All Issue

2025 Vol.30, Issue 1
Real-time Measurement of Dissolved CO2 and Carbon-13 Isotope Using Membrane Contactor

멤브레인 콘택터를 이용한 탈이온수 내 용존 CO2와 탄소 -13 동위원소의 실시간 측정

Gitak Chae1*
,
Ji-Hyun Kim1
,
Soohyeon Moon2
,
Chanhee Jang13
채 기탁1*
,
김 지현1
,
문 수현2
,
장 찬희13
1Korea Institute of Geoscience and Mineral Resources, 124 Gwahak-ro, Yuseoung-gu, Daejeon 34132, Korea
2Korea Testing Laboratory, 87 Digital-ro 26-gil, Guro-gu, Seoul 08339, Korea
3Chungnam National University, 99 Daehak-ro, Yuseoung-gu, Daejeon 34134, Korea
1한국지질자원연구원
2한국산업기술시험원
3충남대학교
*Corresponding Author
28 February 2025. pp. 1-11
PDF XML Citation
Abstract

This study integrated a Membrane Contactor (MC) with a Tedlar Bag Reactor (TBR) for continuous, real-time monitoring of dissolved CO2 and its carbon isotope (δ13C) in deionized water (DIW). Experiments were conducted in two stages across three CO2 concentrations (437, 7,940 ppmv, and 100%). Baseline CO2 (437 ppmv) and δ13C levels were measured in the first stage, while the second stage involved observing changes after injecting 7,940 ppmv or 100% of CO2 into the TBR. CO2 and δ13C levels were tracked using Cavity Ring-Down Spectroscopy (CRDS) on gas samples extracted through the MC. CO2 dissolution led to a significant pH decrease and an increase in electrical conductivity (EC), reflecting CO2’s chemical interactions with water. δ13C values showed substantial variation at lower CO2 concentrations, while higher CO2 levels resulted in more stable δ13C values with clearer shifts. The findings suggest that the MC system is particularly effective for monitoring environments characterized by rapid and dynamic chemical changes, such as geological CO2 storage, volcanic gas emissions, earthquake-related gas dynamics, and CO2-rich waters. This research demonstrates that MC-based systems can enhance field applications by supporting continuous sampling and real-time dissolved gas analysis.

Keywords
Membrane Contactor (MC)
Tedlar Bag Reactor (TBR)
dissolved gas extraction sampling
dissolved CO2 monitoring
dissolved carbon isotope
References
1

Bein, E., Zucker, I., Drewes, J.E., and Hübner, U., 2021, Ozone membrane contactors for water and wastewater treatment: A critical review on materials selection, mass transfer and process design, Chem. Eng. J., 413, 127393. doi.org/10.1016/j.cej.2020.127393

10.1016/j.cej.2020.127393
2

Cheng, A., Sherwood Lollar, B., Gluyas, J.G., and Ballentine, C.J., 2023, Primary N2-He gas field formation in intracratonic sedimentary basins, Nature, 615(7950), 94-99.

10.1038/s41586-022-05659-0
3

Choi, J., Yu, S., Park, S., Park, J., and Yun, S.-T., 2022, Status and implications of hydrogeochemical characterization of deep groundwater for deep geological disposal of high-level radioactive wastes in developed countries, Econ. Environ. Geol., 55(6), 737-760 (in Korean). doi.org/10.9719/EEG.2022.55.6.737

10.9719/EEG.2022.55.6.737
4

Clark, I.D. and Fritz, P., 1997, Environmental Isotope in Hydrology, Lewis Pub., NY USA, 328pp. doi.org/10.1201/9781482242911

10.1201/9781482242911
5

Fang, Y., Hozalski, R.M., Clapp, L.W., Novak, P.J., and Semmens, M.J., 2002, Passive dissolution of hydrogen gas into groundwater using hollow-fiber membranes, Water. Res., 36(14), 3533-3542. doi.org/10.1016/S0043-1354(02)00046-5

10.1016/S0043-1354(02)00046-5
6

Gardner, P. and Solomon, D.K., 2009, An advanced passive diffusion sampler for the determination of dissolved gas concentrations, Water. Resour. Res., 45(6), W06423, doi.org/10.1029/2008WR007399. doi.org/10.1029/2008WR007399

10.1029/2008WR007399
7

Hach, 2013, Technical note: What are the individual part of a pH electrode, https://at.hach.com/asset-get.download.jsa?id=25593629884 [Accessed on 30 August 2024]

8

Hales, B. and Takahashi, T., 2002, The pumping SeaSoar: A high-resolution seawater sampling platform, J. Atmos. Ocean. Technol., 19(7), 1096-1104. doi.org/10.1175/1520-0426(2002)019<1096:TPSAHR>2.0.CO;2

10.1175/1520-0426(2002)019<1096:TPSAHR>2.0.CO;2
9

Ham, B., Choi, B. Y., Chae, G.-T., Kirk, M.F., and Kwon, M.J., 2017, Geochemical influence on microbial communities at CO2-leakage analog sites, Front. Microbiol., 8, 2203, https://doi.org/10.3389/fmicb.2017.02203. doi.org/10.3389/fmicb.2017.02203

10.3389/fmicb.2017.0220329170659PMC5684959
10

Hartmann, J.F., Gentz, T., Schiller, A., Greule, M., Grossart, H.-P.,Ionescu, D., Keppler, F., Martinez-Cruz, K., Sepulveda-Jauregui, A., and Isenbeck‐Schröter, M., 2018, A fast and sensitive method for the continuous in situ determination of dissolved methane and its δ13C‐isotope ratio in surface waters, Limnol Oceanogr: Methods, 16(5), 273-285, doi.org/10.1002/lom3.10244

10.1002/lom3.10244
11

Herbstritt, B., Gralher, B., and Weiler, M., 2019, Continuous, near-real-time observations of water stable isotope ratios during rainfall and throughfall events, Hydrol. Earth. Syst. Sci., 23(7), 3007-3019, doi.org/10.5194/hess-23-3007-2019

10.5194/hess-23-3007-2019
12

Jiang, W., Hu, S.-M., Lu, Z.-T., Ritterbusch, F., and Yang, G.-m., 2020, Latest development of radiokrypton dating - A tool to find and study paleogroundwater, Quater. Inter., 547, 166-171, doi.org/10.1016/j.quaint.2019.04.025

10.1016/j.quaint.2019.04.025
13

Kim, J.H., Ferguson, G., Person, M., Jiang, W., Lu, Z.T., Ritterbusch, F., Yang, G.M., Tyne, R., Bailey, L., Ballentine, C., Reiners, P., and McIntosh, J., 2022, Krypton-81 dating constrains timing of deep groundwater flow activation, Geophys Res. Lett., 49(11), e2021GL097618, doi.org/10.1029/2021GL097618

10.1029/2021GL097618
14

Kim, Y.J., Kang, Y.Y., Hwang, D.G, Jeon, T.W., and Shin, S.K., 2017, Decomposition characteristics of pollutants by time dependent variation of livestock carcass leachate, Anal. Sci. Technol., 30(6) 338-347 (in Korean). doi.org/10.5806/AST.2017.30.6.338

10.5806/AST.2017.30.6.338
15

Koh, H.C., Ha, S.Y., and Nam, S.Y., 2011, Preparation and properties of hollow fiber membrane for gas separation using CTA, Membr. J., 21(1), 98-105 (in Korean)

16

Lee, H., 2024, Revisiting geochemical perspectives on degassing of the subcontinental lithospheric mantle, Geosci. J., 28(5) 781-788, doi.org/10.1007/s12303-024-0026-0

10.1007/s12303-024-0026-0
17

Lee, S., Kang, N., Park, M., Hwang, J.Y., Yun, S.H., and Jeong, H.Y., 2018, A review on volcanic gas compositions related to volcanic activities and non-volcanological effects, Geosci. J., 22, 183-197.

10.1007/s12303-017-0056-y
18

Liu, Y., Koops, G.H., and Strathmann, H., 2003, Characterization of morphology controlled polyethersulfone hollow fiber membranes by the addition of polyethylene glycol to the dope and bore liquid solution, J. Membr. Sci., 223(1-2), 187-199, doi.org/10.1016/S0376-7388(03)00322-3

10.1016/S0376-7388(03)00322-3
19

Loose, B., Stute, M., Alexander, P., and Smethie, W.M., 2009, Design and deployment of a portable membrane equilibrator for sampling aqueous dissolved gases, Water. Resour. Res., 45(4), W00D34, doi.org/10.1029/2008WR006969

10.1029/2008WR006969
20

Lu, Z.T., Schlosser, P., Smethie Jr, W.M., Sturchio, N.C., Fischer, T.P., Kennedy, B.M., Purtschert, R., Severinghaus, J.P., Solomon, D.K., Tanhua, T., and Yokochi, R., 2014, Tracer applications of noble gas radionuclides in the geosciences, Earth.-Sci. Rev., 138, 196-214. doi.org/10.1016/j.earscirev.2013.09.002

10.1016/j.earscirev.2013.09.002
21

Mansourizadeh, A., Rezaei, I., Lau, W.J., Seah, M.Q., and Ismail, A.F., 2022, A review on recent progress in environmental applications of membrane contactor technology, J. Environ. Chem. Eng., 10(3), 107631. doi.org/10.1016/j.jece.2022.107631

10.1016/j.jece.2022.107631
22

Markovich, K.H., Condon, L.E., Carroll, K.C., Purtschert, R., and McIntosh, J.C., 2020, A mountain‐front recharge component characterization approach combining groundwater age distributions, noble gas thermometry, and fluid and energy transport modeling, Water. Resour. Res., 57(1), e2020WR027743. doi.org/10.1029/2020WR027743

10.1029/2020WR027743
23

Matsumoto, T., Han, L.F., Jaklitsch, M., and Aggarwal, P.K., 2013, A portable membrane contactor sampler for analysis of noble gases in groundwater, Ground. Water., 51(3), 461-468, doi.org/10.1111/j.1745-6584.2012.00983.x

10.1111/j.1745-6584.2012.00983.x
24

Parkhurst, D.L. and Appelo, C.A.J., 1999, User’s Guide to PHREEQC(version 2)-A computer program for speciation, batchreaction, one-dimensional transport, and inverse geochemical calculations, USGS, Water-Resource Investigation Report 99-4259. doi.org/10.3133/wri994259

10.3133/wri994259
25

Purtschert, R., Love, A.J., Jiang, W., Lu, Z.T., Yang, G.M., Fulton, S., Wohling, D., Shand, P., Aeschbach, W., Broder, L., Muller, P., and Tosaki, Y., 2023, Residence times of groundwater along a flow path in the Great Artesian Basin determined by 81Kr, 36Cl and 4He: Implications for palaeo hydrogeology, Sci. Total. Environ., 859, 159886. doi.org/10.1016/j.scitotenv.2022.159886

10.1016/j.scitotenv.2022.159886
26

Ram, R., Burg, A., Zappala, J.C., Yokochi, R., Yechieli, Y., Purtschert, R., Jiang, W., Lu, Z.T., Mueller, P., Bernier, R., and Adar, E.M., 2020, Identifying recharge processes into a vast “fossil” aquifer based on dynamic groundwater 81Kr age evolution, J. hydrol., 587, 124946.

10.1016/j.jhydrol.2020.124946
27

Sanford, W.E., Shropshire, R.G., and Solomon, D.K., 2010, Dissolved gas tracers in groundwater: Simplified injection, sampling, and analysis, Water. Resour. Res., 32(6), 1635-1642, doi.org/10.1029/96WR00599

10.1029/96WR00599
28

Sano, Y., Kagoshima, T., Takahata, N., Shirai, K., Park, J.O., Snyder, G.T., Shibata, T., Yamamoto, J., Nishio, Y., Chen, A.-T., Xu, S., Zhao, D., and Pinti, D.L., 2020, Groundwater anomaly related to CCS-CO2 injection and the 2018 Hokkaido Eastern Iburi earthquake in Japan, Front. Earth. Sci., 8, 611010.

10.3389/feart.2020.611010
29

Troncoso, M., Garcia, G., Verdugo, J., and Farias, L., 2018, Toward high-resolution vertical measurements of dissolved greenhouse gases (nitrous oxide and methane) and nutrients in the Eastern South Pacific, Front. Mar. Sci., 5, 148, doi.org/10.3389/fmars.2018.00148

10.3389/fmars.2018.00148
30

Yokochi, R., 2016, Recent developments on field gas extraction and sample preparation methods for radiokrypton dating of groundwater, J. Hydrol., 540, 368-378. doi.org/10.1016/j.jhydrol.2016.06.020

10.1016/j.jhydrol.2016.06.020
31

Zimmer, M., Erzinger, J., and Kujawa, C., 2011, The gas membrane sensor(GMS): A new method for gas measurements in deep boreholes applied at the CO2SINK site, Int. J. Greenh. Gas. Con., 5(4), 995-1001, doi.org/10.1016/j.ijggc.2010.11.007

10.1016/j.ijggc.2010.11.007
Information
  • Publisher :The Korean Society of Soil and Groundwater Environment
  • Publisher(Ko) :한국지하수토양환경학회
  • Journal Title :Journal of Soil and Groundwater Environment
  • Journal Title(Ko) :지하수토양환경
  • Volume : 30
  • No :1
  • Pages :1-11
  • Received Date : 2024-11-25
  • Revised Date : 2024-12-26
  • Accepted Date : 2025-01-29
  • DOI :https://doi.org/10.7857/JSGE.2025.30.1.001
Journal Informaiton Journal of Soil and Groundwater Environment Journal of Soil and Groundwater Environment
Online Submission
  • KOFST
  • KISTI Current Status
  • KISTI Cited-by
  • orcid
  • open access
  • ccl
Journal Informaiton Journal Informaiton - close