Byoung-Young Choi

Hydrochemical and multivariate statistical interpretations of spatial controls of nitrate concentrations in a shallow alluvial aquifer around oxbow lakes (Osong area, central Korea)

Hydrochemical and multivariate statistical interpretations of 16 physicochemical parameters of 45 groundwater samples from a riverside alluvial aquifer underneath an agricultural area in Osong, central Korea, were performed in this study to understand the spatial controls of nitrate concentrations in terms of biogeochemical processes occurring near oxbow lakes within a fluvial plain. Nitrate concentrations in groundwater showed a large variability from 0.1 to 190.6 mg/L (mean=35.0 mg/L) with significantly lower values near oxbow lakes. The evaluation of hydrochemical data indicated that the groundwater chemistry (especially, degree of nitrate contamination) is mainly controlled by two competing processes: 1) agricultural contamination and 2) redox processes. In addition, results of factorial kriging, consisting of two steps (i.e., co-regionalization and factor analysis), reliably showed a spatial control of the concentrations of nitrate and other redox-sensitive species; in particular, significant denitrification was observed restrictedly near oxbow lakes. The results of this study indicate that sub-oxic conditions in an alluvial groundwater system are developed geologically and geochemically in and near oxbow lakes, which can effectively enhance the natural attenuation of nitrate before the groundwater discharges to nearby streams. This study also demonstrates the usefulness of multivariate statistical analysis in groundwater study as a supplementary tool for interpretation of complex hydrochemical data sets.

Distribution of Heavy Metals (Cr, Cu, Zn, Pb, Cd, As) in Roadside Sediments, Seoul Metropolitan City, Korea

Urban roadside sediments were collected for five months from eleven sites in Seoul Metropolitan City and were examined for spatial and temporal variation of heavy metal composition (Cr, Cu, Zn, Pb, Cd and As). Samples for analysis were treated with 0.1 N HCl for partial extraction and with mixed strong acid (HF + HNO3 + HClO4) for total extraction. Using the normalization of the acid extractable metal concentrations with aluminum (element/Al), two statistical approaches, i.e., two-way ANOVA test and R-mode factor analysis (FA), were performed to examine the major sources of variability in the heavy metal composition. The FA results show that Pb and Cr are strongly dependent on site-specific traffic density, whereas Cu, Cd and Zn vary with site characterization (especially the percentage of metal industry) as well as the temporal amount of precipitation. Arsenic, however, does not show any distinct change. As the roadside sediments are heavily polluted with heavy metals (especially Zn and Cu), the management and disposal of the sediments have to be guided by appropriate environmental measures.

Hydrochemistry of urban groundwater, Seoul, Korea: The impact of subway tunnels on groundwater quality

Hydrogeologic and hydrochemical data for subway tunnel seepage waters in Seoul (Republic of Korea) were examined to understand the effect of underground tunnels on the degradation of urban groundwater. A very large quantity of groundwater (up to 63 million m3 year(-1)) is discharged into subway tunnels with a total length of 287 km, resulting in a significant drop of the local groundwater table and the abandonment of groundwater wells. For the tunnel seepage water samples (n = 72) collected from 43 subway stations, at least one parameter among pathogenic microbes (total coliform, heterotrophic bacteria), dissolved Mn and Fe, NH4+, NO3(-), turbidity, and color exceeded the Korean Drinking Water Standards. Locally, tunnel seepage water was enriched in dissolved Mn (avg. 0.70 mg L(-1), max. 5.58 mg L(-1)), in addition to dissolved Fe, NH4+, and pathogenic microbes, likely due to significant inflow of sewage water from broken or leaking sewer pipes. Geochemical modeling of redox reactions was conducted to simulate the characteristic hydrochemistry of subway tunnel seepage. The results show that variations in the reducing conditions occur in urban groundwater, dependent upon the amount of organic matter-rich municipal sewage contaminating the aquifer. The organic matter facilitates the reduction and dissolution of Mn- and Fe-bearing solids in aquifers and/or tunnel construction materials, resulting in the successive increase of dissolved Mn and Fe. The present study clearly demonstrates that locally significant deterioration of urban groundwater is caused by a series of interlinked hydrogeologic and hydrochemical changes induced by underground tunnels.

Atmospheric versus lithogenic contribution to the composition of first- and second-order stream waters in Seoul and its vicinity

The spatial variations in the chemistry of first- and second-order stream waters (N = 65) were investigated in the easterly bound of Seoul in order to assess the effects of urban air pollution on surface water chemistry. The sulfate (SO4(2-)) was high (range 3.9-17.8 mg l(-1), mean 11.8 mg l(-1)) within 30 km away from the center of Seoul, compared to the levels (range 1.1-7.7 mg l(-1), mean 4.3 mg l(-1)) observed in remote areas (30-70 km away). Both graphical examination and statistical evaluation (variogram) of sulfate concentration data consistently showed the decrease of sulfate concentration with increasing distance. The results of mass balance modeling also indicate that the concentrations of SO4(2-), Cl- and Na+ may be affected mainly by dry/wet deposition. However, the spatial variations of major cations such as Ca2+ and Na+ are well explained by the reaction of rainwater with diverse rocks in the watercourse. The water type was found to change from Ca(-Na)-SO4) type to Ca(-a)-HCO3 type with the increasing distance. It is thus inferred that the pollutants like SO2 emitted from strong man-made source areas of Seoul are transported to the considerable distance (at least 30 km away) by westerlies and that such mechanism may lead to the changes of the anion composition in surface water. In the remote area (> 30 km away from Seoul), the stream water chemistry appears to be influenced more effectively by the weathering of rock-forming minerals.

Assessment of mobility and bio-availability of heavy metals in dry depositions of Asian dust and implications for environmental risk.

We assess the potential mobility and bio-availability of selected metals (As, Cd, Co, Cr, Cu, Ni, Mo, Pb, S, Zn, and Zr) in the dry depositions of Asian and non-Asian dust from the city of Daejeon, Korea. For this study, we applied Pb isotopes, total extraction and chemical sequential extraction methods to the dry depositions. In addition, microscopic analysis was performed using X-ray diffraction (XRD) and focused ion beam (FIB)-scanning electron microscopy (SEM-EDS). FIB-SEM cross-section observations and Pb isotope data showed a black carbon is an important carrier of associated heavy metals originating from China. A five-step sequential extraction performed on the dry depositions showed that S and Cd are the most abundant elements in the water-soluble and cation-exchangeable fraction. In addition, Zn and Pb appeared predominantly in the carbonate and reducible fractions. On the other hand, Cu, Mo and, to a lesser degree, As were significantly associated with the organic fraction, while Co, Ni, Cr and Zr were bound to the residual fraction. These results showed that S, Cd, Zn and Pb, which were highly concentrated in potentially mobile fractions, have potential environmental risk because potential changes in redox state and pH may remobilize these metals. In addition, the estimated remobilization concentrations of these metals were significant. Thus, this study shows that frequent and careful monitoring of S, Cd, Z, Pb and, to a lesser degree, Cu, Mo and As is very important for assessing environmental risk in Korea.

Role of oxbow lakes in controlling redox geochemistry of shallow groundwater under a heterogeneous fluvial sedimentary environment in an agricultural field: Coexistence of iron and sulfate reduction

This study aimed to extend the knowledge of the vertical distribution of redox conditions of shallow groundwater in heterogeneous fluvial sediments near oxbow lakes. For this study, we revisited the study area of Kim et al. (2009) to examine the redox zoning in details. Three multi-level samplers were installed along a flow path near two oxbow lakes to obtain vertical profiles of the subsurface geology and hydrochemical and isotopic data (δ(18)O and δD of water, δ(15)N and δ(18)O of nitrate, and δ(34)S of sulfate) of groundwater. Geologic logging showed that characteristics of the heterogeneous subsurface geology are closely related to the pattern of vertical redox zoning. Hydrochemical data in conjunction with nitrogen and sulfur isotope data show that the redox status of groundwater near oxbow lakes is controlled by denitrification, iron reduction, and sulfate reduction. The oxidizing condition of groundwater occurs in the sand-dominant alluvium located in the up-gradient of oxbow lakes, whereas the reducing condition accompanying denitrification, iron reduction, and local sulfate reduction is developed in silt-rich alluvium in and the downgradient of oxbow lakes. The occurrence of sulfate reduction was newly found in this study. However, the vertical profiles of redox-sensitive parameters show that iron reduction and sulfate reduction occur concurrently near oxbow lakes, although the measured redox potentials suggest that thermodynamic conditions are controlled by the stability of Fe(2+)/Fe-oxides. Therefore, this study shows that the redox condition of groundwater in the iron-rich zone should be carefully interpreted. For this purpose, depth-specific sampling and careful examination of sulfur isotope data will be very useful for identifying the redox processes occurring in the zone with overlapping iron reduction and sulfate reduction in heterogeneous fluvial sediments.

Geochemical Influence on Microbial Communities at CO2-Leakage Analog Sites

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.

Impact of SO2 on Alteration of Reservoir Rock with Ca-Deficient Conditions and Poor Buffering Capacity under a CO2 Geologic Storage Condition

The objective of this study is to evaluate the impact of SO2-CO2-water-rock interaction on the alteration of a reservoir rock having Ca-deficient conditions and little buffering capacity and its implication for porosity change near the injection well from a CO2 storage pilot site, Republic of Korea. For our study, three cases of experimental and geochemical modeling were carried out (pure CO2, 0.1% SO2 in CO2, and 1% SO2 in CO2, resp.) under realistic geologic storage conditions. Our results show that SO2 accelerated water-rock interactions by lowering the pH. In the 1% SO2 case, pH remained less than 2 during the experiments because of insufficient buffering capacity. Sulfate minerals were not precipitated because of an insufficient supply of Ca. Because the total volume of precipitated secondary minerals was less than that of the dissolved primary minerals, the porosity of rock increased in all cases. Chlorite largely contributed to the decrease in total rock volume although it formed only 4.8 wt.% of the rock. Our study shows that the coinjection of a certain amount of SO2 at CO2 storage reservoirs without carbonate and Ca-rich minerals can significantly increase the porosity by enhancing water-rock interactions. This procedure can be beneficial to CO2 injection under some conditions.

Status and Implications of Regulatory Frameworks for Environmental Management of Geologic CO 2 Storage in USA and EU

Though geologic storage of (GS) is considered as an attractive technological option to enormously reduce greenhouse gases emission into the atmosphere, many concerns on potential environmental and health risks associated with leakage have been raised. In particular, groundwater contamination due to the brine displacement by a pressure build-up and the acidification by leaked is paid a special attention. Therefore, integrated regulatory frameworks have been established by law in many countries to secure the permanent containment of injected . Regulatory frameworks deal with entire processes of GS, including site selection, monitoring and post-closure environmental management. This review paper provides a summary of regulatory frameworks in USA (U.S. EPA Geologic Sequestration Rule) and EU (Geologic Sequestration Directive). The regulatory framework to properly address environmental issues should be established for the deployment of CCS projects in Korea.