The mobility of uranium (U) in various disposal environments of a deep geological repository is controlled by various geochemical conditions and parameters. In particular, oxidation state of uranium is considered as a major factor to control the mobility of uranium in most of geological environments. In this study, therefore, we investigated the geochemical behaviors of uranium in grounwater samples from natural analogue study sites located in the Ogcheon Metamorphic Belt (OMB). Groundwater samples were taken using a packer system from Boeun Hoenam-myun site and Geumsan Suyoung-ri site where several boreholes were dilled with various depths. The geochemical properties and parameters such as temperature, pH, Eh, EC, and DO were directly measured in the site using an in-line measurement method. The concentrations of major cations and anions in the groundwater samples were measured by using ICP-OES (Inductively Coupled Plasma-Optical Emission Spectrometry) and IC (Ion Chromatography), respectively. The concentrations of trace elements including U and Th were measured by using ICP-MS (Inductively Coupled Plasma-Mass Spectrometry) The concentrations of U in the groundwater samples are very low for the Hoenammyun site (0.03~0.69 ppb) and Suyoung-ro site (0.39~1.74 ppb) even though the two sites are uranium deposits and redox conditions are weakly oxidizing. The speciation, saturation index (SI), pH-Eh (Poubaix) diagram were calculated using the Geochemist’s Workbench (GWB 9.0) program and the recent OECD/NEA thermochemical database for U. Calculation results for U speciation in the groundwater samples show that major dissolved uranium species in the groundwater samples are mainly as calcium uranyl carbonate complexes such as Ca2UO2(CO3)3(aq) and CaUO2(CO3)3 2- for almost all groundwater samples. The calculated results for SI and Poubaix diagram also show that the dominant uranium solid phase is a uranyl silicate mineral, uranophane (Ca(H2O)(UVIO2)2 (SiO2)2(OH)6), not uraninite (UIVO2). Since the determination of Eh values for natural groundwater samples is very difficult and uncertain work, we analyzed and discussed the effect of Eh on the geochemical behaviors of U in the groundwater. However, these calculation results are not consistent with the observation for U minerals in rock samples using electron microscopic techniques. Thus, we need further studies to explain the discrepancy between calculation and observation results.

Time-resolved laser fluorescence spectroscopy (TRLFS) and excitation-emission matrix (EEM) spectroscopy were used to study the interaction of U(VI) and natural organic matters (NOMs) in groundwater. Various types of groundwaters (DB-1, DB-3 from KURT site and OB-1, OB-3 from a U deposit in Ogcheon metamorphic belt) were used as samples. Pulsed Nd-YAG laser at 266 nm (Continuum Minilite) was used as the light source of TRLFS. The laser pulse energy of 1.0 mJ was fixed for all measurements. The luminescence spectrum was recorded using a gated intensified chargecoupled device (Andor, DH-720/18U03 iStar 720D) attached to the spectrograph (Andor, SR-303i). EEM spectra were measured using a spectrofluorometer (Horiba Scientific, Aqualog) equipped with a 150 W ozone-free xenon arc lamp. Excitation spectra were recorded by scanning the excitation wavelength from 200 to 500 nm. Emission spectra were measured using a CCD in the wavelength range of 242–823 nm. In the case of the recently collected DB-1 samples, it was observed that the U and NOM quantities decreased compared to the samples collected before 2016. For some DB-1 samples, the amount of dissolved organic carbon indicating the presence of NOM was significantly reduced, and changes consistent with this phenomenon were observed in the EEM spectrum. The time-resolved luminescence characteristics (peak wavelengths and lifetime) of U(VI) in the DB-1 samples agree well with those of Ca2UO2(CO3)3(aq). This U(VI) species remains stable, even in samples taken five years ago. The estimated amounts of U and NOM from the spectroscopic data of DB-3, OB-1, and OB-3 samples are relatively low compared to DB-1 samples. When a known amount of U(VI) was mixed in each groundwater, the time-resolved luminescence spectrum exhibited a characteristic spectral shape different from the expected luminescence intensity. This phenomenon is presumed to be due to the interaction between U(VI) and NOM in groundwater. The results of this study suggest that the chemical speciation of NOM as well as U(VI) is required to understand U behavior in groundwater.

KURT(KAERI Underground Research Tunnel) 지하수에 존재하는 천연 유기물질과 6가 우라늄(U(VI))화학종의 상호작용을 레이저 분광학 기술을 이용하여 조사하였다. 지하수 시료에 266 nm 파장의 레이저 빛을 입사시켜 자외선 및 파란색 파장 영 역에서 방출되는 천연 유기물질의 발광 스펙트럼을 관측하였다. 0.034-0.788 mg·L-1 농도 범위의 우라늄이 함유된 지하수에 서는 녹색 파장 영역에서 방출되는 U(VI) 화학종의 발광 스펙트럼을 측정하였다. 지하수에 함유된 U(VI) 화학종의 발광 특 성(피크 파장 및 발광 수명)이 실험실에서 제조한 표준용액에 함유된 Ca2UO2(CO3)3(aq)의 발광 특성과 매우 유사하다는 것 을 확인하였다. 지하수에 존재하는 U(VI) 화학종의 발광 세기는 표준용액에 함유된 같은 농도의 Ca2UO2(CO3)3(aq)의 발광 세기에 비해 약하다. 표준용액의 Ca2UO2(CO3)3(aq)를 천연 유기물질이 함유된 지하수에 섞었을 때에도 Ca2UO2(CO3)3(aq)의 발광 세기가 감소한다. 이러한 현상의 원인을 지하수의 천연 유기물질과 Ca-U(VI)-탄산염 화학종의 상호작용으로 인해 비 발광성 U(VI) 착물이 형성되기 때문인 것으로 설명하였다.

The importance of interaction between surface water and groundwater has been increased for the understanding and analyzing hydrological cycle in natural stream system. In this study, the interaction between surface water and groundwater is qualitatively analyzed by using a field measurement of water level and temperature in Guamcheon stream, South Korea. The results show that temperature measurement is necessary to assess the interaction between surface water and ground water not only water level. The interactions between surface water and groundwater in short stream can be analyzed by using this method and the accuracy of stream-groundwater interactions can be enhanced in the concept of hydrological analysis by adding the temperature variation data. Consequently, this method based on field measurement can be expected as a basic procedure for qualitative study on stream-groundwater interactions.