• Economic and Environmental Geology
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• v.47 no.1
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• pp.61-69
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• 2014

As we are trying to in-situ treat (purify or immobilize) heavy metals or radionuclides in groundwater, one of the geochemical factors to be necessarily considered is the value of oxidation/reduction potential (ORP) of the groundwater. A biogeochemical impact on the characteristic ORP change of groundwater taken from the KAERI underground was observed as a function of time by adding electron-donor (lactate), electron-acceptor (sulfate), and indigenous bacteria in a laboratory condition. There was a slight increase of Eh (slow oxidation) of the pure groundwater with time under a $N_2$-filled glove-box. However, most of groundwaters that contained lactate, sulfate or bacteria showed Eh decrease (reduction) characteristics. In particular, when 'Baculatum', a local indigenous sulfate-reducing bacterium, was injected into the KAERI groundwater, it turned to become a highly-reduced one having a decreased Eh to around -500 mV. Although the sulfate-reducing bacterium thus has much greater ability to reduce groundwater than other metal-reducing bacteria, it surely necessitated some dissolved ferrous-sulfate and finally generated sulfide minerals (e.g., mackinawite), which made a prediction for subsequent reactions difficult. As a result, the ORP of groundwater was largely affected even by a slight injection of nutrient without bacteria, indicating that oxidation state, solubility and sorption characteristics of dissolved contaminants, which are affected by the ORP, could be changed and controlled through in-situ biostimulation method.

• Economic and Environmental Geology
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• v.56 no.3
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• pp.311-330
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• 2023

Development of Carbon Capture and Storage (CCS) technique is becoming increasingly important as a method to mitigate the strengthening effects of global warming, generated from the unprecedented increase in released anthropogenic CO₂. In the recent years, the characteristics of basaltic rocks (i.e., large volume, high reactivity and surplus of cation components) have been recognized to be potentially favorable in facilitation of CCS; based on this, research on utilization of basaltic formations for underground CO₂ storage is currently ongoing in various fields. This study investigated the feasibility of underground storage of CO₂ in basalt, based on the examination of the CO₂ storage mechanisms in subsurface, assessment of basalt characteristics, and review of the global research on basaltic CO₂ storage. The global research examined were classified into experimental/modeling/field demonstration, based on the methods utilized. Experimental conditions used in research demonstrated temperatures ranging from 20 to 250 ℃, pressure ranging from 0.1 to 30 MPa, and the rock-fluid reaction time ranging from several hours to four years. Modeling research on basalt involved construction of models similar to the potential storage sites, with examination of changes in fluid dynamics and geochemical factors before and after CO₂-fluid injection. The investigation demonstrated that basalt has large potential for CO₂ storage, along with capacity for rapid mineralization reactions; these factors lessens the environmental constraints (i.e., temperature, pressure, and geological structures) generally required for CO₂ storage. The success of major field demonstration projects, the CarbFix project and the Wallula project, indicate that basalt is promising geological formation to facilitate CCS. However, usage of basalt as storage formation requires additional conditions which must be carefully considered - mineralization mechanism can vary significantly depending on factors such as the basalt composition and injection zone properties: for instance, precipitation of carbonate and silicate minerals can reduce the injectivity into the formation. In addition, there is a risk of polluting the subsurface environment due to the combination of pressure increase and induced rock-CO₂-fluid reactions upon injection. As dissolution of CO₂ into fluids is required prior to injection, monitoring techniques different from conventional methods are needed. Hence, in order to facilitate efficient and stable underground storage of CO₂ in basalt, it is necessary to select a suitable storage formation, accumulate various database of the field, and conduct systematic research utilizing experiments/modeling/field studies to develop comprehensive understanding of the potential storage site.

• Economic and Environmental Geology
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• v.28 no.4
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• pp.351-367
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• 1995

The elemental geochemistry and oxygen isotopes of illite/smectite (I/S) have been studied in relationship to the mineralogical trend in the Reindeer D-27 well, Beaufort-Mackenzie Basin. The increase in concentrations of $K_2O$, Rb and rare earth elements (REE), the decrease in concentrations of tetrahedral elements such as Mg, Ti, Sc, Zn and Zr, and the increase in concentrations of tetrahedral elements such as Be and V can be related to I/S compositions that vary systematically with depth. Layer formulae of S- and I-layers are estimated as $[Al_{1.57}Fe_{.19}Mg_{.31}Ti_{.07}][Si_{3.84}Al_{.16}]O_{10}(OH)_2$ and $[Al_{1.84}Mg_{.16}][Si_{3.33}Al_{.67}]O_{10}(OH)_2$, respectively. The mobilization of REE appears to occur during illitization. The increase in concentrations of REE, especially La and Ce, with depth is probably linked to incorporation of ions with high valency (e.g. $V^{5+}$) in tetrahedral sites. The excess valency due to V is partly counter-balanced by ions with low valency (e.g. $Be^{2+}$) and, in turn, the local valency deficiency caused by $Be^{2+}$ could be compensated by high-charge interlayer cations such as REE (＋3). ${\delta}^{18}O$ values of I/S range from 2.91 to 15.72‰ (SMOW), and increase with depth, contrasting to trends observed in the Gulf Coast and elsewhere. The increase in ${\delta}^{18}O$ of I/S results from the rapid increase in ${\delta}^{18}O$ of pore water that overcomes the decrease in temperature-dependent fractionation values with increasing burial depth (${\delta}^{18}O_{pore\;water}>-d{\Delta}/_{I/S-water};\;d{\delta}^{18}O_{I/S}>0$). Calculated ${\delta}^{18}O$ values of pore water in equilibrium with I/S suggest that the original water was probably meteoric water. The stratification of pore water is postulated from the presence of an isotopically light interval, about 450m thick. The depth range of the isotopically light zone overlaps, but does not coincide with the interval of lowered I-content and $K_2O$ concentrations, suggesting that oxygens may have been exchanged independently of mineralogical and geochemical reactions.

• Korean Journal of Mineralogy and Petrology
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• v.36 no.4
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• pp.355-363
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• 2023

In this study, we explore the nature of clumped isotopes of H₂O molecule using quantum chemical calculations. Particularly, we estimated the relative clumping strength between diverse isotopologues, consisting of oxygen (¹⁶O, ¹⁷O, and ¹⁸O) and hydrogen (hydrogen, deuterium, and tritium) isotopes and quantify the effect of temperature on the extent of isotope clumping. The optimized equilibrium bond lengths and the bond angles of the molecules are 0.9631-0.9633 Å and 104.59-104.62°, respectively, and show a negligible variation among the isotopologues. The calculated frequencies of the modes of H₂O molecules decrease as isotope mass number increases, and show a more prominent change with varying hydrogen isotopes over those with oxygen isotopes. The equilibrium constants of isotope substitution reactions involving these isotopologues reveal a greater effect of hydrogen mass number than oxygen mass number. The calculated equilibrium constants of clumping reaction for four heavy isotopologues showed a strong correlation; particularly, the relative clumping strength of three isotopologues was 1.86 times (HT¹⁸O), 1.16 times (HT¹⁷O), and 0.703 times (HD¹⁷O) relative to HD¹⁸O, respectively. The relative clumping strength decreases with increasing temperature, and therefore, has potential for a novel paleo-temperature proxy. The current calculation results highlight the first theoretical study to establish the nature of clumped isotope fractions in H₂O including ¹⁷O and tritium. The current results help to account for diverse geochemical processes in earth's surface environments. Future efforts include the calculations of isotope fractionations among various phases of H₂O isotopologues with a full consideration of the effect of anharmonicity in molecular vibration.