(2)/2 days) into the different elution media. Chromium release from the 2 materials was also very low (0.06-0.38 microg/cm(2)/2 days from stainless steel and 0.52-1.36 microg/cm(2)/2 days from CoCrMo alloy). In contrast, AS led to abundant cobalt release (maximally 18.94 microg/cm(2)/2 days) from the CoCrMo discs, with concomitant eczematous reaction upon patch testing: 0 of the 52 metal-allergic patients reacted to stainless steel discs and 5 of the 52 patients to CoCrMo discs (all 5 patients were cobalt allergic and 3 also nickel and chromium allergic). None of the controls reacted to the discs. Apart from nickel being a focus of allergological research, our results point to the possibly underestimated association of cobalt release and potential hyperreactivity to CoCrMo alloy.

Acoustic Monitoring of Gravity-Driven Controls on CaCO3 Precipitates in a Fracture

NASA Astrophysics Data System (ADS)

Xu, Z.; Sheets, J.; Zhang, L.; Kim, D.; Kneafsey, T. J.; Cole, D. R.; Jun, Y. S.; Pyrak-Nolte, L. J.

2017-12-01

Sealing fractures by mineral precipitation is an important process for improving caprock integrity in subsurface reservoirs. In this study, the ability to monitor precipitate distribution in fractures with buoyant fluids was examined. Fractures with uniform aperture distributions of 0.5, 1.0 and 2.0 mm were created from acrylic plates to enable direct imaging of precipitate formation over time. CaCO3 precipitation was induced in a fracture from invasion of 1M CaCl2 and 0.3M Na2CO3 solutions. During chemical invasion, a fracture plane was oriented either parallel or perpendicular to gravity. Acoustic (P) wave transmission ( 1 MHz) and optical imaging were used to monitor the sample prior to, during and after fluid injection. Complementary X-ray computed tomography was performed throughout the experiments on vertical fractures and post injection for the horizontal fractures. Precipitate particle sizes during formation were determined using SAXS and WAXS. In both horizontal and vertical fractures, the density contrast between the two solutions affected the spatial distribution of precipitation. In vertical fractures, the denser CaCl2 solution almost completely displaced the NaCO3 solution, causing strong localization of precipitates. However, in the horizontal fractures, flow stratification occurred in the 2 mm aperture fractures, with the less dense Na2CO3 flowing over the CaCl2 solution, resulting in a more even distribution of precipitates cross the fracture plane. P-wave amplitudes increased up to 8% and the arrival time decreased with precipitate accumulation in the horizontal fracture. This is consistent with a three-layered approach as the seismic impedance inside the fracture increases. The initial contact between the two was observed as a decrease in the P-wave amplitude. As precipitates accumulated, the amplitude recovered and increased, with greater increases observed along the mixing flow path. Fractures in the subsurface may seal differently depending on the orientation thus affecting the ability of a fracture to self-heal if oriented vertically. This work was supported by the Center for Nanoscale Controls on Geologic CO (NCGC), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-AC02-05CH11231

Metal release and speciation of released chromium from a biomedical CoCrMo alloy into simulated physiologically relevant solutions.

PubMed

Hedberg, Yolanda; Odnevall Wallinder, Inger

2014-05-01

The objective of this study was to investigate the extent of released Co, Cr(III), Cr(VI), and Mo from a biomedical high-carbon CoCrMo alloy exposed in phosphate-buffered saline (PBS), without and with the addition of 10 µM H2 O2 (PBS + H2 O2 ), and 10 g L(-1) bovine serum albumin (PBS + BSA) for time periods up to 28 days. Comparative studies were made on AISI 316L for the longest time period. No Cr(VI) release was observed for any of the alloys in either PBS or PBS + H2 O2 at open-circuit potential (no applied potential). However, at applied potentials (0.7 V vs. Ag/AgCl), Cr was primarily released as Cr(VI). Co was preferentially released from the CoCrMo alloy at no applied potential. As a consequence, Cr was enriched in the utmost surface oxide reducing the extent of metal release over time. This passivation effect was accelerated in PBS + H2 O2 . As previously reported for 316L, BSA may also enhance metal release from CoCrMo. However, this was not possible to verify due to the precipitation of metal-protein complexes with reduced metal concentrations in solution as a consequence. This was particularly important for Co-BSA complexes after sufficient time and resulted in an underestimation of metals in solution. Copyright © 2013 Wiley Periodicals, Inc.

National Assessment of Geologic Carbon Dioxide Storage Resources -- Trends and Interpretations

NASA Astrophysics Data System (ADS)

Buursink, M. L.; Blondes, M. S.; Brennan, S.; Drake, R., II; Merrill, M. D.; Roberts-Ashby, T. L.; Slucher, E. R.; Warwick, P.

2013-12-01

In 2012, the U.S. Geological Survey (USGS) completed an assessment of the technically accessible storage resource (TASR) for carbon dioxide (CO2) in geologic formations underlying the onshore and State waters area of the United States. The formations assessed are at least 3,000 feet (914 meters) below the ground surface. The TASR is an estimate of the CO2 storage resource that may be available for CO2 injection and storage that is based on present-day geologic and hydrologic knowledge of the subsurface and current engineering practices. Individual storage assessment units (SAUs) for 36 basins or study areas were defined on the basis of geologic and hydrologic characteristics outlined in the USGS assessment methodology. The mean national TASR is approximately 3,000 metric gigatons. To augment the release of the assessment, this study reviews input estimates and output results as a part of the resource calculation. Included in this study are a collection of both cross-plots and maps to demonstrate our trends and interpretations. Alongside the assessment, the input estimates were examined for consistency between SAUs and cross-plotted to verify expected trends, such as decreasing storage formation porosity with increasing SAU depth, for instance, and to show a positive correlation between storage formation porosity and permeability estimates. Following the assessment, the output results were examined for correlation with selected input estimates. For example, there exists a positive correlation between CO2 density and the TASR, and between storage formation porosity and the TASR, as expected. These correlations, in part, serve to verify our estimates for the geologic variables. The USGS assessment concluded that the Coastal Plains Region of the eastern and southeastern United States contains the largest storage resource. Within the Coastal Plains Region, the storage resources from the U.S. Gulf Coast study area represent 59 percent of the national CO2 storage capacity. As part of this follow up study, additional maps were generated to show the geographic distribution of the input estimates and the output results across the U.S. For example, the distribution of the SAUs with fresh, saline or mixed formation water quality is shown. Also mapped is the variation in CO2 density as related to basin location and to related properties such as subsurface temperature and pressure. Furthermore, variation in the estimated SAU depth and resulting TASR are shown across the assessment study areas, and these depend on the geologic basin size and filling history. Ultimately, multiple map displays are possible with the complete data set of input estimates and range of reported results. The findings from this study show the effectiveness of the USGS methodology and the robustness of the assessment.

Further Studies on Oxalic Acid Biosynthesis in Oxalate-accumulating Plants 1

PubMed Central

Nuss, Richard F.; Loewus, Frank A.

1978-01-01

l-Ascorbic acid functions as a precursor of oxalic acid in several oxalate-accumulating plants. The present study extends this observation to include Rumex crispus L. (curly dock), Amaranthus retroflexus L. (red root pigweed), Chenopodium album L. (lamb's-quarters), Beta vulgaris L. (sugar beet), Halogeton glomeratus M. Bieb. (halogeton), and Rheum rhabarbarum L. (rhubarb). Several species with low oxalate content are also examined. When l-[1-14C]ascorbic acid is supplied to young seedlings of R. crispus or H. glomeratus, a major portion of the 14C is released over a 24-hour period as 14CO2 and only a small portion is recovered as [14C]oxalate, unlike cuttings from 2- or 4-month-old plants which retain a large part of the 14C as [14C]oxalic acid and release very little 14CO2. Support for an intermediate role of oxalate in the release of 14CO2 from l-[1-14C]ascorbic acid is seen in the rapid release of 14CO2 by R. crispus and H. glomeratus seedlings labeled with [14C]oxalic acid. The common origin of oxalic acid carbon in the C1 and C2 fragment from l-ascorbic acid is demonstrated by comparison of 14C content of oxalic acid in several oxalate-accumulators after cuttings or seedlings are supplied equal amounts of l-[1-14C]- or l-[UL-14C]ascorbic acid. Theoretically, l-[1-14C]ascorbic acid will produce labeled oxalic acid containing three times as much 14C as l-[UL-14C]ascorbic acid when equal amounts of label are provided. Experimentally, a ratio of 2.7 ± 0.5 is obtained in duplicate experiments with six different species. PMID:16660342

GeoEn -Research on Geo-Energy

NASA Astrophysics Data System (ADS)

Liebscher, A.; Scheck-Wenderoth, M.; GeoEn Research Group

2012-04-01

Axel Liebscher1, Magdalena Scheck-Wenderoth1 and the GeoEn Research Group1, 2,3 1 Helmholtz Centre Potsdam GFZ German Research Centre for Geosciences, Potsdam, Germany 2 University Potsdam, Germany 3 BTU Cottbus, Germany One of the pressing challenges for the 21st century is a secure, sustainable and economical energy supply at simultaneous mitigation of its climate impact. Besides a switch to renewable energy resources, the exploration and exploitation of new, unconventional energy resources will play a major role as will the further use of fossil fuels. With the switch to renewable energies the question of geological energy storage will become an important topic whereas further use of fossil fuels requires strategies like CCS to reduce its negative climate impacts. These different aspects of geo-energy make complementary or competitive demands on the subsurface and its use. It is therefore essential to treat the subsurface as a geo-resource of its own right. So far, geo-resource related research has often focused on specific resource systems, e.g. ore forming systems, hydrocarbon systems or geothermal systems, providing results largely applicable only to the restricted range of physicochemical properties of the respective geo-resource systems. However, with the increasing use of the subsurface as important geo-resource, the different geo-resource systems tend to overlap and interact and also become much more complex due to the additional use or presence of artificial and technical matter, as is the case in geological CO2 storage. On the other hand, the combined use of the subsurface for different purposes may also create synergetic effects. GeoEn is a joint research project explicitly addressing the fundamental questions related to the sustainable and holistic use of the geo-resource subsurface with a special focus on geo-energy. Project partners are the German Research Centre for Geosciences (GFZ), the University of Potsdam (UP) and the Brandenburg University of Technology (BTU). GeoEn research addresses CO2 capture, transport and utilization, CO2 storage, the unconventional energy resource shale gas and geothermal technologies. These four core topics are studied in an integrated approach using the synergy of cross-cutting themes. The latter encompass new exploration and reservoir technologies as well as innovative monitoring methods, both complemented by numerical simulations of the relevant processes including flow dynamics or heat transfer in the subsurface and along the technological process chains. Accordingly, synergies derived from the cross-cutting topics improve both methodological development applicable in equal measure to the utilization of geothermal energy and of shale gas as well as to the use and monitoring of CO2 storage. Complementary, new modelling approaches are developed that allow the simulation of involved processes to predict the occurrence and physical properties of potential reservoirs and the changes that may be induced by their utilization. We present first results with respect to exploration strategies, monitoring technologies and modeling approaches for the pilot storage site for CO2 in Ketzin and the geothermal research platform Groß-Schönebeck, where the respective technologies are tested and monitored.

The Role of Alpine Wetlands as Hot Spots of Dissolved Organic Carbon Fluxes in the East River, Colorado

NASA Astrophysics Data System (ADS)

Winnick, M.; Rainaldi, G. R.; Lawrence, C. R.; McCormick, M. E.; Hsu, H. T.; Druhan, J. L.; Williams, K. H.; Maher, K.

2016-12-01

Dissolved organic carbon (DOC) is a critical chemical attribute of freshwater systems, affecting nutrient availability, toxicity and solubility of metals, and biological activity via the absorption of light and microbial consumption of O2 during DOC mineralization. Although DOC contributions to streams are distributed across the landscape in the shallow subsurface, many studies have demonstrated area-outsized contributions from riparian zones with high biological productivity and low subsurface O2 concentrations. In the East River, CO, a high-elevation watershed located in the central Rocky Mountains, initial observations show that DOC concentrations of two tributaries, Rock Creek and Gothic Creek, are elevated by 3-10 times compared to concentrations in the main East River and its other tributaries. These elevated concentrations are qualitatively linked to the unique presence of large wetlands in the headwaters of Rock and Gothic creeks, which due to potential anoxic conditions, experience reduced rates of organic matter decomposition and serve as an elevated source of DOC. In this study we quantify the cycling of organic matter in these alpine wetlands and their area-outsized contributions to East River DOC fluxes. We present concentration profiles of DOC along stream reaches and along subsurface flowpaths that span the transition from hillslope to wetland coupled with high-resolution mapping of chronically-saturated zones and calculate area-weighted fluxes of DOC from wetlands to Rock and Gothic creeks at multiple times through the 2016 growing season. Additionally, soil and groundwater DOC fluxes are compared with depth-resolved organic carbon content from soil cores, substrate quality (C:N), and soil surface CO2 fluxes to evaluate organic carbon budgets in the hillslope and wetland areas feeding Rock Creek. The characterization of these hotspots of DOC generation and transport in the East River is vital to the ability to predict nutrient cycling changes into the future.

Photodecomposition of Mo(CO)/sub 6/ adsorbed on Si(100)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Creighton, J.R.

1986-01-15

The photochemical properties of Mo(CO)/sub 6/ adsorbed on Si(100) were investigated using temperature programmed desorption (TPD) and Auger spectroscopy. TPD experiments indicate that Mo(CO)/sub 6/ physisorbs on silicon and desorbs at 210--230 K. At 150 K, KrF laser radiation (248 nm) partially decomposes the adsorbed Mo(CO)/sub 6/ releasing gas-phase CO in the process and TPD experiments after irradiation show that additional CO desorbs at 335 K. However, Auger analysis indicates that one CO molecule per molybdenum atom dissociates, leaving the molybdenum overlayer heavily contaminated with carbon and oxygen. The cross section for photodecomposition was measured to be 5 +- 3more » x 10/sup -17/ cm/sup 2/. Decomposition of the excited molecule must compete strongly with energy relaxation to account for the magnitude of this cross section.« less

Organic Combustion in the Presence of Ca-Carbonate and Mg-Perchlorate: A Possible Source for the Low Temperature CO2 Release Seen in Mars Phoenix Thermal and Evolved Gas Analyzer Data

NASA Technical Reports Server (NTRS)

Archer, Douglas; Ming, D.; Niles, P.; Sutter, B.; Lauer, H.

2012-01-01

Two of the most important discoveries of the Phoenix Lander were the detection of approx.0.6% perchlorate [1] and 3-5% carbonate [2] in landing site soils. The Thermal and Evolved Gas Analyzer (TEGA) instrument on the Phoenix lander could heat samples up to approx.1000 C and monitor evolved gases with a mass spectrometer. TEGA detected a low (approx.350 C) and high (approx.750 C) temperature CO2 release. The high temp release was attributed to the thermal decomposition of Ca-carbonate (calcite). The low temperature CO2 release could be due to desorption of CO2, decomposition of a different carbonate mineral, or the combustion of organic material. A new hypothesis has also been proposed that the low temperature CO2 release could be due to the early breakdown of calcite in the presence of the decomposition products of certain perchlorate salts [3]. We have investigated whether or not this new hypothesis is also compatible with organic combustion. Magnesium perchlorate is stable as Mg(ClO4)2-6H2O on the martian surface [4]. During thermal decomposition, this perchlorate salt releases H2O, Cl2, and O2 gases. The Cl2 can react with water to form HCl which then reacts with calcite, releasing CO2 below the standard thermal decomposition temperature of calcite. However, when using concentrations of perchlorate and calcite similar to what was detected by Phoenix, the ratio of high:low temperature CO2 evolved is much larger in the lab, indicating that although this process might contribute to the low temp CO2 release, it cannot account for all of it. While H2O and Cl2 cause calcite decomposition, the O2 evolved during perchlorate decomposition can lead to the combustion of any reduced carbon present in the sample [5]. We investigate the possible contribution of organic molecules to the low temperature CO2 release seen on Mars.

Fast-moving dislocations trigger flash weakening in carbonate-bearing faults during earthquakes.

PubMed

Spagnuolo, Elena; Plümper, Oliver; Violay, Marie; Cavallo, Andrea; Di Toro, Giulio

2015-11-10

Rupture fronts can cause fault displacement, reaching speeds up to several ms(-1) within a few milliseconds, at any distance away from the earthquake nucleation area. In the case of silicate-bearing rocks the abrupt slip acceleration results in melting at asperity contacts causing a large reduction in fault frictional strength (i.e., flash weakening). Flash weakening is also observed in experiments performed in carbonate-bearing rocks but evidence for melting is lacking. To unravel the micro-physical mechanisms associated with flash weakening in carbonates, experiments were conducted on pre-cut Carrara marble cylinders using a rotary shear apparatus at conditions relevant to earthquakes propagation. In the first 5 mm of slip the shear stress was reduced up to 30% and CO2 was released. Focused ion beam, scanning and transmission electron microscopy investigations of the slipping zones reveal the presence of calcite nanograins and amorphous carbon. We interpret the CO2 release, the formation of nanograins and amorphous carbon to be the result of a shock-like stress release associated with the migration of fast-moving dislocations. Amorphous carbon, given its low friction coefficient, is responsible for flash weakening and promotes the propagation of the seismic rupture in carbonate-bearing fault patches.

Biogenic hydrogen peroxide as a possible adaptation of life on Mars: the search for biosignatures

NASA Astrophysics Data System (ADS)

Houtkooper, J. M.; Schulze-Makuch, D.

2007-08-01

The hypothesis that putative Martian organisms incorporate H2O2 into their intracellular liquids (Houtkooper and Schulze-Makuch, 2007) has significant implications, as it explains the Viking observations quite well; it provides a functional adaptation to Martian environmental conditions; and, it is feasible as an adaptation based on the biochemistry of terrestrial organisms. It would explain many of the puzzling Viking observations such as (1) the lack of organics detected by GC-MS, (2) the lack of detected oxidant(s) to support a chemical explanation, (3) evolution of O2 upon wetting (GEx experiment), (4) limited organic synthesis reactions (PR experiment), and (5) the gas release observations made (LR experiment). An intracellular liquid containing a high concentration of H2O2 has advantages such as providing a low freezing point, a source of oxygen, and hygroscopicity, allowing an organism to obtain water vapor from the Martian atmosphere or from the adsorbed layers of water molecules on mineral grains. Perhaps surprisingly, H2O2 is used by many terrestrial organisms for diverse purposes, e.g., metabolism (Acetobacter peroxidans), as defense mechanism (Bombardier beetle), and also to mediate diverse physiological responses such as cell proliferation, differentiation, and migration. The detection of H2O2-containing organisms may well suffer from the same problems as the Viking experiments: Because of the excess oxidative contents, as derived from the GEx experiment, the organisms may decompose completely into H2O, CO2, O2 and N2. This can happen when exposed to an excess of water vapor (through hyperhydration), too high a temperature or a combination of both. Therefore, the addition of too much water vapor may be fatal. Moreover, employing pyrolysis in order to detect organic molecules may result in the organisms autooxidizing completely. Although the instrument suite aboard the Phoenix Lander offers some interesting possibilities (Schulze-Makuch and Houtkooper, 2007), it may be interesting to consider possible biosignatures in the environment, based on what might be inferred from the putative organisms. The metabolism is constrained by the necessity to produce an excess of H2O2 from the environment and the release of possible metabolites. The production of H2O2 can be realized from the available constituents in the atmosphere, CO2, H2O and O2. The last two components are present as a small fraction of the Martian atmosphere, but so is CO2 in Earth's atmosphere. Possible overall metabolic pathways are: CO2 + 3 H2O !CH2O + 2 H2O2(1) CO2 + 6 H2O !CH4 + 4 H2O2(2) CO2 + H2O !CO + H2O2(3) O2 + 2 H2O !2 H2O2(4) These pathways produce the following metabolites: (1) either organic macromolecules, which stay in or at the organisms, or, formaldehyde, released into the atmosphere; (2) methane, released into the atmosphere; (3) carbon monoxide, released into the atmosphere; and (4) only H2O2; this last pathway is energetically the least costly way to produce H2O2, despite O2 being a minor component (0.1%) of the atmosphere. As the amount of biomass in the Martian soil could be as high as 1300 ppm (Houtkooper and Schulze-Makuch, 2007), it might be possible to detect seasonal variations in the metabolic endproducts of formaldehyde, CH4, CO and O2. Even more interesting would be the observation of local variations in the surface boundary layer, in which diurnal rhythms might be revealed. Since a metabolic pathway would be involved, an additional signature could be the isotopic ratios of carbon and oxygen. Continuous monitoring of the composition, especially of the minor constituents of the atmosphere should therefore have a high priority in future missions to Mars, especially lander missions. Other signatures to be watched for are the spectral absorption of pigments providing UV shielding and photosynthesis. References: Houtkooper, J.M., and Schulze-Makuch, D. (2007) A Possible Biogenic Origin for Hydrogen Peroxide on Mars: The Viking Results Reinterpreted. In press at Int. J. of Astrobiology. Schulze-Makuch, D., and Houtkooper, J.M. (2007) Martian Extremophiles? The H2O-H2O2 Hypothesis and Its Implications for the Mars Phoenix Mission. LPSC XXXVIII, abstract #1171.

Mineral dissolution and secondary precipitation on quartz sand in simulated Hanford tank solutions affecting subsurface porosity

NASA Astrophysics Data System (ADS)

Wang, Guohui; Um, Wooyong

2012-11-01

Highly alkaline nuclear waste solutions have been released from underground nuclear waste storage tanks and pipelines into the vadose zone at the US Department of Energy's Hanford Site in Washington, causing mineral dissolution and re-precipitation upon contact with subsurface sediments. High pH caustic NaNO3 solutions with and without dissolved Al were reacted with quartz sand through flow-through columns stepwise at 45, 51, and 89 °C to simulate possible reactions between leaked nuclear waste solution and primary subsurface mineral. Upon reaction, Si was released from the dissolution of quartz sand, and nitrate-cancrinite [Na8Si6Al6O24(NO3)2] precipitated on the quartz surface as a secondary mineral phase. Both steady-state dissolution and precipitation kinetics were quantified, and quartz dissolution apparent activation energy was determined. Mineral alteration through dissolution and precipitation processes results in pore volume and structure changes in the subsurface porous media. In this study, the column porosity increased up to 40.3% in the pure dissolution column when no dissolved Al was present in the leachate, whereas up to a 26.5% porosity decrease was found in columns where both dissolution and precipitation were observed because of the presence of Al in the input solution. The porosity change was also confirmed by calculation using the dissolution and precipitation rates and mineral volume changes.

Differential retention and release of CO 2 and CH 4 in kerogen nanopores: Implications for gas extraction and carbon sequestration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ho, Tuan Anh; Wang, Yifeng; Xiong, Yongliang

Methane (CH 4) and carbon dioxide (CO 2), the two major components generated from kerogen maturation, are stored dominantly in nanometer-sized pores in shale matrix as (1) a compressed gas, (2) an adsorbed surface species and/or (3) a species dissolved in pore water (H 2O). In addition, supercritical CO 2 has been proposed as a fracturing fluid for simultaneous enhanced oil/gas recovery (EOR) and carbon sequestration. A mechanistic understanding of CH 4-CO 2-H 2O interactions in shale nanopores is critical for designing effective operational processes. Using molecular simulations, we show that kerogen preferentially retains CO 2 over CH 4 andmore » that the majority of CO 2 either generated during kerogen maturation or injected in EOR will remain trapped in the kerogen matrix. The trapped CO 2 may be released only if the reservoir pressure drops below the supercritical CO 2 pressure. When water is present in the kerogen matrix, it may block CH 4 release. Furthermore, the addition of CO 2 may enhance CH 4 release because CO 2 can diffuse through water and exchange for adsorbed methane in the kerogen nanopores.« less

Differential retention and release of CO 2 and CH 4 in kerogen nanopores: Implications for gas extraction and carbon sequestration

DOE PAGES

Ho, Tuan Anh; Wang, Yifeng; Xiong, Yongliang; ...

2018-02-06

Methane (CH 4) and carbon dioxide (CO 2), the two major components generated from kerogen maturation, are stored dominantly in nanometer-sized pores in shale matrix as (1) a compressed gas, (2) an adsorbed surface species and/or (3) a species dissolved in pore water (H 2O). In addition, supercritical CO 2 has been proposed as a fracturing fluid for simultaneous enhanced oil/gas recovery (EOR) and carbon sequestration. A mechanistic understanding of CH 4-CO 2-H 2O interactions in shale nanopores is critical for designing effective operational processes. Using molecular simulations, we show that kerogen preferentially retains CO 2 over CH 4 andmore » that the majority of CO 2 either generated during kerogen maturation or injected in EOR will remain trapped in the kerogen matrix. The trapped CO 2 may be released only if the reservoir pressure drops below the supercritical CO 2 pressure. When water is present in the kerogen matrix, it may block CH 4 release. Furthermore, the addition of CO 2 may enhance CH 4 release because CO 2 can diffuse through water and exchange for adsorbed methane in the kerogen nanopores.« less

Hyperspectral detection of a subsurface CO2 leak in the presence of water stressed vegetation.

PubMed

Bellante, Gabriel J; Powell, Scott L; Lawrence, Rick L; Repasky, Kevin S; Dougher, Tracy

2014-01-01

Remote sensing of vegetation stress has been posed as a possible large area monitoring tool for surface CO2 leakage from geologic carbon sequestration (GCS) sites since vegetation is adversely affected by elevated CO2 levels in soil. However, the extent to which remote sensing could be used for CO2 leak detection depends on the spectral separability of the plant stress signal caused by various factors, including elevated soil CO2 and water stress. This distinction is crucial to determining the seasonality and appropriateness of remote GCS site monitoring. A greenhouse experiment tested the degree to which plants stressed by elevated soil CO2 could be distinguished from plants that were water stressed. A randomized block design assigned Alfalfa plants (Medicago sativa) to one of four possible treatment groups: 1) a CO2 injection group; 2) a water stress group; 3) an interaction group that was subjected to both water stress and CO2 injection; or 4) a group that received adequate water and no CO2 injection. Single date classification trees were developed to identify individual spectral bands that were significant in distinguishing between CO2 and water stress agents, in addition to a random forest classifier that was used to further understand and validate predictive accuracies. Overall peak classification accuracy was 90% (Kappa of 0.87) for the classification tree analysis and 83% (Kappa of 0.77) for the random forest classifier, demonstrating that vegetation stressed from an underground CO2 leak could be accurately discerned from healthy vegetation and areas of co-occurring water stressed vegetation at certain times. Plants appear to hit a stress threshold, however, that would render detection of a CO2 leak unlikely during severe drought conditions. Our findings suggest that early detection of a CO2 leak with an aerial or ground-based hyperspectral imaging system is possible and could be an important GCS monitoring tool.

Hyperspectral Detection of a Subsurface CO2 Leak in the Presence of Water Stressed Vegetation

PubMed Central

Bellante, Gabriel J.; Powell, Scott L.; Lawrence, Rick L.; Repasky, Kevin S.; Dougher, Tracy

2014-01-01

Remote sensing of vegetation stress has been posed as a possible large area monitoring tool for surface CO2 leakage from geologic carbon sequestration (GCS) sites since vegetation is adversely affected by elevated CO2 levels in soil. However, the extent to which remote sensing could be used for CO2 leak detection depends on the spectral separability of the plant stress signal caused by various factors, including elevated soil CO2 and water stress. This distinction is crucial to determining the seasonality and appropriateness of remote GCS site monitoring. A greenhouse experiment tested the degree to which plants stressed by elevated soil CO2 could be distinguished from plants that were water stressed. A randomized block design assigned Alfalfa plants (Medicago sativa) to one of four possible treatment groups: 1) a CO2 injection group; 2) a water stress group; 3) an interaction group that was subjected to both water stress and CO2 injection; or 4) a group that received adequate water and no CO2 injection. Single date classification trees were developed to identify individual spectral bands that were significant in distinguishing between CO2 and water stress agents, in addition to a random forest classifier that was used to further understand and validate predictive accuracies. Overall peak classification accuracy was 90% (Kappa of 0.87) for the classification tree analysis and 83% (Kappa of 0.77) for the random forest classifier, demonstrating that vegetation stressed from an underground CO2 leak could be accurately discerned from healthy vegetation and areas of co-occurring water stressed vegetation at certain times. Plants appear to hit a stress threshold, however, that would render detection of a CO2 leak unlikely during severe drought conditions. Our findings suggest that early detection of a CO2 leak with an aerial or ground-based hyperspectral imaging system is possible and could be an important GCS monitoring tool. PMID:25330232

Coenzyme Q10 inhibits the release of glutamate in rat cerebrocortical nerve terminals by suppression of voltage-dependent calcium influx and mitogen-activated protein kinase signaling pathway.

PubMed

Chang, Yi; Huang, Shu-Kuei; Wang, Su-Jane

2012-12-05

This study investigates the effects and possible mechanism of coenzyme Q10 (CoQ10) on endogenous glutamate release in the cerebral cortex nerve terminals of rats. CoQ10 inhibited the release of glutamate evoked by the K+ channel blocker 4-aminopyridine (4-AP). CoQ10 reduced the depolarization-induced increase in cytosolic [Ca2+]c but did not alter the 4-AP-mediated depolarization. The effect of CoQ10 on evoked glutamate release was abolished by blocking the Cav2.2 (N-type) and Cav2.1 (P/Q-type) Ca2+ channels and mitogen-activated protein kinase kinase (MEK). In addition, CoQ10 decreased the 4-AP-induced phosphorylation of extracellular signal-regulated kinase 1 and 2 (ERK1/2) and synaptic vesicle-associated protein synapsin I, a major presynaptic substrate for ERK. Moreover, the inhibition of glutamate release by CoQ10 was strongly attenuated in mice without synapsin I. These results suggest that CoQ10 inhibits glutamate release from cortical synaptosomes in rats through the suppression of the presynaptic voltage-dependent Ca2+ entry and ERK/synapsin I signaling pathway.

Dissolution rates of subsoil limestone in a doline on the Akiyoshi-dai Plateau, Japan: An approach from a weathering experiment, hydrological observations, and electrical resistivity tomography

NASA Astrophysics Data System (ADS)

Akiyama, Sanae; Hattanji, Tsuyoshi; Matsushi, Yuki; Matsukura, Yukinori

2015-10-01

This study aims at estimating the controlling factors for the denudation rates of limestone, which often forms solution dolines on karst tablelands. Our approaches include (1) electrical resistivity tomography (ERT) to reveal shallow subsurface structures and hydrological settings, (2) automated monitoring of volumetric water content in soil profiles and manual measurements of subsurface CO2 concentrations and soil water chemistry, and (3) a field weathering experiment using limestone tablets with the micro-weight loss technique for determining current denudation rates. The field experiment and monitoring were carried out over 768 days from 2009-2011 at four sites with varying topographic and hydrological conditions along the sideslope of a doline on the Akiyoshi-dai karst plateau in SW-Japan. The installation depths of the limestone tablets were 15 cm or 50 cm below the slope surface. The soil moisture conditions varied site by site. Water-saturated conditions continued for 40-50% of the whole experimental period at 50-cm depth of upper and middle sites, while only 0-10% of the experimental period was water-saturated at the other sites. Chemical analysis revealed that the soil water was chemically unsaturated with calcite for all the sites. Spatial differences in concentrations of CO2 in soil pore air were statistically less significant. The denudation rates of the buried limestone tablets were 17.7-21.9 mg cm- 2 a- 1 at the upper and middle slopes, where the soil was water-saturated for a long time after precipitation. The lowest denudation of 3.9 mg cm- 2 a- 1 was observed on lower slopes where soil was not capable of maintaining water at a near saturation level even after precipitation. Statistical analysis revealed that the denudation rates of the tablets were strongly controlled by the duration for which soil pores were saturated by water (the conditions defined here are degrees of water saturation greater than 97%). Electrical resistivity tomography indicated that areas with high soil moisture conditions were located at the deeper zone on the lower slopes and the bottom of the doline, where denudation would be faster.

An Experimental Study of Effects in Soils by Potential CO2 Seepage

NASA Astrophysics Data System (ADS)

Wei, Y.; Caramanna, G.; Nathanail, P.; Steven, M.; Maroto-Valer, M.

2011-12-01

Potential CO2 seepage during a CCS project will not only reduce its performing efficiency, but can also impact the local environment. Though scientists announce with confidence that CCS is a safe technology to store CO2 deep underground, it is essential to study the effects of CO2 seepage, to avoid any possible influences on soils. As a simplified environment, laboratory experiments can easily be controlled and vital to be studied to be compared with more complex natural analogues and modelling works. Recent research focuses on the effects on ecosystems of CO2 leakage. However, the impacts of long-term, low level exposure for both surface and subsurface ecosystems, as well as soil geochemistry changes are currently not clear. Moreover, previous work has focussed on pure CO2 leakage only and its impacts on the ecosystem. However, in a more realistic scenario the gas coming from a capture process may contain impurities, such as SO2, which are more dangerous than pure CO2 and could cause more severe consequences. Therefore, it is critical to assess the potential additional risks caused by CO2 leakage with impurities. Accordingly, both a batch and a continuous flow reactor were designed and used to study potential impacts caused by the CO2 seepage, focusing on soil geochemistry changes, due to different concentrations of CO2/SO2 mixtures. Stage 1- Batch experiments. In this stage, a soil sample was collected from the field and exposed to a controlled CO2/SO2 gas mixtures (100% CO2 and CO2:SO2=99:1). The water soluble fractions were measured before and after incubation. With 100% CO2 incubation it was found that: 1) the pH in the soil sample did not change significantly; 2) for soils with different moisture levels, greater moisture in the soil results in higher CO2 uptake during incubation; and 3) for sandy soils, small changes in CaCl2-exchangeable metal concentration, were observed after CO2 incubation. However, the increased concentration of toxic elements is still below plant tolerance limits. With a gas mixture of 99% CO2 and 1% SO2, it was found that: 1) pH changed significantly from 5.54 to ~3.00; 2) consistent but minor changes were found in some of the nutrients; and 3) high concentrations of the toxic element, Al, were found, at approximately ~200 mg/l compared to an initial value of <0.1 mg/l. Stage 2- A continuous flow reactor. At this stage, a continuous vertical flow reactor was designed and used to assess the impact in soil caused by different mixtures of CO2/SO2. With limestone sand and 100% CO2, it was found that: 1) pH dropped quickly at the first hour and stabilised around 6.10 until CO2 injecting was stopped; 2) limestone had strong buffering capacity but only after stopping CO2 injection; 3) a change was found for soil permeability and porosity during the gas injecting process; 4) with saturated soil, a dome was always formed at the top of the soil column at the end of each experiment. More experiments are planned in the near future.

Surface electrical properties experiment study phase, volume 2

NASA Technical Reports Server (NTRS)

1973-01-01

The choice of an antenna for a subsurface radio sounding experiment is discussed. The radiation properties of the antennas as placed on the surface of the medium is examined. The objective of the lunar surface electrical properties experiment is described. A numerical analysis of the dielectric permittivity and magnetic permeability of a subsurface domain is developed. The application of electromagnetic field measurements between one or more transmitting antennas and a roving receiving station is explained.

New stable isotope results for reservoir and above zone monitoring in CCS from the Ketzin pilot site, Germany

NASA Astrophysics Data System (ADS)

Nowak, Martin; van Geldern, Robert; Myrttinen, Anssi; Veith, Becker; Zimmer, Martin; Barth, Johannes

2013-04-01

With rising atmospheric greenhouse gas concentrations, CCS technologies are a feasible option to diminish consequences of uncontrolled anthropogenic CO2 emissions and related climate change. However, application of CCS technologies requires appropriate and routine monitoring tools in order to ensure a safe and effective CO2 injection. Stable isotope techniques have proven as a useful geochemical monitoring tool at several CCS pilot projects worldwide. They can provide important information about gas - water - rock interactions, mass balances and CO2 migration in the reservoir and may serve as a tool to detect CO2 leakage in the subsurface and surface. Since the beginning of injection in 2008 at the Ketzin pilot site in Germany, more than 450 samples of fluids and gases have been analysed for their carbon and oxygen isotopic composition. Analytical advancements were achieved by modifying a conventional isotope ratio mass-spectrometer with a He dilution system. This allowed analyses of a larger number of CO2 gas samples from the injection well and observation wells. With this, a high-resolution monitoring program was established over a time period of one year. Results revealed that two isotopical distinct kinds of CO2 are injected at the Ketzin pilot site. The most commonly injected CO2 is so-called 'technical' CO2 with an average carbon isotopic value of about -31 ‰. Sporadically, natural source CO2 with an average δ13C value of -3 ‰ was injected. The injection of natural source CO2 generated a distinct isotope signal at the injection well that can be used as an ideal tracer. CO2 isotope values analysed at the observation wells indicate a highly dispersive migration of the supercritical CO2 that results in mixing of the two kinds of CO2 within the reservoir. Above-reservoir monitoring includes the first overlying aquifer above the cap rock. An observation well within this zone comprises an U-tube sampling device that allows frequent sampling of unaltered brine. The fluids were analysed among others for their carbon isotopic compositions of dissolved inorganic carbon (DIC). δ13CDIC values allowed to assess impacts of the carbonate-based drilling fluid during well development and helped to monitor successive geochemical re-equilibration processes of the brine. Based on the determined δ13C baseline values of the aquifer fluid, first concepts indicate the scale of change of the δ13CDIC values that would be necessary to detect CO2 leakage from the underlying storage reservoir. Recent efforts aim at applications of new laser-based isotope sensors that allow online measurements in the field. These devices are applied for CO2 gas tracer experiments as well as for monitoring of isotope composition of soil gases in the vicinity of the pilot site. This new development will allow much better temporal and spatial resolution of measurements at a lower price. Therefore, stable isotope analyses can become a strong and promising tool for subsurface as well as surface monitoring at future CCS sites.

Biosolids affect soil barium in a dryland wheat agroecosystem.

PubMed

Ippolito, J A; Barbarick, K A

2006-01-01

In December 2003, the USEPA released an amended list of 15 "candidate pollutants for exposure and hazard screening" with regard to biosolids land application, including Ba. Therefore, we decided to monitor soil Ba concentrations from a dryland wheat (Triticum aestivum L.)-fallow agroecosystem experiment. This experiment received 10 biennial biosolids applications (1982-2003) at rates from 0 to 26.8 dry Mg ha(-1) per application year. The study was conducted on a Platner loam (Aridic Paleustoll), approximately 30 km east of Brighton, CO. Total soil Ba, as measured by 4 M HNO(3), increased with increasing biosolids application rate. In the soil-extraction data from 1988 to 2003, however, we observed significant (P < 0.10) linear or exponential declines in ammonium bicarbonate-diethylenetriaminepentaacetic acid (AB-DTPA) extractable Ba concentrations as a function of increasing biosolids application rates. This was observed in 6 of 7 and 3 of 7 yr for the 0- to 20- and 20- to 60-cm soil depths, respectively. Results suggest that while total soil Ba increased as a result of biosolids application with time, the mineral form of Ba was present in forms not extractable with AB-DTPA. Scanning electron microscopy using energy dispersive spectroscopy verified soil Ba-S compounds in the soil surface, probably BaSO(4). Wet chemistry sequential extraction suggested BaCO(3) precipitation was increasing in the soil subsurface. Our research showed that biosolids application may increase total soil Ba, but soil Ba precipitates are insoluble and should not be an environmental concern in similar soils under similar climatic and management conditions.

Interactions among hydraulic conductivity distributions, subsurface topography, and transport thresholds revealed by a multitracer hillslope irrigation experiment

DOE PAGES

Jackson, C. Rhett; Du, Enhao; Klaus, Julian; ...

2016-08-12

Interactions among hydraulic conductivity distributions, subsurface topography, and lateral flow are poorly understood. We applied 407 mm of water and a suite of tracers over 51 h to a 12 by 16.5 m forested hillslope segment to determine interflow thresholds, preferential pathway pore velocities, large-scale conductivities, the time series of event water fractions, and the fate of dissolved nutrients. The 12% hillslope featured loamy sand A and E horizons overlying a sandy clay loam Bt at 1.25 m average depth. Interflow measured from two drains within an interception trench commenced after 131 and 208 mm of irrigation. Cumulative interflow equaledmore » 49% of applied water. Conservative tracer differences between the collection drains indicated differences in flow paths and storages within the plot. Event water fractions rose steadily throughout irrigation, peaking at 50% sixteen h after irrigation ceased. Data implied that tightly held water exchanged with event water throughout the experiment and a substantial portion of preevent water was released from the argillic layer. Surface-applied dye tracers bypassed the matrix, with peak concentrations measured shortly after flow commencement, indicating preferential network conductivities of 864–2240 mm/h, yet no macropore flow was observed. Near steady-state flow conditions indicated average conductivities of 460 mm/h and 2.5 mm/h for topsoils and the Bt horizon, respectively. Low ammonium and phosphorus concentrations in the interflow suggested rapid uptake or sorption, while higher nitrate concentrations suggested more conservative transport. Lastly, these results reveal how hydraulic conductivity variation and subsurface topographic complexity explain otherwise paradoxical solute and flow behaviors.« less

A Continuing Analysis of Possible Activity Drivers for the Enigmatic Comet 29P/Schwassmann-Wachmann 1

NASA Astrophysics Data System (ADS)

Schambeau, Charles; Fernández, Yanga; Samarasinha, Nalin H.; Mueller, Beatrice E. A.; Sarid, Gal; Meech, Karen Jean; Woodney, Laura

2016-01-01

We present results from our effort to understand activity drivers in Comet 29P/Schwassmann-Wachmann 1 (SW1). In a nearly circular orbit around 6 AU, outside of the water-sublimation zone, SW1 is continuously active and experiences frequent outbursts. Our group's effort is focusing on finding constraints on physical and dynamical properties of SW1's nucleus and their incorporation into a thermophysical model [1,2] to explain this behavior. We are currently analyzing coma morphology of SW1 before, during, and after outburst placing constraints on the spin-pole direction, spin period, and surface areas of activity. In addition, we are using the thermal model to investigate if the continuous activity comes from one or multiple processes, such as the release of trapped supervolatiles during the amorphous to crystalline (A-C) water ice phase transition and/or the direct sublimation of pockets of supervolatile ices. The supervolatile ices may be primordial or from the condensation of gases released during the A-C phase transition. To explain the possibly quasi-periodic but frequent outbursts, we are looking into subsurface cavities where internal pressures can build, reaching and exceeding surrounding material strengths [3,4] and/or thermal waves reaching a pocket of supervolatile ices, causing a rapid increase in the sublimation rate. For all these phenomena, the model is constrained by comparing the output dust mass loss rate and its variability with what has been observed through optical imaging of the comet at various points in its orbit. We will present preliminary thermal modeling of a homogeneous progenitor nucleus that evolves into a body showing internal material layering, the generation of CO and CO2 ice pockets, and the production of outbursts, thus bringing us closer to explaining the behavior of this intriguing comet. [1] Sarid, G., et al.: 2005, PASP, 117, 843. [2] Sarid, G.: 2009, PhD Thesis, Tel Aviv Univ. [3] Gronkowski, P., 2014, Astron. Nachr./AN 2, No. 335, 124-134. [4] Gronkowski, P. and Wesolowski, M., 2015, MNRAS, 451, 3068-3077. We thank the NASA Outer Planets Research Program (NNX12AK50G) and the Center for Lunar and Asteroid Surface Science (CLASS, NNA14AB05A) for support of this work.

A Continuing Analysis of Possible Activity Drivers for the Enigmatic Comet 29P/Schwassmann-Wachmann 1

NASA Astrophysics Data System (ADS)

Schambeau, Charles Alfred; Fernandez, Yanga; Samarasinha, Nalin; Sarid, Gal; Mueller, Beatrice; Meech, Karen; Woodney, Laura

2015-11-01

We present results from our continuing effort to understand activity drivers in Comet 29P/Schwassmann-Wachmann 1 (SW1). While being in a nearly circular orbit around 6 AU, SW1 is continuously active and experiences frequent outbursts. Our group’s effort is focusing on finding constraints on physical and dynamical properties of SW1’s nucleus and their incorporation into a thermophysical model [1,2] to explain this behavior. Now we are analyzing coma morphology of SW1 before, during, and after outburst to place constraints on the spin-pole direction, spin period, and surface areas of activity (a spin period lower limit has been measured). Also, we are using the thermal model to investigate if the continuous activity comes from one or multiple processes, such as the release of trapped supervolatiles during the amorphous to crystalline (A-C) water ice phase transition and/or the direct sublimation of pockets of supervolatile ices, which may be primordial or from the condensation of gases released during the A-C phase transition. To explain the possibly quasi-periodic but frequent outbursts, we are looking into subsurface cavities where internal pressures can build, reaching and exceeding surrounding material strengths [3,4] and/or thermal waves reaching a pocket of supervolatile ices, causing a rapid increase in the sublimation rate. For all these phenomena, the model is constrained by comparing the output dust mass loss rate and its variability with what has been observed through optical imaging of the comet at various points in its orbit. We will present preliminary thermal modeling of a homogeneous progenitor nucleus that evolves into a body showing internal material layering, the generation of CO and CO2 ice pockets, and the production of outbursts, thus bringing us closer to explaining the behavior of this intriguing comet.[1] Sarid, G., et al.: 2005, PASP, 117, 843. [2] Sarid, G.: 2009, PhD Thesis, Tel Aviv Univ. [3] Gronkowski, P., 2014, Astron. Nachr./AN 2, No. 335, 124-134. [4] Gronkowski, P. and Wesolowski, M., 2015, MNRAS, 451, 3068-3077. We thank the NASA Outer Planets Research Program (NNX12AK50G) and the Center for Lunar and Asteroid Surface Science (CLASS, NNA14AB05A) for support of this work.

Aseptically Sampled Organics in Subsurface Rocks From the Mars Analog Rio Tinto Experiment: An Analog For The Search for Deep Subsurface Life on Mars.}

NASA Astrophysics Data System (ADS)

Bonaccorsi, R.; Stoker, C. R.

2005-12-01

The subsurface is the key environment for searching for life on planets lacking surface life. Subsurface ecosystems are of great relevance to astrobiology including the search for past/present life on Mars. The surface of Mars has conditions preventing current life but the subsurface might preserve organics and even host some life [1]. The Mars-Analog-Rio-Tinto-Experiment (MARTE) is performing a simulation of a Mars drilling experiment. This comprises conventional and robotic drilling of cores in a volcanically-hosted-massive-pyrite deposit [2] from the Iberian Pyritic Belt (IBP) and life detection experiments applying anti-contamination protocols (e.g., ATP Luminometry assay). The RT is considered an important analog of the Sinus Meridiani site on Mars and an ideal model analog for a deep subsurface Martian environment. Former results from MARTE suggest the existence of a relatively complex subsurface life including aerobic and anaerobic chemoautotrophs and strict anaerobic methanogens sustained by Fe and S minerals in anoxic conditions. A key requirement for the analysis of a subsurface sample on Mars is a set of simple tests that can help determine if the sample contains organic material of biological origin, and its potential for retaining definitive biosignatures. We report here on the presence of bulk organic matter Corg (0.03-0.05 Wt%), and Ntot (0.01-0.04 Wt%) and amount of measured ATP (Lightning MVP, Biocontrol) in weathered rocks (tuffs, gossan, pyrite stockwork from Borehole #8; >166m). This provides key insight on the type of trophic system sustaining the subsurface biosphere (i.e., heterotrophs vs. autotrophs) at RT. ATP data (Relative-Luminosity-Units, RLU) provide information on possible contamination and distribution of viable biomass with core depth (BH#8, and BH#7, ~3m). Avg. 153 RLU, i.e., surface vs. center of core, suggest that cleaness/sterility can be maintained when using a simple sterile protocol under field conditions. Results from this research will support future drilling mission planned on Mars. [1] Boston, P.J., et al., 1992. Icarus 95,300-308; [2] Leistel et al., 1998.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gutierrez, Marte

Colorado School of Mines conducted research and training in the development and validation of an advanced CO{sub 2} GS (Geological Sequestration) probabilistic simulation and risk assessment model. CO{sub 2} GS simulation and risk assessment is used to develop advanced numerical simulation models of the subsurface to forecast CO2 behavior and transport; optimize site operational practices; ensure site safety; and refine site monitoring, verification, and accounting efforts. As simulation models are refined with new data, the uncertainty surrounding the identified risks decrease, thereby providing more accurate risk assessment. The models considered the full coupling of multiple physical processes (geomechanical and fluidmore » flow) and describe the effects of stochastic hydro-mechanical (H-M) parameters on the modeling of CO{sub 2} flow and transport in fractured porous rocks. Graduate students were involved in the development and validation of the model that can be used to predict the fate, movement, and storage of CO{sub 2} in subsurface formations, and to evaluate the risk of potential leakage to the atmosphere and underground aquifers. The main major contributions from the project include the development of: 1) an improved procedure to rigorously couple the simulations of hydro-thermomechanical (H-M) processes involved in CO{sub 2} GS; 2) models for the hydro-mechanical behavior of fractured porous rocks with random fracture patterns; and 3) probabilistic methods to account for the effects of stochastic fluid flow and geomechanical properties on flow, transport, storage and leakage associated with CO{sub 2} GS. The research project provided the means to educate and train graduate students in the science and technology of CO{sub 2} GS, with a focus on geologic storage. Specifically, the training included the investigation of an advanced CO{sub 2} GS simulation and risk assessment model that can be used to predict the fate, movement, and storage of CO{sub 2} in underground formations, and the evaluation of the risk of potential CO{sub 2} leakage to the atmosphere and underground aquifers.« less

Designs for Risk Evaluation and Management

DOE Office of Scientific and Technical Information (OSTI.GOV)

The Designs for Risk Evaluation and Management (DREAM) tool was developed as part of the effort to quantify the risk of geologic storage of carbon dioxide (CO 2) under the U.S. Department of Energy's National Risk Assessment Partnership (NRAP). DREAM is an optimization tool created to identify optimal monitoring schemes that minimize the time to first detection of CO 2 leakage from a subsurface storage formation. DREAM acts as a post-processer on user-provided output from subsurface leakage simulations. While DREAM was developed for CO 2 leakage scenarios, it is applicable to any subsurface leakage simulation of the same output format.more » The DREAM tool is comprised of three main components: (1) a Java wizard used to configure and execute the simulations, (2) a visualization tool to view the domain space and optimization results, and (3) a plotting tool used to analyze the results. A secondary Java application is provided to aid users in converting common American Standard Code for Information Interchange (ASCII) output data to the standard DREAM hierarchical data format (HDF5). DREAM employs a simulated annealing approach that searches the solution space by iteratively mutating potential monitoring schemes built of various configurations of monitoring locations and leak detection parameters. This approach has proven to be orders of magnitude faster than an exhaustive search of the entire solution space. The user's manual illustrates the program graphical user interface (GUI), describes the tool inputs, and includes an example application.« less

Thermal Imaging of Subsurface Coal Fires by means of an Unmanned Aerial Vehicle (UAV) in the Autonomous Province Xinjiang, PRC

NASA Astrophysics Data System (ADS)

Vasterling, Margarete; Schloemer, Stefan; Fischer, Christian; Ehrler, Christoph

2010-05-01

Spontaneous combustion of coal and resulting coal fires lead to very high temperatures in the subsurface. To a large amount the heat is transferred to the surface by convective and conductive transport inducing a more or less pronounced thermal anomaly. During the past decade satellite-based infrared-imaging (ASTER, MODIS) was the method of choice for coal fire detection on a local and regional scale. However, the resolution is by far too low for a detailed analysis of single coal fires which is essential prerequisite for corrective measures (i.e. fire fighting) and calculation of carbon dioxide emission based on a complex correlation between energy release and CO2 generation. Consequently, within the framework of the Sino-German research project "Innovative Technologies for Exploration, Extinction and Monitoring of Coal Fires in Northern China", a new concept was developed and successfully tested. An unmanned aerial vehicle (UAV) was equipped with a lightweight camera for thermografic (resolution 160 by 120 pixel, dynamic range -20 to 250°C) and for visual imaging. The UAV designed as an octocopter is able to hover at GPS controlled waypoints during predefined flight missions. The application of a UAV has several advantages. Compared to point measurements on the ground the thermal imagery quickly provides the spatial distribution of the temperature anomaly with a much better resolution. Areas otherwise not accessible (due to topography, fire induced cracks, etc.) can easily be investigated. The results of areal surveys on two coal fires in Xinjiang are presented. Georeferenced thermal and visual images were mosaicked together and analyzed. UAV-born data do well compared to temperatures measured directly on the ground and cover large areas in detail. However, measuring surface temperature alone is not sufficient. Simultaneous measurements made at the surface and in roughly 15cm depth proved substantial temperature gradients in the upper soil. Thus the temperature measured at the surface underestimates the energy emitted by the subsurface coal fire. In addition, surface temperature is strongly influenced by solar radiation and the prevailing ambient conditions (wind, temperature, humidity). As a consequence there is no simple correlation between surface and subsurface soil temperature. Efforts have been made to set up a coupled energy transport and energy balance model for the near surface considering thermal conduction, solar irradiation, thermal radiative energy and ambient temperature so far. The model can help to validate space-born and UAV-born thermal imagery and link surface to subsurface temperature but depends on in-situ measurements for input parameter determination and calibration. Results obtained so far strongly necessitate the integration of different data sources (in-situ / remote; point / area; local / medium scale) to obtain a reliable energy release estimation which is then used for coal fire characterization.

High-throughput screening of metal-porphyrin-like graphenes for selective capture of carbon dioxide

PubMed Central

Bae, Hyeonhu; Park, Minwoo; Jang, Byungryul; Kang, Yura; Park, Jinwoo; Lee, Hosik; Chung, Haegeun; Chung, ChiHye; Hong, Suklyun; Kwon, Yongkyung; Yakobson, Boris I.; Lee, Hoonkyung

2016-01-01

Nanostructured materials, such as zeolites and metal-organic frameworks, have been considered to capture CO2. However, their application has been limited largely because they exhibit poor selectivity for flue gases and low capture capacity under low pressures. We perform a high-throughput screening for selective CO2 capture from flue gases by using first principles thermodynamics. We find that elements with empty d orbitals selectively attract CO2 from gaseous mixtures under low CO2 pressures (~10−3 bar) at 300 K and release it at ~450 K. CO2 binding to elements involves hybridization of the metal d orbitals with the CO2 π orbitals and CO2-transition metal complexes were observed in experiments. This result allows us to perform high-throughput screening to discover novel promising CO2 capture materials with empty d orbitals (e.g., Sc– or V–porphyrin-like graphene) and predict their capture performance under various conditions. Moreover, these findings provide physical insights into selective CO2 capture and open a new path to explore CO2 capture materials. PMID:26902156

High-throughput screening of metal-porphyrin-like graphenes for selective capture of carbon dioxide.

PubMed

Bae, Hyeonhu; Park, Minwoo; Jang, Byungryul; Kang, Yura; Park, Jinwoo; Lee, Hosik; Chung, Haegeun; Chung, ChiHye; Hong, Suklyun; Kwon, Yongkyung; Yakobson, Boris I; Lee, Hoonkyung

2016-02-23

Nanostructured materials, such as zeolites and metal-organic frameworks, have been considered to capture CO2. However, their application has been limited largely because they exhibit poor selectivity for flue gases and low capture capacity under low pressures. We perform a high-throughput screening for selective CO2 capture from flue gases by using first principles thermodynamics. We find that elements with empty d orbitals selectively attract CO2 from gaseous mixtures under low CO2 pressures (~10(-3) bar) at 300 K and release it at ~450 K. CO2 binding to elements involves hybridization of the metal d orbitals with the CO2 π orbitals and CO2-transition metal complexes were observed in experiments. This result allows us to perform high-throughput screening to discover novel promising CO2 capture materials with empty d orbitals (e.g., Sc- or V-porphyrin-like graphene) and predict their capture performance under various conditions. Moreover, these findings provide physical insights into selective CO2 capture and open a new path to explore CO2 capture materials.

High-throughput screening of metal-porphyrin-like graphenes for selective capture of carbon dioxide

NASA Astrophysics Data System (ADS)

Bae, Hyeonhu; Park, Minwoo; Jang, Byungryul; Kang, Yura; Park, Jinwoo; Lee, Hosik; Chung, Haegeun; Chung, Chihye; Hong, Suklyun; Kwon, Yongkyung; Yakobson, Boris I.; Lee, Hoonkyung

2016-02-01

Nanostructured materials, such as zeolites and metal-organic frameworks, have been considered to capture CO2. However, their application has been limited largely because they exhibit poor selectivity for flue gases and low capture capacity under low pressures. We perform a high-throughput screening for selective CO2 capture from flue gases by using first principles thermodynamics. We find that elements with empty d orbitals selectively attract CO2 from gaseous mixtures under low CO2 pressures (~10-3 bar) at 300 K and release it at ~450 K. CO2 binding to elements involves hybridization of the metal d orbitals with the CO2 π orbitals and CO2-transition metal complexes were observed in experiments. This result allows us to perform high-throughput screening to discover novel promising CO2 capture materials with empty d orbitals (e.g., Sc- or V-porphyrin-like graphene) and predict their capture performance under various conditions. Moreover, these findings provide physical insights into selective CO2 capture and open a new path to explore CO2 capture materials.

Negative CO2 emissions via enhanced silicate weathering in coastal environments

PubMed Central

Montserrat, Francesc

2017-01-01

Negative emission technologies (NETs) target the removal of carbon dioxide (CO2) from the atmosphere, and are being actively investigated as a strategy to limit global warming to within the 1.5–2°C targets of the 2015 UN climate agreement. Enhanced silicate weathering (ESW) proposes to exploit the natural process of mineral weathering for the removal of CO2 from the atmosphere. Here, we discuss the potential of applying ESW in coastal environments as a climate change mitigation option. By deliberately introducing fast-weathering silicate minerals onto coastal sediments, alkalinity is released into the overlying waters, thus creating a coastal CO2 sink. Compared with other NETs, coastal ESW has the advantage that it counteracts ocean acidification, does not interfere with terrestrial land use and can be directly integrated into existing coastal management programmes with existing (dredging) technology. Yet presently, the concept is still at an early stage, and so two major research challenges relate to the efficiency and environmental impact of ESW. Dedicated experiments are needed (i) to more precisely determine the weathering rate under in situ conditions within the seabed and (ii) to evaluate the ecosystem impacts—both positive and negative—from the released weathering products. PMID:28381634

Capturing Hot Moments of Carbon Cycling in the Hyporheic Zone of an Intermittent Stream

NASA Astrophysics Data System (ADS)

Brandt, T.; Harjung, A.; Vieweg, M.; Butturini, A.; Schmidt, C.; Fleckenstein, J. H.; Sabater, F.

2016-12-01

Intermittent streams are increasingly recognized as a factor for underestimating potential CO2 emissions of aquatic ecosystems, because they are neglected during their dry phase. This can be partly attributed to poor understanding of dissolved organic matter (DOM) processing at highly reactive interfaces such as the hyporheic zone (HZ). Here, hydrological transitions drive rapid changes in the spatiotemporal distribution of dissolved oxygen (DO), thus creating hot moments of increased biogeochemical cycling. However, capturing these process-dynamics requires a continuous monitoring of hyporheic pore water at a sufficient temporal and spatial resolution. In order to investigate the transitions between the wet and dry phase, we used a combination of automated pore water sampling and in situ measurements. By combining conventional pumping approaches with recently developed technology we achieved a high resolution multi-scale, quasi continuous monitoring of relevant parameters of the carbon cycle. Our novel approach coupled continuous fluorescence DOM and infrared CO2 sensor measurements with spatially continuous vertical oxygen profiling in situ. A proof-of-concept application was established in a semi-pristine Mediterranean stream during the drying period in summer 2015. Previous sampling campaigns already identified the water level as a driver of DOM composition in the HZ. Once the surface flow switches to subsurface flow, the HZ becomes a sink for aromatic, high molecular weight compounds, while protein-like, autochthonous DOM gets released. Generally, we observed exponential increases in hyporheic CO2 from this point on, co-occurring with a sharp vertical DO gradient as a function of changing hydrological conditions.

A Deeply Branching Thermophilic Bacterium with an Ancient Acetyl-CoA Pathway Dominates a Subsurface Ecosystem

PubMed Central

Takami, Hideto; Noguchi, Hideki; Takaki, Yoshihiro; Uchiyama, Ikuo; Toyoda, Atsushi; Nishi, Shinro; Chee, Gab-Joo; Arai, Wataru; Nunoura, Takuro; Itoh, Takehiko; Hattori, Masahira; Takai, Ken

2012-01-01

A nearly complete genome sequence of Candidatus ‘Acetothermum autotrophicum’, a presently uncultivated bacterium in candidate division OP1, was revealed by metagenomic analysis of a subsurface thermophilic microbial mat community. Phylogenetic analysis based on the concatenated sequences of proteins common among 367 prokaryotes suggests that Ca. ‘A. autotrophicum’ is one of the earliest diverging bacterial lineages. It possesses a folate-dependent Wood-Ljungdahl (acetyl-CoA) pathway of CO2 fixation, is predicted to have an acetogenic lifestyle, and possesses the newly discovered archaeal-autotrophic type of bifunctional fructose 1,6-bisphosphate aldolase/phosphatase. A phylogenetic analysis of the core gene cluster of the acethyl-CoA pathway, shared by acetogens, methanogens, some sulfur- and iron-reducers and dechlorinators, supports the hypothesis that the core gene cluster of Ca. ‘A. autotrophicum’ is a particularly ancient bacterial pathway. The habitat, physiology and phylogenetic position of Ca. ‘A. autotrophicum’ support the view that the first bacterial and archaeal lineages were H2-dependent acetogens and methanogenes living in hydrothermal environments. PMID:22303444

Energy, chemical disequilibrium, and geological constraints on Europa.

PubMed

Hand, Kevin P; Carlson, Robert W; Chyba, Christopher F

2007-12-01

Europa is a prime target for astrobiology. The presence of a global subsurface liquid water ocean and a composition likely to contain a suite of biogenic elements make it a compelling world in the search for a second origin of life. Critical to these factors, however, may be the availability of energy for biological processes on Europa. We have examined the production and availability of oxidants and carbon-containing reductants on Europa to better understand the habitability of the subsurface ocean. Data from the Galileo Near-Infrared Mapping Spectrometer were used to constrain the surface abundance of CO(2) to 0.036% by number relative to water. Laboratory results indicate that radiolytically processed CO(2)-rich ices yield CO and H(2)CO(3); the reductants H(2)CO, CH(3)OH, and CH(4) are at most minor species. We analyzed chemical sources and sinks and concluded that the radiolytically processed surface of Europa could serve to maintain an oxidized ocean even if the surface oxidants (O(2), H(2)O(2), CO(2), SO(2), and SO(4) (2)) are delivered only once every approximately 0.5 Gyr. If delivery periods are comparable to the observed surface age (30-70 Myr), then Europa's ocean could reach O(2) concentrations comparable to those found in terrestrial surface waters, even if approximately 10(9) moles yr(1) of hydrothermally delivered reductants consume most of the oxidant flux. Such an ocean would be energetically hospitable for terrestrial marine macrofauna. The availability of reductants could be the limiting factor for biologically useful chemical energy on Europa.

Aerobic biodegradability of methyldiethanolamine (MDEA) used in natural gas sweetening plants in batch tests and continuous flow experiments.

PubMed

Fürhacker, M; Pressl, A; Allabashi, R

2003-09-01

Mixtures of different amines including tertiary amines (methyldiethanolamine, MDEA) are commonly used for the removal of CO2 from gas mixtures or in gas sweetening processes for the extraction of CO2 and H2S. The absorber solutions used can be released into the industrial waste water due to continuous substitution of degraded MDEA, periodically cleaning processes or an accidental spill. In this study, the aerobic biodegradability of MDEA was investigated in a standardised batch test and a continuous flow experiment (40 l/d). The results of the batch test indicated that the MDEA-solution was non-biodegradable during the test period of 28 days, whereas the continuous flow experiments showed biodegradation of more than 96% based on TOC-measurements. This was probably due to the adaptation of the microorganisms to this particular waste water contamination during continuous flow experiment.

Comparison Between North and South Near Polar Regions of Mars from HEND/Odyssey Data

NASA Technical Reports Server (NTRS)

Litvak, M. L.; Mitrofanov, I. G.; Kozyrev, A. S.; Sanin, A. B.; Tretyakov, V.; Boynton, W. V.; Hamara, D. K.; Shinohara, C.; Saunders, R. S.; Drake, D.

2003-01-01

It is known that North and South near polar regions are affected by global redistribution of atmospheric CO2. The maximal thickness of CO2 snow depth may be as high as 1 m at latitudes close to martian poles. It explains why neutron flux above martian poles significantly varies from summer to winter seasons. It occurs because CO2 frost hides upper surface layer from the orbit observations. This fact was used to estimate thickness of CO2 deposit at different latitudes. Here we suggest to make comparison between martian near polar regions in both ways as in terms of subsurface regolith structure as in terms of distribution of CO2 deposits.

Streamlined Approach for Environmental Restoration (SAFER) Plan for Corrective Action Unit 415: Project 57 No. 1 Plutonium Dispersion (NTTR), Nevada, Revision 0

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matthews, Patrick; Burmeister, Mark

2014-04-01

This Streamlined Approach for Environmental Restoration (SAFER) Plan addresses the actions needed to achieve closure for Corrective Action Unit (CAU) 415, Project 57 No. 1 Plutonium Dispersion (NTTR). CAU 415 is located on Range 4808A of the Nevada Test and Training Range (NTTR) and consists of one corrective action site: NAFR-23-02, Pu Contaminated Soil. The CAU 415 site consists of the atmospheric release of radiological contaminants to surface soil from the Project 57 safety experiment conducted in 1957. The safety experiment released plutonium (Pu), uranium (U), and americium (Am) to the surface soil over an area of approximately 1.9 squaremore » miles. This area is currently fenced and posted as a radiological contamination area. Vehicles and debris contaminated by the experiment were subsequently buried in a disposal trench within the surface-contaminated, fenced area and are assumed to have released radiological contamination to subsurface soils. Potential source materials in the form of pole-mounted electrical transformers were also identified at the site and will be removed as part of closure activities.« less

Factors Effecting the Fate and Transport of CL-20 in the Vadose Zone and Groundwater: Final Report 2002 - 2004 SERDP Project CP-1255

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szecsody, James E.; Riley, Robert G.; Devary, Brooks J.

2005-06-01

This SERDP-funded project was initiated to investigate the fate of CL-20 in the subsurface environment, with a focus on identification and quantification of geochemical and microbial reactions of CL-20. CL-20 can be released to the surface and subsurface terrestrial environment by: a) manufacturing processes, b) munition storage, and c) use with low order detonation or unexploded ordnance. The risk of far-field subsurface migration was assessed through labora-tory experiments with a variety of sediments and subsurface materials to quantify processes that control CL-20 sorption-limited migration and degradation. Results of this study show that CL-20 will exhibit differing behavior in the subsurfacemore » terrestrial environment: 1. CL-20 on the sediment surface will photodegrade and interact with plants/animals (described in other SERDP projects CU 1254, 1256). CL-20 will exhibit greater sorption in humid sediments to organic matter. Transport will be solubility limited (i.e., low CL-20 aqueous solubility). 2. CL-20 infiltration into soils (<2 m) from spills will be subject to sorption to soil organic matter (if present), and low to high biodegradation rates (weeks to years) depending on the microbial population (greater in humid environment). 3. CL-20 in the vadose zone (>2 m) will be, in most cases, subject to low sorption and low degradation rates, so would persist in the subsurface environment and be at risk for deep migration. Low water content in arid regions will result in a decrease in both sorption and the degradation rate. Measured degradation rates in unsaturated sediments of years would result in significant subsurface migration distances. 4. CL-20 in groundwater will be subject to some sorption but likely very slow degradation rates. CL-20 sorption will be greater than RDX. Most CL-20 degradation will be abiotic (ferrous iron and other transition metals), because most deep subsurface systems have extremely low natural microbial populations. Degradation rates will range from weeks (iron reducing systems) to years. Although CL-20 will move rapidly through most sediments in the terrestrial environment, subsurface remediation can be utilized for cleanup. Transformation of CL-20 to intermediates can be rapidly accomplished under: a) reducing conditions (CL-20 4.1 min. half-life, RDX 18 min. half-life), b) alkaline (pH >10) conditions, and c) bioremediation with added nutrients. CL-20 degradation to intermediates may be insufficient to mitigate environmental impact, as the toxicity of many of these compounds is unknown. Biostimulation in oxic to reducing systems by carbon and nutrient addition can mineralize CL-20, with the most rapid rates occurring under reducing conditions.« less

The metal oxide fraction of pelagic sediment in the equatorial North Pacific Ocean: A source of metals in ferromanganese nodules

USGS Publications Warehouse

Piper, D.Z.

1988-01-01

Pelagic sediment recovered at DOMES Site A in the equatorial North Pacific (151??W, 9?? 15???N) consists of a surface homogeneous layer, approximately 10 cm thick, overlying a strongly mottled layer that is lighter in color. The radiolarian composition of both units is Quaternary. In areas where this sediment was only a few centimeters thick, the underlying sediment was early Tertiary. Clay mineralogy and major oxide composition of the two Quaternary sediments are uniform. Their similarity to continental shale suggests that the sediment has a terrigenous source. Clay mineralogy and major oxide composition of the Tertiary sediment also are uniform, although they differ markedly from the Quarternary sediment. In contrast to the major oxides, concentrations of Mn, Co, Cu, and Ni soluble in hydroxylamine hydrochlorideacetic acid are strongly different in the surface and subsurface Quaternary sediment. Mn and Ni exhibit pronounced depletions in the subsurface sediment, Ni slightly more than Mn. Cu is also depleted in the subsurface sediment, but less than Mn. It is also depleted in the subsurface Tertiary sediment, whereas the Mn concentration remains high. Concentration of Co relative to Mn increases into the subsurface Quaternary sediment to a constant Co:Mn ratio of 3 ?? 10-2. The trivalent REE (the REE exclusive of Ce) and Fe exhibit little down-core variation. Distribution of elements in these sediments is closely related to their concentration in associated surface ferromanganese nodules. The nodules are of two distinct types: those from the area where the Quaternary sediment is relatively thick have ??-MnO2 as the dominant manganese mineral. The ratios of Ni:Mn, Cu:Mn, and Fe:Mn in these nodules approximate the corresponding ratios of the soluble fraction of surface sediment. Todorokite is the dominant mineral of nodules recovered from areas where the Quaternary sediment is thin. Relatively high Cu/Mn, Ni/Mn, and low Fe/Mn ratios of these nodules mirror differences between the soluble fraction of surface and subsurface Quaternary sediment. These compositional trends of sediment and nodules at DOMES Site A reflect a diagenetic origin for the todorokite nodules and a predominantly hydrogenous origin for the ??-MnO2 nodules. ?? 1988.

Biogeochemical Controls on Microbial CO2 and CH4 Production in Polygonal Soils From the Barrow Environmental Observatory

NASA Astrophysics Data System (ADS)

Graham, D. E.; Roy Chowdhury, T.; Herndon, E.; Gu, B.; Liang, L.; Wullschleger, S. D.

2014-12-01

Organic matter buried in Arctic soils and permafrost will become accessible to increased microbial degradation as the ground warms due to climate change. The rates of organic matter degradation and the proportion of CH4 and CO2 greenhouse gasses released in a potential warming feedback cycle depend on the microbial response to warming, organic carbon structure and availability, the pore-water quantity and geochemistry, and available electron acceptors. Significant amounts of iron(II) ions in organic and mineral soils of the active layer in low-centered ice wedge polygons indicate anoxic conditions in most soil horizons. To adapt and improve the representation of these Arctic subsurface processes in terrestrial ecosystem models for the NGEE Arctic project, we examined soil organic matter transformations from elevated and subsided areas of low- and high-centered polygons from interstitial tundra on the Barrow Environmental Observatory (Barrow, AK). Using microcosm incubations at fixed temperatures and controlled thawing systems for frozen soil cores, we investigated the microbiological processes and rates of soil organic matter degradation and greenhouse gas production under anoxic conditions, at ecologically relevant temperatures of -2, +4 or +8 °C. In contrast to the low-centered polygon incubations representing in situ water-saturated conditions, microcosms with unsaturated high-centered polygon samples displayed lower carbon mineralization as either CH4 or CO2. Substantial differences in CH4 and CO2 response curves from different microtopographic samples separate the thermodynamic controls on biological activity from the kinetic controls of microbial growth and migration that together determine the temperature response for greenhouse gas emissions in a warming Arctic.

Coupled Geochemical Impacts of Leaking CO2 and Contaminants from Subsurface Storage Reservoirs on Groundwater Quality

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shao, Hongbo; Qafoku, Nikolla; Lawter, Amanda R.

2015-07-07

The leakage of CO2 and the concomitant saline solutions from deep storage reservoirs to overlying groundwater aquifers is considered one of the major potential risks associated with geologic CO2 sequestration (GCS). Batch and column experiments were conducted to determine the fate of trace metals in groundwater in the scenarios of CO2 and metal contaminated brine leakage. The sediments used in this work were collected from an unconsolidated sand and gravel aquifer in Kansas, and contained 0-4 wt% carbonates. Cd and As were spiked into the reaction system to represent potential contaminants from the reservoir brine that could intrude into groundwatermore » aquifers with leaking CO2 at initial concentrations of 114 and 40 ppb, respectively. Through this research we demonstrated that Cd and As were adsorbed on the sediments, in spite of the lowered pH due to CO2 dissolution in the groundwater. Cd concentrations were well below its MCL in both batch and column studies, even for sediment samples without detectable carbonate to buffer the pH. Arsenic concentrations in the effluent were also significantly lower than influent concentration, suggesting that the sediments tested have the capacity to mitigate the coupled adverse effects of CO2 leakage and brine intrusion. However, the mitigation capacity of sediment is a function of its geochemical properties [e.g., the calcite content; the presence of adsorbed As(III); and the presence of P in the natural sediment]. The competitive adsorption between phosphate and arsenate may result in higher concentrations of As in the aqueous phase.« less

Effects of Nitrogen Addition on Litter Decomposition and CO2 Release: Considering Changes in Litter Quantity

PubMed Central

Li, Hui-Chao; Hu, Ya-Lin; Mao, Rong; Zhao, Qiong; Zeng, De-Hui

2015-01-01

This study aims to evaluate the impacts of changes in litter quantity under simulated N deposition on litter decomposition, CO2 release, and soil C loss potential in a larch plantation in Northeast China. We conducted a laboratory incubation experiment using soil and litter collected from control and N addition (100 kg ha−1 year−1 for 10 years) plots. Different quantities of litter (0, 1, 2 and 4 g) were placed on 150 g soils collected from the same plots and incubated in microcosms for 270 days. We found that increased litter input strongly stimulated litter decomposition rate and CO2 release in both control and N fertilization microcosms, though reduced soil microbial biomass C (MBC) and dissolved inorganic N (DIN) concentration. Carbon input (C loss from litter decomposition) and carbon output (the cumulative C loss due to respiration) elevated with increasing litter input in both control and N fertilization microcosms. However, soil C loss potentials (C output–C input) reduced by 62% in control microcosms and 111% in N fertilization microcosms when litter addition increased from 1 g to 4 g, respectively. Our results indicated that increased litter input had a potential to suppress soil organic C loss especially for N addition plots. PMID:26657180

Incipient rifting accompanied by the release of subcontinental lithospheric mantle volatiles in the Magadi and Natron basin, East Africa

NASA Astrophysics Data System (ADS)

Lee, Hyunwoo; Fischer, Tobias P.; Muirhead, James D.; Ebinger, Cynthia J.; Kattenhorn, Simon A.; Sharp, Zachary D.; Kianji, Gladys; Takahata, Naoto; Sano, Yuji

2017-10-01

Geochemical investigations of volatiles in hydrothermal systems are used to understand heat sources and subsurface processes occurring at volcanic-tectonic settings. This study reports new results of gas chemistry and isotopes (O, H, N, C, and He) of thermal spring samples (T = 36.8-83.5 °C; pH = 8.5-10.3) from the Magadi and Natron basin (MNB) in the East African Rift (EAR). Although a number of thermal springs are shown to ascend along normal faults and feed into major lakes (Magadi, Little Magadi, and Natron), volatile sources and fluxes of these fluids are poorly constrained. CO2 is the most abundant phase (up to 996.325 mmol/mol), and the N2-He-Ar abundances show a mixture of dissolved gases from deep (mantle-derived) and shallow (air/air saturated water) sources. The H2-Ar-CH4-CO2 geothermometers indicate that equilibrium temperatures range from 100 to 150 °C. δ18O (- 4.4 to - 0.2‰) and δD (- 28.9 to - 3.9‰) values of the MNB thermal waters still lie slightly to the right of the local meteoric water lines, reflecting minor evaporation. Each mixing relationship of N2 (δ15N = - 1.5 to 0.4‰; N2/3He = 3.92 × 106-1.33 × 109, except for an anomalous biogenic sample (δ15N = 5.9‰)) and CO2 (δ13C = - 5.7 to 1.6‰; CO2/3He = 7.24 × 108-1.81 × 1011) suggests that the predominant mantle component of the MNB volatiles is Subcontinental Lithospheric Mantle (SCLM). However, N2 is mostly atmospheric, and minor CO2 is contributed by the limestone end-member. 3He/4He ratios (0.64-4.00 Ra) also indicate a contribution of SCLM (R/Ra = 6.1 ± 0.9), with radiogenic 4He derived from a crustal source (R/Ra = 0.02). The MNB 4He flux rates (3.64 × 1011 to 3.34 × 1014 atoms/m2 s) are significantly greater than the reported mean of global continental flux values (4.18 × 1010 atoms/m2 s), implying that magma intrusions could supply mantle 4He, and related heating and fracturing release crustal 4He from the Tanzanian craton and Mozambique belt. Total flux values (mol/yr) of 3He, N2, and CO2 are 8.18, 4.07 × 107, and 5.31 × 109, which are 1.28%, 2.04%, and 0.24% of global fluxes, respectively. Our results suggest that the primary source of magmatic volatiles in the MNB is SCLM, with additional crustal contributions, which is different from the KRV volatiles that have more asthenospheric mantle components. Volatiles from SCLM in magmas stall in the crust to heat and fracture country rock, with accompanying crustal volatile release. These volatile signatures reveal that MORB-type mantle replaces a relatively small volume of SCLM during incipient rifting (< 10 Ma) in the EAR.

Role of Biotic and Abiotic Processes on Soil CO2 Dynamics in the McMurdo Dry Valleys, Antarctica

NASA Astrophysics Data System (ADS)

Risk, D. A.; Macintyre, C. M.; Lee, C.; Cary, C.; Shanhun, F.; Almond, P. C.

2016-12-01

In the harsh conditions of the Antarctic Dry Valleys, microbial activity has been recorded via measurements of soil carbon dioxide (CO2) concentration and surface efflux. However, high temporal resolution studies in the Dry Valleys have also shown that abiotic solubility-driven processes can strongly influence (and perhaps even dominate) the CO2 dynamics in these low flux environments and suggests that biological activity may be lower than previously thought. In this study, we aim to improve our understanding of CO2 dynamics (biotic and abiotic) in Antarctic Dry Valley soils using long-term automated measurements of soil CO2 surface flux and soil profile concentration at several sites, often at sub-diel frequency. We hypothesize that soil CO2 variations are driven primarily by environmental factors affecting CO2 solubility in soil solution, mainly temperature, and that these processes may even overprint biologic production in representative Dry Valley soils. Monitoring of all sites revealed only one likely biotic CO2 production event, lasting three weeks during the Austral summer and reaching fluxes of 0.4 µmol/m2/s. Under more typical low flux conditions (<0.10 µmol/m2/s) we observed a cyclical daily sink/source pattern consistent with CO2 solubility cycling that would not generally have been evident with normal synoptic afternoon sampling campaigns. Subsurface CO2 monitoring and a lab-controlled Antarctic soil simulation experiment confirmed that abiotic processes are capable of dominating soil CO2 variability. Diel temperature cycles crossing the freezing boundary revealed a dual abiotic cycle of solubility cycling and gas exclusion from ice formation observed only by high temporal frequency measurements (30 min). This work demonstrates a need for a numerical model to partition the dynamic abiotic processes underlying any biotic CO2 production in order to understand potential climate-change induced increases in microbial productivity in terrestrial Antarctica.

Methane emissions and contaminant degradation rates at sites affected by accidental releases of denatured fuel-grade ethanol

NASA Astrophysics Data System (ADS)

Sihota, Natasha J.; Mayer, K. Ulrich; Toso, Mark A.; Atwater, Joel F.

2013-08-01

The recent increase in the use of denatured fuel-grade ethanol (DFE) has enhanced the probability of its environmental release. Due to the highly labile nature of ethanol (EtOH), it is expected to rapidly biodegrade, increasing the potential for inducing methanogenic conditions in the subsurface. As environmental releases of DFE can be expected to occur at the ground surface or in the vadose zone (e.g., due to surficial spills from rail lines or tanker trucks and leaking underground storage tanks), the potential for methane (CH4) generation at DFE spill sites requires evaluation. An assessment is needed because high CH4 generation rates may lead to CH4 fluxes towards the ground surface, which is of particular concern if spills are located close to human habitation—related to concerns of soil vapor intrusion (SVI). This work demonstrates, for the first time, the measurement of surficial gas release rates at large volume DFE spill sites. Two study sites, near Cambria and Balaton, in MN are investigated. Total carbon emissions at the ground surface (summing carbon dioxide (CO2) and CH4 emissions) are used to quantify depth-integrated DFE degradation rates. Results from both sites demonstrate that substantial CO2 and CH4 emissions do occur—even years after a spill. However, large total carbon fluxes, and CH4 emissions in particular, were restricted to a localized area within the DFE source zone. At the Balaton site, estimates of total DFE carbon losses in the source zone ranged between 5 and 174 μmol m- 2 s- 1, and CH4 effluxes ranged between non-detect and 9 μmol m- 2 s- 1. At the Cambria site estimates of total DFE carbon losses in the source zone ranged between 8 and 500 μmol m- 2 s- 1, and CH4 effluxes ranged between non-detect and 393 μmol m- 2 s- 1. Substantial CH4 accumulation, coupled with oxygen (O2) depletion, measured in samples collected from custom-designed gas collection chambers at the Cambria site suggests that the development of explosion or asphyxiation hazards is possible in confined spaces above a rapidly degrading DFE release. However, the results also indicate that the development of such hazards is locally constrained, will require a high degree of soil moisture, close proximity to the source zone, a good connection between the soil and the confined space, and poorly aerated conditions.

Methane emissions and contaminant degradation rates at sites affected by accidental releases of denatured fuel-grade ethanol.

PubMed

Sihota, Natasha J; Mayer, K Ulrich; Toso, Mark A; Atwater, Joel F

2013-08-01

The recent increase in the use of denatured fuel-grade ethanol (DFE) has enhanced the probability of its environmental release. Due to the highly labile nature of ethanol (EtOH), it is expected to rapidly biodegrade, increasing the potential for inducing methanogenic conditions in the subsurface. As environmental releases of DFE can be expected to occur at the ground surface or in the vadose zone (e.g., due to surficial spills from rail lines or tanker trucks and leaking underground storage tanks), the potential for methane (CH4) generation at DFE spill sites requires evaluation. An assessment is needed because high CH4 generation rates may lead to CH4 fluxes towards the ground surface, which is of particular concern if spills are located close to human habitation-related to concerns of soil vapor intrusion (SVI). This work demonstrates, for the first time, the measurement of surficial gas release rates at large volume DFE spill sites. Two study sites, near Cambria and Balaton, in MN are investigated. Total carbon emissions at the ground surface (summing carbon dioxide (CO2) and CH4 emissions) are used to quantify depth-integrated DFE degradation rates. Results from both sites demonstrate that substantial CO2 and CH4 emissions do occur-even years after a spill. However, large total carbon fluxes, and CH4 emissions in particular, were restricted to a localized area within the DFE source zone. At the Balaton site, estimates of total DFE carbon losses in the source zone ranged between 5 and 174 μmol m(-2) s(-1), and CH4 effluxes ranged between non-detect and 9 μmol m(-2) s(-1). At the Cambria site estimates of total DFE carbon losses in the source zone ranged between 8 and 500 μmol m(-2) s(-1), and CH4 effluxes ranged between non-detect and 393 μmol m(-2) s(-1). Substantial CH4 accumulation, coupled with oxygen (O2) depletion, measured in samples collected from custom-designed gas collection chambers at the Cambria site suggests that the development of explosion or asphyxiation hazards is possible in confined spaces above a rapidly degrading DFE release. However, the results also indicate that the development of such hazards is locally constrained, will require a high degree of soil moisture, close proximity to the source zone, a good connection between the soil and the confined space, and poorly aerated conditions. Copyright © 2013 Elsevier B.V. All rights reserved.

Shifts in Geochemical Parameters and Greenhouse Gas Fluxes following Insect-Induced Tree Mortality

NASA Astrophysics Data System (ADS)

Brouillard, B.; Mikkelson, K. M.; Berryman, E.; Sharp, J.; Leonard, L.; Vega, M.

2016-12-01

Extensive insect infestations and resultant expansive tree mortality are occurring globally due in part to warmer temperatures and persistent drought. These forest disturbances are expected to cause shifts in the biogeochemical cycle due to the cessation of below ground root outputs, changes in soil microbial communities, hydrologic perturbations, and altered woody material deposits to the forest floor. To better understand biogeochemical alterations and resolve potentially conflicting findings, we studied a lodgepole pine forest recently impacted by mountain pine beetles to determine the response of subsurface geochemical parameters and gaseous flux to the effects of surrounding tree mortality. While many parameters were found to be significantly different under recently killed trees compared to their healthy counterparts (pH, soil moisture, C/N-species), notable biogeochemically relevant parameters displayed shifts that tracked with the level of surrounding tree mortality. For instance, aromatic carbon (TSUVA) and CO2 respiration were found to have an increasing linear response under grey trees as the surrounding tree mortality within an 8m radius also increased. Rather than a linear increase, ammonium and nitrogen associated bacterial communities displayed a threshold effect, not increasing until a certain level of tree mortality of approximately 40% was surpassed. Gas flux was also correlated to measured parameters in three near surface soil horizons to determine drivers of CO2 and N2O release and their interactions with biogeochemical cycles. Collectively, these results aid in elucidating the extent of forest mortality required to overcome compensatory terrestrial biogeochemical processes. A heightened understanding of these shifts will aid the scientific and resource management community through enhanced predictive understanding of greenhouse gas release or potential water quality impacts following forest disturbance.

Effects of fault-controlled CO2 alteration on mineralogical and geomechanical properties of reservoir and seal rocks, Crystal Geyser, Green River, Utah

NASA Astrophysics Data System (ADS)

Major, J. R.; Eichhubl, P.; Urquhart, A.; Dewers, T. A.

2012-12-01

An understanding of the coupled chemical and mechanical properties of reservoir and seal units undergoing CO2 injection is critical for modeling reservoir behavior in response to the introduction of CO2. The implementation of CO2 sequestration as a mitigation strategy for climate change requires extensive risk assessment that relies heavily on computer models of subsurface reservoirs. Numerical models are fundamentally limited by the quality and validity of their input parameters. Existing models generally lack constraints on diagenesis, failing to account for the coupled geochemical or geomechanical processes that affect reservoir and seal unit properties during and after CO2 injection. For example, carbonate dissolution or precipitation after injection of CO2 into subsurface brines may significantly alter the geomechanical properties of reservoir and seal units and thus lead to solution-enhancement or self-sealing of fractures. Acidified brines may erode and breach sealing units. In addition, subcritical fracture growth enhanced by the presence of CO2 could ultimately compromise the integrity of sealing units, or enhance permeability and porosity of the reservoir itself. Such unknown responses to the introduction of CO2 can be addressed by laboratory and field-based observations and measurements. Studies of natural analogs like Crystal Geyser, Utah are thus a critical part of CO2 sequestration research. The Little Grand Wash and Salt Wash fault systems near Green River, Utah, host many fossil and active CO2 seeps, including Crystal Geyser, serving as a faulted anticline CO2 reservoir analog. The site has been extensively studied for sequestration and reservoir applications, but less attention has been paid to the diagenetic and geomechanical aspects of the fault zone. XRD analysis of reservoir and sealing rocks collected along transects across the Little Grand Wash Fault reveal mineralogical trends in the Summerville Fm (a siltstone seal unit) with calcite and smectite increasing toward to the fault, whereas illite decreases. These trends are likely the result of CO2-related diagenesis, and similar trends are also observed in sandstone units at the site. Fracture mechanics testing of unaltered and CO2-altered sandstone and siltstone samples shows that CO2-related diagenesis, which is indicated by bleaching of the Entrada Fm, has significantly decreased the fracture resistance. The subcritical fracture index is similarly affected by alteration. These compositional and mechanical changes are expected to affect the extent, geometry, and flow properties of fracture networks in CO2 sequestration systems, and thus may significantly affect reservoir and seal performance in CO2 reservoirs. This work was funded in part by the Center for Frontiers of Subsurface Energy Security, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001114. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Long-term ground penetrating radar monitoring of a small volume DNAPL release in a natural groundwater flow field.

PubMed

Hwang, Yong Keun; Endres, Anthony L; Piggott, Scott D; Parker, Beth L

2008-04-04

An earlier field experiment at Canadian Forces Base Borden by Brewster and Annan [Geophysics 59 (1994) 1211] clearly demonstrated the capability of ground penetrating radar (GPR) reflection profiling to detect and monitor the formation of DNAPL layers in the subsurface. Their experiment involved a large volume release (770 L) of tetrachloroethylene into a portion of the sand aquifer that was hydraulically isolated from groundwater flow by sheet pile walls. In this study, we evaluated the ability of GPR profiling to detect and monitor much smaller volume releases (50 L). No subsurface confining structure was used in this experiment; hence, the DNAPL impacted zone was subjected to the natural groundwater flow regime. This condition allowed us to geophysically monitor the DNAPL mass loss over a 66 month period. Reflectivity variations on the GPR profiles were used to infer the presence and evolution of the solvent layers. GPR imaging found significant reflectivity increases due to solvent layer formation during the two week period immediately after the release. These results demonstrated the capacity of GPR profiling for the detection and monitoring of lesser volume DNAPL releases that are more representative of small-scale industrial spills. The GPR imaged solvent layers subsequently reduced in both areal extent and reflectivity after 29 months and almost completely disappeared by the end of the 66 month monitoring period. Total DNAPL mass estimates based on GPR profiling data indicated that the solvent mass was reduced to 34%-36% of its maximum value after 29 months; only 4%-9% of the solvent mass remained in the study area after 66 months. These results are consistent with independent hydrogeological estimates of remaining DNAPL mass based on the downgradient monitoring of the dissolved solvent phase. Hence, we have concluded that the long-term GPR reflectivity changes of the DNAPL layers are likely the result from the dissolution of chlorinated solvents residing in those layers. The long-term monitoring results demonstrated that GPR profiling is a promising non-invasive method for use at DNAPL contaminated sites in sandy aquifers where temporal information about immiscible contaminant mass depletion due to either natural flow or remediation is needed. However, our results also indicated that the GPR signature of older DNAPL impacted zones may not differ greatly from the uncontaminated background if significant mass reduction due to dissolution has occurred.

Goddard Institute for Space Studies (GISS) 3-Dimensional (3-D) Global Tracer Transport Model (DB1006)

DOE Data Explorer

Fung, I.

1993-01-01

This directory contains the input files used in simulations of atmospheric CO2 using the GISS 3-D global tracer transport model. The directory contains 16 files including a help file (CO2FUNG.HLP), 12 files containing monthly exchanges with vegetation and soils (CO2VEG.JAN - DEC), 1 file containing releases of CO2 from fossil fuel burning (CO2FOS.MRL), 1 file containing releases of CO2 from land transformations (CO2DEF.HOU), and 1 file containing the patterns of CO2 exchange with the oceans (CO2OCN.TAK).

Post-injection Multiphase Flow Modeling and Risk Assessments for Subsurface CO2 Storage in Naturally Fractured Reservoirs

NASA Astrophysics Data System (ADS)

Jin, G.

2015-12-01

Subsurface storage of carbon dioxide in geological formations is widely regarded as a promising tool for reducing global atmospheric CO2 emissions. Successful geologic storage for sequestrated carbon dioxides must prove to be safe by means of risk assessments including post-injection analysis of injected CO2 plumes. Because fractured reservoirs exhibit a higher degree of heterogeneity, it is imperative to conduct such simulation studies in order to reliably predict the geometric evolution of plumes and risk assessment of post CO2injection. The research has addressed the pressure footprint of CO2 plumes through the development of new techniques which combine discrete fracture network and stochastic continuum modeling of multiphase flow in fractured geologic formations. A subsequent permeability tensor map in 3-D, derived from our preciously developed method, can accurately describe the heterogeneity of fracture reservoirs. A comprehensive workflow integrating the fracture permeability characterization and multiphase flow modeling has been developed to simulate the CO2plume migration and risk assessments. A simulated fractured reservoir model based on high-priority geological carbon sinks in central Alabama has been employed for preliminary study. Discrete fracture networks were generated with an NE-oriented regional fracture set and orthogonal NW-fractures. Fracture permeability characterization revealed high permeability heterogeneity with an order of magnitude of up to three. A multiphase flow model composed of supercritical CO2 and saline water was then applied to predict CO2 plume volume, geometry, pressure footprint, and containment during and post injection. Injection simulation reveals significant permeability anisotropy that favors development of northeast-elongate CO2 plumes, which are aligned with systematic fractures. The diffusive spreading front of the CO2 plume shows strong viscous fingering effects. Post-injection simulation indicates significant upward lateral spreading of CO2 resulting in accumulation of CO2 directly under the seal unit because of its buoyancy and strata-bound vertical fractures. Risk assessment shows that lateral movement of CO2 along interconnected fractures requires widespread seals with high integrity to confine the injected CO2.

Mobilization and Transport of Organic Compounds from Reservoir Rock and Caprock in Geological Carbon Sequestration Sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhong, Lirong; Cantrell, Kirk J.; Mitroshkov, Alexandre V.

2014-05-06

Supercritical CO2 (scCO2) is an excellent solvent for organic compounds, including benzene, toluene, ethyl-benzene, and xylene (BTEX), phenols, and polycyclic aromatic hydrocarbons (PAHs). Monitoring results from geological carbon sequestration (GCS) field tests has shown that organic compounds are mobilized following CO2 injection. Such results have raised concerns regarding the potential for groundwater contamination by toxic organic compounds mobilized during GCS. Knowledge of the mobilization mechanism of organic compounds and their transport and fate in the subsurface is essential for assessing risks associated with GCS. Extraction tests using scCO2 and methylene chloride (CH2Cl2) were conducted to study the mobilization of volatilemore » organic compounds (VOCs, including BTEX), the PAH naphthalene, and n-alkanes (n-C20 – n-C30) by scCO2 from representative reservoir rock and caprock obtained from depleted oil reservoirs and coal from an enhanced coal-bed methane recovery site. More VOCs and naphthalene were extractable by scCO2 compared to the CH2Cl2 extractions, while scCO2 extractable alkane concentrations were much lower than concentrations extractable by CH2Cl2. In addition, dry scCO2 was found to extract more VOCs than water saturated scCO2, but water saturated scCO2 mobilized more naphthalene than dry scCO2. In sand column experiments, moisture content was found to have an important influence on the transport of the organic compounds. In dry sand columns the majority of the compounds were retained in the column except benzene and toluene. In wet sand columns the mobility of the BTEX was much higher than that of naphthalene. Based upon results determined for the reservoir rock, caprock, and coal samples studied here, the risk to aquifers from contamination by organic compounds appears to be relatively low; however, further work is necessary to fully evaluate risks from depleted oil reservoirs.« less

Multi-Sensor Mapping of Diffuse Degassing of C-O-H Compounds in Terrestrial Hydrothermal Systems

NASA Astrophysics Data System (ADS)

Schwandner, F. M.; Shock, E. L.

2004-12-01

In-situ single-sensor detection and mapping of diffuse degassing phenomena in hydrothermal and volcanic areas can be used to elucidate subsurface tectonic structures, assess emission rates, and to monitor emission variability (Williams 1985; Chiodini et al. 1996, Werner et al., 2003). More than one technique has been deployed to measure several gas species simultaneously (e.g., Crenshaw et al. 1982), and correlations of one gas species (usually CO2) with physical parameters like heat flux (Brombach et al., 2001), or with one other gas species (Rn, He) have been demonstrated (Barberi & Carapezza 1994; Williams-Jones et al., 2000). Recently, correlations of multiple gas species with one another were reported (Schwandner et al., 2004), leading to the possibility of quantitative mapping of subsurface hydrothermal chemical processes by simultaneous measurement of reaction partners and products that continuously and diffusely degas. In the present study, we joined a fully-quantitative multi-sensor instrument (Draeger Multiwarn II) to a modified accumulation-chamber sensing method (Chiodini et al., 1996) and measured diffuse degassing of CH4, H2, CO2, CO, and H2S. In this approach, each batch of gas that is recirculated through the detector is simultaneously analyzed by all sensors. To test this approach we chose two magmatically influenced, hydrothermally active areas at Yellowstone National Park (USA): Sylvan Springs and the Greater Obsidian Pool Area. The area near Obsidian Pool was previously studied during a diffuse CO2 degassing campaign (Werner & Brantley, 2004). Preliminary results show that elevated reduced gas emissions appear to be most prominent near hydrothermal pools, whereas CO2-dominated degassing anomalies highlight subsurface tectonic structures. This multimodal distribution allows us to distinguish deep degassing sources (CO2 anomalies) from shallow localized hydrothermal processes (reduced gas anomalies). The results permit us to positively identify and partially map a previously-inferred active lineament in the Obsidian Pool area. In addition, reduced gas data are yielding areal ratio distributions of CO/CO2, H2/CH4, and CO/CH4, that may be indicative of reactions such as the catalytic hydrogenation of CO2 (Sabatier-Process) and of CO (Fischer-Tropsch-Process) within the shallow hydrothermal system. Barberi & Carapezza (1994). Bull. Volcanol. 56(5): 335-342. Brombach, et al. (2001). Geophys. Res. Lett. 28(1): 69-72. Crenshaw et al. (1982). Nature 300: 345-346. Chiodini et al. (1996). Bull. Volcanol. 58(1): 41-50. Schwandner et al. (2004). JGR D 109: D04301, doi:10.1029/2003JD003890. Werner & Brantley (2004) JGR B 105: 10,831-10,846. Werner et al. (2003). Earth Planet. Sci. Lett. 210: 561-577. Williams (1985). Science 229(4713): 551-553. Williams-Jones et al. (2000). Bull. Volcanol. 62: 130-142.

Photoregulation of fructose and glucose respiration in the intact chloroplasts of Chlamydomonas reinhardtii F-60 and spinach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singh, K.K.; Changguo Chen; Gibbs, M.

1993-04-01

The photoregulation of chloroplastic respiration was studied by monitoring in darkness and in light the release of [sup 14]CO[sub 2] from whole chloroplasts of Chlamydomonas reinhardtii F-60 and spinach (Spinacia oleracea L.) supplied externally with [[sup 14]C]glucose and [[sup 14]C]fructose, respectively. CO[sub 2] release was inhibited more than 90% in both chloroplasts by a light intensity of 4 W m[sup [minus]2]. Oxidants, oxaloacetate in Chlamydomonas, nitrite in spinach, and phenazine methosulfate in both chloroplasts, reversed the inhibition. The onset of the photoinhibitory effect on CO[sub 2] release was relatively rapid compared to the restoration of CO[sub 2] release following illumination.more » In both darkened chloroplasts, dithiothreitol inhibited release. Of the four enzymes (fructokinase, phosphoglucose isomerase, glucose-6-P dehydrogenase, and gluconate-6-P dehydrogenase) in the pathway catalyzing the release of CO[sub 2] from fructose, only glucose-6-P dehydrogenase was deactivated by light and by dithiothreitol. 33 refs., 3 figs., 4 tabs.« less

Fundamental study of CO2-H2O-mineral interactions for carbon sequestration, with emphasis on the nature of the supercritical fluid-mineral interface.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bryan, Charles R.; Dewers, Thomas A.; Heath, Jason E.

2013-09-01

In the supercritical CO2-water-mineral systems relevant to subsurface CO2 sequestration, interfacial processes at the supercritical fluid-mineral interface will strongly affect core- and reservoir-scale hydrologic properties. Experimental and theoretical studies have shown that water films will form on mineral surfaces in supercritical CO2, but will be thinner than those that form in vadose zone environments at any given matric potential. The theoretical model presented here allows assessment of water saturation as a function of matric potential, a critical step for evaluating relative permeabilities the CO2 sequestration environment. The experimental water adsorption studies, using Quartz Crystal Microbalance and Fourier Transform Infrared Spectroscopymore » methods, confirm the major conclusions of the adsorption/condensation model. Additional data provided by the FTIR study is that CO2 intercalation into clays, if it occurs, does not involve carbonate or bicarbonate formation, or significant restriction of CO2 mobility. We have shown that the water film that forms in supercritical CO2 is reactive with common rock-forming minerals, including albite, orthoclase, labradorite, and muscovite. The experimental data indicate that reactivity is a function of water film thickness; at an activity of water of 0.9, the greatest extent of reaction in scCO2 occurred in areas (step edges, surface pits) where capillary condensation thickened the water films. This suggests that dissolution/precipitation reactions may occur preferentially in small pores and pore throats, where it may have a disproportionately large effect on rock hydrologic properties. Finally, a theoretical model is presented here that describes the formation and movement of CO2 ganglia in porous media, allowing assessment of the effect of pore size and structural heterogeneity on capillary trapping efficiency. The model results also suggest possible engineering approaches for optimizing trapping capacity and for monitoring ganglion formation in the subsurface.« less

Project ERIC - The search for environmental reactions induced by comets

NASA Astrophysics Data System (ADS)

Mendillo, M.; Sigwarth, J. B.; Craven, J. D.; Frank, L. A.; Holt, J.; Tetenbaum, D.

A sounding rocket experiment was conducted to release molecules of H2O and CO2 into the daytime ionosphere within the simultaneous fields of view of the Millstone Hill radar and the Dynamics Explorer UV imager. Preliminary results confirm the creation of chemically-induced F-region plasma depletions and reduced UV intensities from the modified region.

Synthesis of amphiphilic alternating polyesters with oligo(ethylene glycol) side chains and potential use for sustained release drug delivery.

PubMed

Wang, Wei; Ding, Jianxun; Xiao, Chunsheng; Tang, Zhaohui; Li, Di; Chen, Jie; Zhuang, Xiuli; Chen, Xuesi

2011-07-11

Novel amphiphilic alternating polyesters, poly((N-phthaloyl-l-glutamic anhydride)-co-(2-(2-(2-methoxyethoxy)ethoxy)methyl)oxirane) (P(PGA-co-ME(2)MO)), were synthesized by alternating copolymerization of PGA and ME(2)MO. The structures of the synthesized polyesters were characterized by (1)H NMR, (13)C NMR, FT-IR, and GPC analyses. Because of the presence of oligo(ethylene glycol) (OEG) side chains, the polyesters could self-assemble into thermosensitive micelles. Dynamic light scattering (DLS) showed that these micelles underwent thermoinduced size decrease without intermicellar aggregation. In vitro methyl thiazolyl tetrazolium (MTT) assay demonstrated that the polyesters were biocompatible to Henrietta Lacks (HeLa) cells, rendering their potential for drug delivery applications. Two hydrophobic drugs, rifampin and doxorubicin (DOX), were loaded into the polyester micelles and observed to be released in a zero-order sustained manner. The sustained release could be accelerated in lower pH or in the presence of proteinase K, due to the degradation of the polyester under these conditions. Remarkably, in vitro cell experiments showed that the polyester micelles accomplished fast release of DOX inside cells and higher anticancer efficacy as compared with the free DOX. With enhanced stability during circulation condition and accelerated drug release at the target sites (e.g., low pH or enzyme presence), these novel polyesters with amphiphilic structures are promising to be used in sustained release drug delivery systems.

Evaluating reaction pathways of hydrothermal abiotic organic synthesis at elevated temperatures and pressures using carbon isotopes

NASA Astrophysics Data System (ADS)

Fu, Qi; Socki, Richard A.; Niles, Paul B.

2015-04-01

Experiments were performed to better understand the role of environmental factors on reaction pathways and corresponding carbon isotope fractionations during abiotic hydrothermal synthesis of organic compounds using piston cylinder apparatus at 750 °C and 5.5 kbars. Chemical compositions of experimental products and corresponding carbon isotopic values were obtained by a Pyrolysis-GC-MS-IRMS system. Alkanes (methane and ethane), straight-chain saturated alcohols (ethanol and n-butanol) and monocarboxylic acids (formic and acetic acids) were generated with ethanol being the only organic compound with higher δ13C than CO2. CO was not detected in experimental products owing to the favorable water-gas shift reaction under high water pressure conditions. The pattern of δ13C values of CO2, carboxylic acids and alkanes are consistent with their equilibrium isotope relationships: CO2 > carboxylic acids > alkanes, but the magnitude of the fractionation among them is higher than predicted isotope equilibrium values. In particular, the isotopic fractionation between CO2 and CH4 remained constant at ∼31‰, indicating a kinetic effect during CO2 reduction processes. No "isotope reversal" of δ13C values for alkanes or carboxylic acids was observed, which indicates a different reaction pathway than what is typically observed during Fischer-Tropsch synthesis under gas phase conditions. Under constraints imposed in experiments, the anomalous 13C isotope enrichment in ethanol suggests that hydroxymethylene is the organic intermediate, and that the generation of other organic compounds enriched in 12C were facilitated by subsequent Rayleigh fractionation of hydroxymethylene reacting with H2 and/or H2O. Carbon isotope fractionation data obtained in this study are instrumental in assessing the controlling factors on abiotic formation of organic compounds in hydrothermal systems. Knowledge on how environmental conditions affect reaction pathways of abiotic synthesis of organic compounds is critical for understanding deep subsurface ecosystems and the origin of organic compounds on Mars and other planets.

The Effect of Mars-relevant Minerals on the Water Uptake of Magnesium Perchlorate and Implications for the Near-surface of Mars

NASA Astrophysics Data System (ADS)

Primm, Katherine; Gough, Raina; Rivera-Valentin, Edgard G.; Tolbert, Margaret

2017-10-01

The water uptake and release by hygroscopic salts such as perchlorate has been well studied in the decade since they were first discovered on the surface of Mars. However, there have been few studies on the effect of the insoluble regolith minerals on this well documented interaction of perchlorate and water vapor. In this work, we investigate the effect that two insoluble Mars-relevant minerals, montmorillonite and Mojave Mars Simulant (MMS), have on the water uptake (deliquescence), ice formation, and recrystallization (efflorescence) of pure magnesium perchlorate. We studied mixtures of equal parts (by mass) magnesium perchlorate hexahydrate and either montmorillonite or MMS. Although montmorillonite and MMS are insoluble minerals that may serve as nuclei for either ice nucleation or salt efflorescence, we find that these minerals did not affect any of the phase transitions of magnesium perchlorate. The salt-mineral mixture behaved like pure magnesium perchlorate in all cases, with stable deliquescence as well as metastable brine supersaturation and supercooling observed. Experiments were performed in both N2 and CO2 atmospheres, with no detectable difference. We use data from the Rover Environmental Monitoring Station instrument on MSL and from the Thermal and Electrical Conductivity Probe instrument on Phoenix, as well as modeling of the shallow subsurface near the rover and lander, to determine the likelihood of liquid water and water ice at Gale Crater and the Phoenix landing site.