[논문]pH가 낮은 탄산수의 CO2 탈기에 따른 용존탄소동위원소 변화

채기탁; 유순영; 김찬영; 박진영; 방하은; 이인혜; 고동찬; 신영재; 오진만

doi:10.7857/jsge.2019.24.3.024

pH가 낮은 탄산수의 CO2 탈기에 따른 용존탄소동위원소 변화
Changes of carbon-13 Isotope of Dissolved Inorganic Carbon Within Low-pH CO2-rich Water during CO2 Degassing 원문보기

지하수토양환경 = Journal of soil and groundwater environment, v.24 no.3, 2019년, pp.24 - 35

채기탁 (한국지질자원연구원) , 유순영 (고려대학교 지구환경과학과 K-COSEM 사업단) , 김찬영 (한국지질자원연구원) , 박진영 (한국지질자원연구원) , 방하은 (한국지질자원연구원) , 이인혜 (한국지질자원연구원) , 고동찬 (한국지질자원연구원) , 신영재 (한국지질자원연구원) , 오진만 (KNJ 엔지니어링(주))

Abstract ▼ AI-Helper

It is known that ${\delta}^{13}C_{DIC}$ (carbon-13 isotope of dissolved inorganic carbonate (DIC) ions) of water increases when dissolved $CO_2$ degases. However, ${\delta}^{13}C_{DIC}$ could decrease when the pH of water is lower than 5.5 at the early stage of degassing. Laboratory experiments were performed to observe the changes of ${\delta}^{13}C_{DIC}$ as $CO_2$ degassed from three different artificial $CO_2$-rich waters (ACWs) in which the initial pH was 4.9, 5.4, and 6.4, respectively. The pH, alkalinity and ${\delta}^{13}C_{DIC}$ were measured until 240 hours after degassing began and those data were compared with kinetic isotope fractionation calculations. Furthermore, same experiment was conducted with the natural $CO_2$-rich water (pH 4.9) from Daepyeong, Sejong City. As a result of experiments, we could observe the decrease of DIC and increase of pH as the degassing progressed. ACW with an initial pH of 6.4, ${\delta}^{13}C_{DIC}$ kept increasing but, in cases where the initial pH was lower than 5.5, ${\delta}^{13}C_{DIC}$ decreased until 6 hours. After 6 hours ${\delta}^{13}C_{DIC}$ increased within all cases because the $CO_2$ degassing caused pH increase and subsequently the ratio of $HCO_3{^-}$ in solution. In the early stage of $CO_2$ degassing, the laboratory measurements were well matched with the calculations, but after about 48 hours, the experiment results were deviated from the calculations, probably due to the equilibrium interaction with the atmosphere and precipitation of carbonates. The result of this study may be not applicable to all natural environments because the pressure and $CO_2$ concentration in headspace of reaction vessels was not maintained constant as well as the temperature. Nevertheless, this study provides fundamental knowledge on the ${\delta}^{13}C_{DIC}$ evolution during $CO_2$ degassing, and therefore it can be utilized in the studies about carbonated water with low pH and the monitoring of geologic carbon sequestration.

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$Fig. 1. (a) εDIC-CO2(g) calculated using Eq. (12) at different temperatures and pH. Carbon isotopic fractionation factors between each carbon species (i.e., H2CO3*, HCO3, CO3) and CO2(g) refer to Clark and Fritz (1997). The blue dotted line indicates the εDIC-CO2(g) of Zhang et al. (1995). (b) δ13CDIC variations as CO2 degassed and DIC decreased when the initial pH was 4.5, 5.5, 6.5 or 7.5. Numbers on the lines indicate the pH at the DIC fraction. The yellow dots represent the point where pH increased by 0.5.$ 그림 Fig. 1. (a) ε_DIC-CO2(g) calculated using Eq. (12) at different temperatures and pH. Carbon isotopic fractionation factors between each carbon species (i.e., H₂CO₃^*, HCO₃, CO₃) and CO_2(g) refer to Clark and Fritz (1997). The blue dotted line indicates the ε_DIC-CO2(g) of Zhang et al. (1995). (b) δ¹³C_DIC variations as CO₂ degassed and DIC decreased when the initial pH was 4.5, 5.5, 6.5 or 7.5. Numbers on the lines indicate the pH at the DIC fraction. The yellow dots represent the point where pH increased by 0.5.
그림 Fig. 2. Diagram for the laboratory CO₂ degassing experiment of CO₂-rich waters. pH and alkalinity were measured using the Mettler Toledo titrator, T50 while δ¹³C_DIC was analyzed using the Picarro G2121-i Isotopic CO₂ Analyzer. Dissolved inorganic carbon (DIC) in CO₂-rich waters was precipitated as BaCO₃which was converted to CO_2(g) by a pre-treatment device (Automate FX Inc.).
그림 Fig. 3. Temporal variations in CO₂-rich waters during CO₂ degassing. (a) pH, (b) alkalinity, (c) dissolved inorganic carbon (DIC), (d) CO₂ partial pressure of solution (P_CO2), (3) Carbon-13 isotope of DIC (δ¹³C_DIC). In (b) and (c), the values indicate the ratios to the intial values.
표 Table 1. pH, PCO₂, calculated and measured δ¹³CDIC values 48 hours after CO₂ degassing
그림 Fig. 4. Decrease of DIC due to CO₂ degassing versus pH in (a) to (d) and δ¹³C_DIC in (e) to (h). (a) and (e) for w-2, (b) and (f) for ACW 4.9 (Artificial CO₂-rich Water with the intial pH of 4.9), (c) and (g) for ACW5.4, (d) and (h) for ACW6.4. The blue lines indicate the calculated values using Eq. (5) with assuming an open system, while the red dots and lines indicates measurements. Numbers indicate the elapsed time(hour) after CO₂ degassing began.
그림 Fig. 5. δ¹³C_DIC variations versus DIC during CO₂ degassing depending on intial pH conditions.
표 Table 2. Previous studies on the δ¹³CDIC variations during CO₂ degassing in which the intial pH of natural/artifical waters were higher than 5.5

질의응답

핵심어	질문	논문에서 추출한 답변
	왜 국내외에서는 CO2 지중저장 부지의 천부 모니터링 기술을 활발히 개발하는가?	이산화탄소 포집지중저장(CCS)은 지구온난화를 2℃ 이내로 묶어두기 위한 핵심 기술로 여겨지고 있다(UNFCCC, 2017). 그러나 높은 포집비용과 환경 리스크는 CCS 사업을 대규모로 수행하는데 걸림돌로 작용하고 있다(Celia, 2017). 이에 따라 국내외에서는 CO2 지중저장 부지의 천부 모니터링 기술을 활발히 개발하고 있다(Jenkins et al.
	CO2 탈기에 따른 δ13CDIC의 변화에 대한 연구는 무엇을 목적으로 수행되었는가?	CO2 탈기에 따른 δ13CDIC의 변화에 대한 연구는 CO2 지중저장 분야 외에 (1) 지표수 또는 탄산수를 이용한 탄산염계의 해석 및 탄소 순환에 관한 연구, (2) 동굴침전물(speleothem) 생성과정에서 탄소동위원소 변화 해석, (3) 탄산염 군집 동위원소 지온계(carbonate clumped isotope thermometry)에 응용하기 위한 기초연구를 목적으로 수행되었다. 이러한 연구는 (1) 하천수의 유동경로에 따른δ13CDIC의 변화 관찰/해석(van Geldern et al.
	이산화탄소 포집지중저장(CCS)은 어떤 기술인가?	이산화탄소 포집지중저장(CCS)은 지구온난화를 2℃ 이내로 묶어두기 위한 핵심 기술로 여겨지고 있다(UNFCCC, 2017). 그러나 높은 포집비용과 환경 리스크는 CCS 사업을 대규모로 수행하는데 걸림돌로 작용하고 있다(Celia, 2017).

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