Economic and Environmental Geology (자원환경지질)

The Korean Society of Economic and Environmental Geology (대한자원환경지질학회)
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Lithium Distribution in Thermal Groundwater: A Study on Li Geochemistry in South Korean Deep Groundwater Environment

온천수 내 리튬 분포: 국내 심부 지하수환경의 리튬 지화학 연구

  • Hyunsoo Seo (Department of Earth and Environmental Sciences, Korea University) ;
  • Jeong-Hwan Lee (Korea Radioactive Waste Agency) ;
  • SunJu Park (Earth ENG Co.) ;
  • Junseop Oh (Department of Earth and Environmental Sciences, Korea University) ;
  • Jaehoon Choi (Department of Earth and Environmental Sciences, Korea University) ;
  • Jong-Tae Lee (Korea Central Hot Spring Institute) ;
  • Seong-Taek Yun (Department of Earth and Environmental Sciences, Korea University)
  • 서현수 (고려대학교 지구환경과학과) ;
  • 이정환 (한국원자력환경공단) ;
  • 박선주 ((주)어스이엔지) ;
  • 오준섭 (고려대학교 지구환경과학과) ;
  • 최재훈 (고려대학교 지구환경과학과) ;
  • 이종태 (한국중앙온천연구소) ;
  • 윤성택 (고려대학교 지구환경과학과)
  • Received : 2023.12.07
  • Accepted : 2023.12.10
  • Published : 2023.12.29
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Abstract

The value of lithium has significantly increased due to the rising demand for electric cars and batteries. Lithium is primarily found in pegmatites, hydrothermally altered tuffaceous clays, and continental brines. Globally, groundwater-fed salt lakes and oil field brines are attracting attention as major sources of lithium in continental brines, accounting for about 70% of global lithium production. Recently, deep groundwater, especially geothermal water, is also studied for a potential source of lithium. Lithium concentrations in deep groundwater can increase through substantial water-rock reaction and mixing with brines. For the exploration of lithim in deep groundwater, it is important to understand its origin and behavior. Therefore, based on a nationwide preliminary study on the hydrogeochemical characteristics and evolution of thermal groundwater in South Korea, this study aims to investigate the distribution of lithium in the deep groundwater environment and understand the geochemical factors that affect its concentration. A total of 555 thermal groundwater samples were classified into five hydrochemical types showing distinct hydrogeochemical evolution. To investigate the enrichment mechanism, samples (n = 56) with lithium concentrations exceeding the 90th percentile (0.94 mg/L) were studied in detail. Lithium concentrations varied depending upon the type, with Na(Ca)-Cl type being the highest, followed by Ca(Na)-SO4 type and low-pH Ca(Na)-HCO3 type. In the Ca(Na)-Cl type, lithium enrichment is due to reverse cation exchange due to seawater intrusion. The enrichment of dissolved lithium in the Ca(Na)-SO4 type groundwater occurring in Cretaceous volcanic sedimentary basins is related to the occurrence of hydrothermally altered clay minerals and volcanic activities, while enriched lithium in the low-pH Ca(Na)-HCO3 type groundwater is due to enhanced weathering of basement rocks by ascending deep CO2. This reconnaissance geochemical study provides valuable insights into hydrogeochemical evolution and economic lithium exploration in deep geologic environments.

전기 자동차 및 배터리에 대한 수요가 증가함에 따라 리튬의 가치가 크게 증가하였다. 리튬은 주로 페그마타이트, 열수변질을 받은 응회암질 퇴적 점토 및 대륙성 염수에서 발견된다. 전 세계적으로 지하수로 공급되는 염호와 유전 염수는 세계 리튬 생산량의 약 70%를 차지하는 대륙 염수의 주요 리튬 공급원으로 주목받고 있다. 최근에는 심부 지하수, 특히 지열수도 리튬의 잠재적 공급원으로 연구되고 있다. 심부 지하수의 리튬 농도는 상당한 물-암석 반응과 염수와의 혼합을 통해 증가할 수 있다. 심부 지하수 중의 리튬 탐사를 위해서는 그 기원과 거동을 이해하는 것이 중요하다. 따라서 본 연구에서는 전국적인 규모에서 국내 온천지역 지열수의 수문지화학 특성과 진화에 관한 예비연구를 바탕으로, 심부 지하수 환경에서의 리튬의 분포를 평가하고 그 농도에 영향을 미치는 지구화학적 요인을 이해하고자 하였다. 총 555개의 온천 지하수 시료 자료는 수화학적 특성에 따라 뚜렷한 지화학 진화 특성을 갖는 5가지 유형으로 분류되었다. 또한, 리튬의 부화 기작을 평가하기 위해 리튬 농도가 90번째 백분위수(0.94 mg/L)를 초과하는 시료(n = 56)에 대해 자세히 고찰하였다. 리튬의 농도는 수화학 유형에 따라 유의미한 차이를 보였는데, Na(Ca)-Cl유형, Ca(Na)-SO4유형, pH가 낮은 Ca(Na)-HCO3 유형 순이었다. Ca(Na)-Cl 유형에서 리튬 부화는 해수침투에 따른 역이온 교환으로 발생한다. 백악기 화산퇴적 분지에서 특징적으로 나타나는 Ca(Na)-SO4 유형 지하수에서 용존 리튬의 부화는 열수 변질 점토 광물의 산출 및 화산활동과 관련이 있는 반면, 낮은 pH의 Ca(Na)-HCO3 유형 지하수에서는 심부 CO2의 상승 혼입에 의한 기반암의 풍화 촉진으로 인해 리튬 부화가 일어난 것으로 해석된다. 본 광역 예비 지화학 연구 결과는 심부 지질환경에서의 수문지화학 진화에 대한 이해와 함께 향후 경제성 있는 리튬 탐사 지침과 관련하여 유용한 정보를 제공할 것이다.

Keywords

Acknowledgement

이 논문은 2022년도 정부(산업통상자원부)의 재원으로 "사용후핵연료관리핵심기술개발사업단" 및 한국에너지기술평가원의 지원을 받아 수행된 연구사업의 결과임(과제번호 2021040101003C; 과제명 "사용후핵연료 처분 부지평가기술 및 안전성 입증체계 구축").

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