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Title: Arsenic mobilization in shallow aquifers due to CO 2 intrusion from storage reservoirs

Abstract

We developed an integrated framework of combined batch experiments and reactive transport simulations to quantify water-rock-CO 2 interactions and arsenic (As) mobilization responses to CO 2 and/or saline water leakage into USDWs. Experimental and simulation results suggest that when CO 2 is introduced, pH drops immediately that initiates release of As from clay minerals. Calcite dissolution can increase pH slightly and cause As re-adsorption. Thus, the mineralogy of the USDW is ultimately a determining factor of arsenic fate and transport. Salient results suggest that: (1) As desorption/adsorption from/onto clay minerals is the major reaction controlling its mobilization, and clay minerals could mitigate As mobilization with surface complexation reactions; (2) dissolution of available calcite plays a critical role in buffering pH; (3) high salinity in general hinders As release from minerals; and (4) the magnitude and quantitative uncertainty of As mobilization are predicated on the values of reaction rates and surface area of calcite, adsorption surface areas and equilibrium constants of clay minerals, and cation exchange capacity. Results of this study are intended to improve ability to quantify risks associated with potential leakage of reservoir fluids into shallow aquifers, in particular the possible environmental impacts of As mobilization at carbon sequestrationmore » sites.« less

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1];  [2];  [3];  [4];  [1];  [4]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)
  3. New Mexico Inst. of Mining and Technology, Socorro, NM (United States)
  4. Univ. of Utah, Salt Lake City, UT (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1369173
Report Number(s):
LA-UR-16-28763
Journal ID: ISSN 2045-2322
Grant/Contract Number:
AC52-06NA25396
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 7; Journal Issue: 1; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Earth Sciences; Arsenic mobilization, adsorption/desorption, clay mineral, surface complexation, integrated framework, batch experiment.

Citation Formats

Xiao, Ting, Dai, Zhenxue, Viswanathan, Hari S., Hakala, Alexandra, Cather, Martha, Jia, Wei, Zhang, Yongchao, and McPherson, Brian. Arsenic mobilization in shallow aquifers due to CO2 intrusion from storage reservoirs. United States: N. p., 2017. Web. doi:10.1038/s41598-017-02849-z.
Xiao, Ting, Dai, Zhenxue, Viswanathan, Hari S., Hakala, Alexandra, Cather, Martha, Jia, Wei, Zhang, Yongchao, & McPherson, Brian. Arsenic mobilization in shallow aquifers due to CO2 intrusion from storage reservoirs. United States. doi:10.1038/s41598-017-02849-z.
Xiao, Ting, Dai, Zhenxue, Viswanathan, Hari S., Hakala, Alexandra, Cather, Martha, Jia, Wei, Zhang, Yongchao, and McPherson, Brian. 2017. "Arsenic mobilization in shallow aquifers due to CO2 intrusion from storage reservoirs". United States. doi:10.1038/s41598-017-02849-z. https://www.osti.gov/servlets/purl/1369173.
@article{osti_1369173,
title = {Arsenic mobilization in shallow aquifers due to CO2 intrusion from storage reservoirs},
author = {Xiao, Ting and Dai, Zhenxue and Viswanathan, Hari S. and Hakala, Alexandra and Cather, Martha and Jia, Wei and Zhang, Yongchao and McPherson, Brian},
abstractNote = {We developed an integrated framework of combined batch experiments and reactive transport simulations to quantify water-rock-CO2 interactions and arsenic (As) mobilization responses to CO2 and/or saline water leakage into USDWs. Experimental and simulation results suggest that when CO2 is introduced, pH drops immediately that initiates release of As from clay minerals. Calcite dissolution can increase pH slightly and cause As re-adsorption. Thus, the mineralogy of the USDW is ultimately a determining factor of arsenic fate and transport. Salient results suggest that: (1) As desorption/adsorption from/onto clay minerals is the major reaction controlling its mobilization, and clay minerals could mitigate As mobilization with surface complexation reactions; (2) dissolution of available calcite plays a critical role in buffering pH; (3) high salinity in general hinders As release from minerals; and (4) the magnitude and quantitative uncertainty of As mobilization are predicated on the values of reaction rates and surface area of calcite, adsorption surface areas and equilibrium constants of clay minerals, and cation exchange capacity. Results of this study are intended to improve ability to quantify risks associated with potential leakage of reservoir fluids into shallow aquifers, in particular the possible environmental impacts of As mobilization at carbon sequestration sites.},
doi = {10.1038/s41598-017-02849-z},
journal = {Scientific Reports},
number = 1,
volume = 7,
place = {United States},
year = 2017,
month = 6
}

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  • In spite of the numerous studies on changes within the reservoir following CO 2 injection and the effects of CO 2 release into overlying aquifers, little or no literature is available on the effect of CO 2 release on rock between the storage reservoirs and subsurface. This is important, because the interactions that occur in this zone between the CO 2 storage reservoir and the subsurface may have a significant impact on risk analysis for CO 2 storage projects. To address this knowledge gap, relevant rock materials, temperatures and pressures were used to study mineralogical and elemental changes in thismore » intermediate zone. Furthermore, after rocks reacted with CO 2-acidified 0.01 M NaCl, liquid analysis showed an increase of major elements (e.g., Ca and Mg) and variable concentrations of potential contaminants (e.g., Sr and Ba); lower aqueous concentrations of these elements were observed in N 2 control experiments, likely due to differences in pH between the CO 2 and N 2 experiments. In experiments with As/Cd and/or organic spikes, representing potential contaminants in the CO 2 plume originating in the storage reservoir, most or all of these contaminants were removed from the aqueous phase. SEM and M√∂ssbauer spectroscopy results showed the formation of new minerals and Fe oxides in some CO 2-reacted samples, indicating potential for contaminant removal through mineral incorporation or adsorption onto Fe oxides. These experiments show the interactions between the CO 2-laden plume and the rock between storage reservoirs and overlying aquifers have the potential to affect the level of risk to overlying groundwater, and should be considered during site selection and risk evaluation.« less
  • If carbon dioxide stored in deep saline aquifers were to leak into an overlying aquifer containing potable groundwater, the intruding CO{sub 2} would change the geochemical conditions and cause secondary effects mainly induced by changes in pH In particular, hazardous trace elements such as lead and arsenic, which are present in the aquifer host rock, could be mobilized. In an effort to evaluate the potential risks to potable water quality, reactive transport simulations were conducted to evaluate to what extent and mechanisms through which lead and arsenic might be mobilized by intrusion of CO{sub 2}. An earlier geochemical evaluation ofmore » more than 38,000 groundwater quality analyses from aquifers throughout the United States and an associated literature review provided the basis for setting up a reactive transport model and examining its sensitivity to model variation. The evaluation included identification of potential mineral hosts containing hazardous trace elements, characterization of the modal bulk mineralogy for an arenaceous aquifer, and augmentation of the required thermodynamic data. The reactive transport simulations suggest that CO{sub 2} ingress into a shallow aquifer can mobilize significant lead and arsenic, contaminating the groundwater near the location of intrusion and further downstream. Although substantial increases in aqueous concentrations are predicted compared to the background values, the maximum permitted concentration for arsenic in drinking water was exceeded in only a few cases, whereas that for lead was never exceeded.« less
  • More than 80 years of silver mining in the Cobalt area (Ontario, Canada) has led to widespread contamination of water with arsenic. The objective of this study was to determine the impact of changes in redox conditions on the stability of As in samples collected from a tailings wetland in the historic mining camp. Dissolved metal concentrations were monitored while tailings samples ({approx}1300 mg of As kg{sup -1}, pH 7.4) were subjected to 30 days of reduction. Reoxidation of the samples was accomplished by air drying. The As oxidation states in the original, reduced, and reoxidized samples were determined usingmore » X-ray absorption spectroscopy (XAS). Arsenic speciation was affected by changes in redox conditions, resulting in rapid mobilization of As during reduction. Glucose input had a significant impact on the dissolution and speciation of As, suggesting that the As transformation was microbially mediated. When carbon was not limiting, the combination of reducing conditions and lower pH favored the formation of As(-) species.« less
  • We examined the hypothesis that sulfide drives arsenic mobilization from pyritic black shale by a sulfide-arsenide exchange and oxidation reaction in which sulfide replaces arsenic in arsenopyrite forming pyrite, and arsenide (As-1) is concurrently oxidized to soluble arsenite (As+3). This hypothesis was tested in a series of sulfide-arsenide exchange experiments with arsenopyrite (FeAsS), homogenized black shale from the Newark Basin (Lockatong formation), and pyrite isolated from Newark Basin black shale incubated under oxic (21% O2), hypoxic (2% O2, 98% N2), and anoxic (5% H2, 95% N2) conditions. The oxidation state of arsenic in Newark Basin black shale pyrite was determinedmore » using X-ray absorption-near edge structure spectroscopy (XANES). Incubation results show that sulfide (1 mM initial concentration) increases arsenic mobilization to the dissolved phase from all three solids under oxic and hypoxic, but not anoxic conditions. Indeed under oxic and hypoxic conditions, the presence of sulfide resulted in the mobilization in 48 h of 13-16 times more arsenic from arsenopyrite and 6-11 times more arsenic from isolated black shale pyrite than in sulfide-free controls. XANES results show that arsenic in Newark Basin black shale pyrite has the same oxidation state as that in FeAsS (-1) and thus extend the sulfide-arsenide exchange mechanism of arsenic mobilization to sedimentary rock, black shale pyrite. Biologically active incubations of whole black shale and its resident microorganisms under sulfate reducing conditions resulted in sevenfold higher mobilization of soluble arsenic than sterile controls. Taken together, our results indicate that sulfide-driven arsenic mobilization would be most important under conditions of redox disequilibrium, such as when sulfate-reducing bacteria release sulfide into oxic groundwater, and that microbial sulfide production is expected to enhance arsenic mobilization in sedimentary rock aquifers with major pyrite-bearing, black shale formations.« less