Yongje Kim

Tracing the sources of nitrate in the Han River watershed in Korea, using δ15N-NO3− and δ18O-NO3− values

The dissolved nitrate concentrations and their nitrogen and oxygen isotopic ratios were analyzed in seasonal samples from Koreas Han River to ascertain the seasonal and spatial variations of dissolved nitrate and its possible sources. Nitrate concentrations in the South Han River (SHR) were much higher than those in the North Han River (NHR), probably because of the more extensive distribution of agricultural fields, residential areas and animal farms in the SHR drainage basin. The nitrogen isotopic composition of dissolved nitrate indicates that nitrate-nitrogen (NO(3)(-)-N) is derived mainly from atmospheric deposition and/or soil organic matter in the NHR but comes principally from manure or sewage, with only a minor contribution from atmospheric deposition or soil organic matter, in the SHR. The oxygen isotopic compositions of dissolved nitrate suggest that most atmospheric nitrate undergoes microbial nitrification before entering the river.

Rare earth elements as indicators of groundwater environment changes in a fractured rock system: evidence from fracture-filling calcite

Rare earth element (REE) abundances in core samples from Precambrian crystalline rocks at the Samkwang Mine site provide evidence of the solution chemistry involved in precipitation of calcite on fractures. The rock types collected in core samples are mainly banded-gneisses, with mineral assemblages dominated by biotite, K-feldspar, quartz and plagioclase. Calcite, chlorite, muscovite and sericite occur as secondary minerals, with calcite being the main filling material in fractures. In general, the core samples from 4 boreholes are enriched in light REE (LREE) and depleted in heavy REE (HREE), with negative Eu anomalies. However, positive Eu anomalies also occur at specific depths within 3 boreholes. Variation of chondrite-normalized REE patterns results from the fracture-filling calcite in core samples. Calcite fracture fillings provide a record of paleo-hydrology, where Eu has been reduced and selectively concentrated in the solutions from which calcite has precipitated.

Photoautotrophic hydrogen production by eukaryotic microalgae under aerobic conditions

Eukaryotic algae and cyanobacteria produce hydrogen under anaerobic and limited aerobic conditions. Here we show that novel microalgal strains (Chlorella vulgaris YSL01 and YSL16) upregulate the expression of the hydrogenase gene (HYDA) and simultaneously produce hydrogen through photosynthesis, using CO2 as the sole source of carbon under aerobic conditions with continuous illumination. We employ dissolved oxygen regimes that represent natural aquatic conditions for microalgae. The experimental expression of HYDA and the specific activity of hydrogenase demonstrate that C. vulgaris YSL01 and YSL16 enzymatically produce hydrogen, even under atmospheric conditions, which was previously considered infeasible. Photoautotrophic H2 production has important implications for assessing ecological and algae-based photolysis.

Feasibility of hydrogen production from ripened fruits by a combined two-stage (dark/dark) fermentation system

Anaerobic fermentation for hydrogen (H2) production was studied in a two-stage fermentation system fed with different ripened fruit feedstocks (apple, pear, and grape). Among the feedstocks, ripened apple was the most efficient substrate for cumulative H2 production (4463.7 mL-H2 L(-1)-culture) with a maximum H2 yield (2.2 mol H2 mol(-1) glucose) in the first stage at a hydraulic retention time (HRT) of 18 h. The additional cumulative biohydrogen (3337.4 mL-H2 L(-1)-culture) was produced in the second stage with the reused residual substrate from the first stage. The major byproducts in this study were butyrate, acetate, and ethanol, and butyrate was dominant among them in all test runs. During the two-stage system, the energy efficiency (H(2) conversion) obtained from mixed ripened fruits (RF) increased from 4.6% (in the first stage) to 15.5% (in the second stage), which indicated the energy efficiency can be improved by combined hydrogen production process. The RF could be used as substrates for biohydrogen fermentation in a two-stage (dark/dark) fermentation system.

The role of clay minerals in the reduction of nitrate in groundwater by zero-valent iron

Bench-scale batch experiments were performed to investigate the feasibility of using different types of clay minerals (bentonite, fullers earth, and biotite) with zero-valent iron for their potential utility in enhancing nitrate reduction and ammonium control. Kinetics experiments performed with deionized water (DW) and groundwater (GW) revealed nitrate reduction by Fe(0) proceeded at significantly faster rate in GW than in DW, and such a difference was attributed to the formation of green rust in GW. The amendment of the minerals at the dose of 25 g L(-1) in Fe(0) reaction in GW resulted in approximately 41%, 43%, and 33% more removal of nitrate in 64 h reaction for bentonite, fullers earth, and biotite, respectively, compared to Fe(0) alone reaction. The presumed role of the minerals in the rate enhancement was to provide sites for the formation of surface bound green rust. Bentonite and fullers earth also effectively removed ammonium produced from nitrate reduction by adsorption, with the removal efficiencies significantly increased with the increase in mineral dose above 5:1 Fe(0) to mineral mass ratio. Such a removal of ammonium was not observed for biotite, presumably due to its lack of swelling property. Equilibrium adsorption experiments indicated bentonite and fullers earth had maximum ammonium adsorption capacity of 5.6 and 2.1 mg g(-1), respectively.

Model-based evaluation of controlled-release systems in the remediation of dissolved plumes in groundwater

Controlled-release, semi-passive reactive barrier systems have been recently developed as a long-term treatment option for controlling the spread of contaminant plumes in groundwater. This paper describes a new computer code, and applies it to study coupled processes of solute release, reaction, and mass transport in an in situ remediation scheme using the controlled release of potassium permanganate. Confidence with the modeling approach was developed by model verifications and simulating results of a pilot-scale test-cell experiment. Sensitivity analyses indicated the possibilities of treatment inefficiencies due to inability of transverse dispersion to mix the permanganate (MnO(4)(-)) within the zone of reaction, fluctuations in source strength due to variations in flow velocity, and the small length of treatment zone due to strong soil utilization of MnO(4)(-). Although problems associated with the fluctuating source strength and strong soil utilization can be addressed by optimizing the release rate, the inefficiency of transverse dispersion to create mixing could pose a serious limitation. Through a series of model simulations, a system of injection/withdrawal wells in a doublet arrangement was developed to facilitate lateral spreading and mixing of MnO(4)(-). A well-mixed, stable MnO(4)(-) zone with predetermined size (DxL=8m x 2m) and concentration ranges (1.5-20 mg l(-1)) was created by four 1-day injection/withdrawal pumping periods over 24 d. This type of mixing zone may persist for many years with periodic well mixing and replacements of exhausted controlled-release forms. Coupled use of the generalized code with field hydrologic data will help to optimize the design and operation of controlled-release systems in practice.

The effect of granular ferric hydroxide amendment on the reduction of nitrate in groundwater by zero-valent iron

The feasibility of using granular ferric hydroxide (GFH) with zero-valent iron (Fe(0)) for its potential utility in enhancing nitrate reduction was investigated. The addition of 10gL(-1) GFH to 25gL(-1) Fe(0) significantly enhanced nitrate removal, resulting in 93% removal of 52.2mg-NL(-1) in 36-h as compared to 23% removal with Fe(0) alone. Surface analyses of the reacted Fe(0)/GFH revealed the presence of magnetite on the Fe(0) surface, which probably served as an electron mediator for nitrate reduction. Addition of GFH to Fe(0) also resulted in lower solution pH compared to Fe(0). The rate enhancing effect of GFH on nitrate reduction was attributed to the combined effects of magnetite formation and pH buffering by GFH. GFH amendment (100gL(-1)) significantly increased reduction capacity and longevity of Fe(0) to complete several nitrate reduction cycles before inactivation, giving a total nitrate removal of 205mg-NL(-1), while unamended Fe(0) gave only 20mg-NL(-1) before inactivation during the first reduction cycle. The overall result demonstrated the potential utility of Fe(0)/GFH system that may be developed into a viable technology for removal of nitrate from groundwater.

Sorption properties of152Eu and241 Am in geological materials: Eu as an analogue for monitoring the Am behaviour in heterogeneous geological environments

In order to confirm the similar behavior of Eu and Am in heterogeneous geological materials, we carried out the batch experiments for determining the sorption property of radionuclides,152Eu and241Am. We used four different types of core rocks including biotite banded gneiss, biotite gneiss, metabasite and andestic tuff, and selected two samples per each lithology, one of which is fracture-bearing and another is fracture-free. Except for metabasites, rock samples of each type are similar in their compositions. We calculated sorption ratios of two radionuclides from the experimental results. Biotite gneiss and tuff had similar sorption trends for152Eu and241Am regardless of the existence of fractures, whereas two metabasite samples showed very different sorption properties. Such difference in the sorption trends revealed a close relationship with chemical compositions of the host rocks. Nevertheless,152Eu and241Am showed similar adsorption trends for all the samples with variable contact times regardless of petrography and pH variations, and particularly, the sorption trends of152Eu and241Am in the metabasites were similar. This observation suggests that Eu and Am have similar sorption properties on geological materials. Therefore, Eu can be used as a useful analogue of Am in all kinds of geological environments regardless of variations in lithology and pH of groundwater. In addition, sorption ratios of152Eu and241 Am are correlated with the contents of P2O5 and TiO2, suggesting that the chemical components such as P2O5 and TiO2 might be important for deciphering the interaction between the radionuclide and groundwater.

Nitrate and ammonium ions removal from groundwater by a hybrid system of zero-valent iron combined with adsorbents

Nitrate (NO(3)(-)) is a commonly found contaminant in groundwater and surface water. It has created a major water quality problem worldwide. The laboratory batch experiments were conducted to investigate the feasibility of HCl-treated zero-valent iron (Fe(0)) combined with different adsorbents as hybrid systems for simultaneous removal of nitrate (NO(3)(-)) and ammonium (NH(4)(+)) ions from aqueous solution. The maximum NO(3)(-) removal in combined Fe(0)-granular activated carbon (GAC), Fe(0)-filtralite and Fe(0)-sepiolite systems was 86, 96 and 99%, respectively, at 45 °C for 24 h reaction time. The NO(3)(-) removal rate increased with the increase in initial NO(3)(-) concentration. The NO(3)(-) removal efficiency by hybrid systems was in the order of sepiolite > filtralite > GAC. The NH(4)(+) produced during the denitrification process by Fe(0) was successfully removed by the adsorbents, with the removal efficiency in the order of GAC > sepiolite > filtralite. Results of the present study suggest that the use of a hybrid system could be a promising technology for achieving simultaneous removal of NO(3)(-) and NH(4)(+) ions from aqueous solution.

Site Prioritization for Artificial Recharge in Korea using GIS Mapping

It is getting difficult to manage water resources in South Korea because more than half of annual precipitation is concentrated in the summer season and its intensity is increasing due to global warming and climate change. Artificial recharge schemes such as well recharge of surface water and roof-top rainwater harvesting can be a useful method to manage water resources in Korea. In this study, potential artificial recharge site is evaluated using geographic information system with hydrogeological and social factors. The hydrogeological factors include annual precipitation, geological classification based on geological map, specific capacity and depth to water level of national groundwater monitoring wells. These factors were selected to evaluate potential artificial recharge site because annual precipitation is closely related to source water availability for artificial recharge, geological features and specific capacity are related to injection capacity and depth to water is related to storage capacity of the subsurface medium. In addition to those hydrogeological factors, social aspect was taken into consideration by selecting the areas that is not serviced by national water works and have been suffered from drought. These factors are graded into five rates and integrated together in the GIS system resulting in spatial distribution of artificial recharge potential. Cheongsong, Yeongdeok in Gyeongsangbuk-do and Hadong in Gyeongsangnam-do, and Suncheon in Jeollanam-do were proven as favorable areas for applying artificial recharge schemes. Although the potential map for artificial recharge in South Korea developed in this study need to be improved by using other scientific factors such as evaporation and topographical features, and other social factors such as water-curtain cultivation area, hot spring resorts and industrial area where groundwater level is severely lowered, it can be used in a rough site-selection, preliminary and/or feasibility study for artificial recharge.