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.
The mobility of uranium (U) in the environment 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 mobility of uranium in a deep geological repository by a natural analogue approach using a uranium deposit in the Ogcheon Metamorphic Belt (OMB). Uranium contents of rock samples from the study site ranged from 1.3 to 71 ppm (average 17.4 ppm). Uranium minerals found in the study site were mostly uraninite (UIVO2+x) and uranothorite ((UIV, Th)SiO4). The concentrations of U in the groundwater samples were very low (0.025~0.690 ppb) even though redox conditions are weakly oxidizing. Calculation results for U speciation in groundwater samples showed that major dissolved uranium species in the groundwater samples are mainly as calcium uranyl (UO2 2+) carbonate complexes such as Ca2UO2(CO3)3(aq) and CaUO2(CO3)3 2-. However, the activity ratios between 234U and 238U (AR(234U/238U)) showed U behavior in reducing conditions although the groundwater conditions were not reducing conditions and major dissolved U species were U(VI) species. Results from electron microscopic analyses for rock samples showed that major uranium minerals were U(IV) minerals such as uraninite and uranothorite. We could not identify other uranyl minerals and altered minerals from uraninite. This means that the geochemical condition of the study site has been maintained a reducing condition although the groundwater condition was a weakly oxidizing condition. Thus, the dissolution of uranium is strongly limited by the low solubility of uraninite. It is not obvious how the reducing condition of the study site has been maintained. Reducing agents such as pyrite, organic materials, and reducing bacteria might contribute to maintaining the reducing condition although further studies will be necessary. Results from this study imply that uranium mobility will be greatly limited by low dissolution of uraninite into groundwater if the reducing condition is well reserved. This limited mobility of uranium will be also contributed by low possibility of uraninite alteration into uranyl minerals which have a higher solubility than uraninite.
In south Korea, most of uranium deposits are distributed in the Ogcheon belt, which is one of two late Precambrian to Paleozoic fold belts (the Imjingang and Ogcheon belts). A study site of the Ogcheon metamorphic belt (OMB) in Hoenam-myun, Boeun-gun was selected for the natural analogue study by preliminary site investigation for several candidate study sites. Three boreholes were drilled in the site and some rock cores and groundwater samples were taken from the boreholes. Various analytical studies for the samples are now being performed. Thus, in this study, various basic characteristics of the study site such as occurrence, geological, mineralogical, and chemical properties were investigated for a future study. Base rocks containing uranium in the OMB are usually black slate and coaly slate. Coaly slate usually shows a higher content of uranium and larger grain size of uranium than black slate. Uranium minerals found in the OMB are uraninite, uranothorite, brannerite, ekanite, coffinite, francevillite, uranophane, autunite, and torbernite depending on the base rock types. Uranothorite is abundant in black slate whereas uraninite is mostly abundant in coaly slate. Chemical compositions of the solid and groundwater samples from the study site were also analyzed by using ICP-MS/OES (Inductively Coupled Plasma Mass Spectrometry) and XRF (X-ray Fluorescence). This will contribute to determine uranium minerals in the solid samples and uranium speciation in the groundwater. The results of this study will contribute to performing future natural analogue studies in domestic uranium deposits and provide basic information and knowledge for understanding long-term geochemical behaviors of radionuclides in a high-level radioactive repository.
옥천대 우라늄 광화대 부근 퇴적암 지하수에 대한 수리지화학적 연구를 수행하여 옥천대 우라늄 광화대와 대전지역 우라늄 지하수와의 성인적 관련성을 고찰하였다. 지하수의 pH는 6.4-8.1의 범위로 중성에서 약칼리성 특성을 보이며, Eh는 대체로 -50-225 mV의 범위로서 일부는 환원성 환경의 특성을 보인다. 지하수는 탄산염광물의 용해반응으로 Ca2+ 및 HCO3- 함량이 우세한 Ca-HCO3 유형에 해당된다. 석탄광산 폐수에서는 1165μg/L의 우라늄이 검출되었으나 지하수내 우라늄 함량은 3.2μg/L 이하로 매우 낮다. 우라늄 광화대 부근 지하수에서 낮은 우라늄 함량은 낮은 Eh를 보이는 수리지화학적 특성에 기인한다. 대전지역 지하수 내 우라늄은 옥천대 우라늄 광화대로부터 공급되지는 않은 것으로 판단된다.
옥천습곡대의 서남부지역에서 분포하는 쥬라기 화강암류의 석영내에 존재하는 아문 미세균열과 유체표유물을 분석하여 이 지역에 작용한 고응력장을 해석하였다. 연구지역에서 나타나는 아문 미세균열의 방향성은 전체적으로 N30˚W의 방향이 가장 우세하며 N70˚W의 방향도 나타난다. 연구지역의 아문 미세균열 생성온도는 380-550˚C 범위를 보이며, 이들 아문 미세균열은 약 166-200Ma의 기간 동안 형성되었을 것으로 추정된다. 아문 미세균열의 방향성을 통한 고응력장의 작용 방향과 유체포유물에 의한 아문 미세균열의 형성시기를 비교하여 볼 때, 연구지역 내에서 발달하는 화강암질암체는 NNW-SSE와 WNW-ESE 방향의 최대수평주응력인 고응력장이 쥬라기 초기에서 쥬라기 중기 기간 동안 작용하였을 것으로 사료된다.
Main aspects of this study are to clarify igneous activity of igneous rocks, which is a member of various intrusives and volcanics exposed in the SE-zone of Ogcheon Geosynclinal belt, one of basement of Korean peninsula. Igneous rocks of study area along marginal area between SE-zone and C-zone of Ogcheon Geosynclinal belt consist of Pre-Cambrian orthogneiss, Triassic foliated granites and Namweon granites, Jurassic diorite-gabbro and granites, and Cretaceous granites and volcanics. Foliated granites in so-called Honam shear belt of study area is divided into four rock units based on the geologic age, mineralogy and texture : Daegang foliated granite, foliated hornblende biotite grandiorite, foliated biotite granodiorite and foliated two mica granite. Foliation of foliated granites generated by dextral strike slip movement at deep ductile shear zone. The individual synchronous plutons plottes on Harker diagram show mostly similar trend to the Daly's values. Each plots of the foliated granites, Jurassic granites and Cretaceous igneous rocks concentrate near trend of talc-alkali rock series on the AMF diagram. Igneous rocks of study area vary wide range in total REE content(83.27-377.49ppm) show LREE enriched than HREE in REE amount, and LREE have more steep negative slope in Eu(-) anomaly. From the date mentioned above, it is concluded the synchronous plutons which composed of several rock facies is considered to formed by differentiation of a series of magma. Geochronological episodes of igneous activity from early proterozoic to late Cretaceous between Jinan and Naju are two more Pre-Cambrian Orogenies, Songrim Disturbance, Daebo Orogeny and Bulkuksa Disturbance.
옥천대의 탄질 흑색 점파암에 최대 1000 ppm까지 부화되어 있는 몰리브덴의 광물학적 존재형태를 밝히기 위하여 충청북도 괴산군 덕평지역 흑색점판암에 대하여 박편제작, X선회절분석, 중성자활성화학분석, 주사전자현미경관찰, 에너지분산 X선분석, 파장분산 X선분석 등을 실시하였다. 그결과 몰리브덴은 두께 1~2μm 정도의 극미립 엽상 휘수연석(MoS2)으로 존재함이 판명되었다. 휘수연석은 흔히나이트의 포획물로 산출된다. 탄질흑색 점판암에 우라늄 및 바다듐과 함께 다량의 몰리브덴이 함유되어 있음에도 과거의 연구에서 그 존재형태가 규명되지 않은원인은, 극미립 휘수연석이 불투명한 세립 탄질기질에 분산 분포하기 때문이다.
Spotted cordierite occurs as the result of intrusion of Wolaksan Granite of Cretaceous age in the northern part of the Ogcheon Metamorphic Belt, forming a contact metamorphic zoning in accordance with the distance from the granite body: a cordierite-muscovite-biotite-quartz assemblage and the higher-temperature cordierite-biotite-quartz-(cummingtonite). These quartz-ubiquitous mineral assemblages identified in the cordierite spot seem to reflect Al-deficient condition of the protolith. TEM observations of textural relations between the cordierite and mica within the cordierite spot clearly reflect that cordierite was formed at the expense of micaceous matrix. A structure refinement of the poikiloblastic cordierite was performed by the Rietveld refinement method. Unit cell of the cordierite was determined to be as follows : lower-temperature type: a=17.1480(9)a, b=9.7743(6)a, c=9.3184(5)a, V=1561.9(4)a3, higher-temperature type: a=17.136(2)a, b=9.751(1)a, c=9.322(1)a, V=1557.7(4)a3. They show a remarkable difference in the unit cell dimension. The refinement results indicate that structural sites of lower-temperature cordierite are wholly occupied by appropriating ions. Compared to this, tetrahedral sites of the higher-temperature type exhibit an order/disorder ranging about 5-8% as the result of substitution between Si4+ and Al3+, except for T26 site occupied wholly by Al3+. These structural differences seem to be related to the formation temperatures of both cordierite types.