Experimental Evaluation of an Analytical Method for Chlorofluorocarbons (CFSs) in Air and Water Using Gas Chromatography

가스 크로마토그래피를 이용한 대기와 물시료의 CFCs(chlorofluorocarbons) 분석법의 실험적 평가

  • Published : 2007.02.28

Abstract

CFC(CFC-12, CFC-11 and CFC-113) analytical system for air and water was constructed using a customized purge and trap extraction device and a gas chromatograph with an electron capture detector. Sampling methods of air and water for CFCs were also established. The analytical system was experimentally optimized to result in reproducibilities of triplicates less than 2% for current air samples and less than 5% for groundwater samples with CFC-12 concentration of 160 to 180 pg/kg, and verified with respect to the CFC system in USGS, which showed analytical results were in agreement within 10%. CFCs in air were monitored at three sites over 19-month period in the central part of South Korea, and the result indicates no significant local sources of CFCs in those areas. For groundwater in Jeju Island, CFCs were measured over a year with a two-month interval. The time-series data showed seasonal fluctuations which could be interpreted by the effect of recharge pulse derived from large amount of rainfall during monsoon period with a few month delay, which indicates high permeability of basaltic rocks in Jeju Island.

대기와 물에서의 CFCs(CFC-12, CFC-11, CFC-113)를 분석할 수 있는 시스템을 자체 제작된 퍼지-트랩 추출 장치와 전자포획검출기가 설치된 가스 크로마토그래피를 이용하여 구축하였다. 대기와 물에 대한 시료 채취방법도 확립되었다. 분석 시스템은 실험적으로 최적화되어 최근 대기 시료는 2% 이내, 제주도의 지하수 시료 (CFC-12 농도가 $160{\sim}180pg/kg$)는 5% 이내의 삼중복시료에 대한 재현성을 보였고, 미국지질조사소(USGS)의 분석시스템과 교차 분석을 실시하였으며, 10% 오차 범위내에서 일치하였다. 한반도 중부 지역의 세 지점에 대해 19개월에 걸쳐 대기 중의 CFCs를 관측하여 이 지역에서 국지적인 CFCs 근원이 크지 않음을 확인하였다. 제주도의 한 농업용 공공 관정에서 2개월 간격으로 1년 동안 지하수의 CFCs를 관측한 결과 8월까지 지하수의 CFCs 농도가 감소하고 10월 이후에 다시 증가하는 계절적인 변동을 보여 주었다. 이것은 여름철 우기에 발생한 지하수 함양이 수 개월 지연되어 나타난 결과로 볼 수 있으며, 제주도 현무암 대수층의 높은 투수성을 지시한다.

Keywords

References

  1. Bohlke, J.K. and Denver, J.M. (1995) Combined use of groundwater dating, chemical, and isotopic analyses to resolve the history and fate of nitrate contamination in two agricultural watersheds, Atlantic coastal plain, Maryland. Water Resources Research v. 31, p. 2319-2339 https://doi.org/10.1029/95WR01584
  2. Bohlke, J.K., Busenberg, E. and Plummer, L.N. (1999) Principles and Applications of Dating Young Groundwater: Primary Emphasis on CFCs and $^{3}$H/$^{3}$He Dating. U. S. Geological Survey Western Region Workshop. Sacramento, CA, November 16-18, 790p
  3. Bullister, J.L. and Weiss, R.F. (1988)Determination of $CCl_{3}$F and $CCl_{2}$$F_{2}$ in seawater and air. Deep-Sea Research, v. 35, p. 839-853 https://doi.org/10.1016/0198-0149(88)90033-7
  4. Bums, D.A., Plummer, L.N., McDonnell, J.J., Busenberg, E., Casile, G.C., Kendall, C., Hooper, R.P., Freer, J.E., Peters, N.E., Beven, K., and Schlosser, P. (2003) The geochemical evolution of riparian groundwater in a forested piedmont catchment. Ground Water, v. 41, p. 913-925 https://doi.org/10.1111/j.1745-6584.2003.tb02434.x
  5. Busenberg, E. and Plummer, L.N. (1992) Use of chlorofluorocarbons ($CCl_{3}$F and $CCl_{2}$$F_{2}$) as hydrologic tracers and age-dating tools: the alluvium and terrace system of central Oklahoma. Water Resources Research, v. 28, p. 2257-2283 https://doi.org/10.1029/92WR01263
  6. Burton, W.C., Plummer, L.N., Busenberg, E., Lindsey, B.D. and Gburek, W.J. (2002) Influence of fracture anisotropy on groundwater ages and chemistry, Valley and Ridge Province, Pennsylvania. Ground Water, v. 40, p. 242-257 https://doi.org/10.1111/j.1745-6584.2002.tb02652.x
  7. Bu, X. and Warner, M.J. (1995) Solubility of chlorofluorocarbon 113 in water and seawater. Deep-Sea Research, v. 42, p. 1151-1161 https://doi.org/10.1016/0967-0637(95)00052-8
  8. Cook, P.G., Solomon, D.K., Plummer, L.N., Busenberg, E. and Schiff, S.L. (1995) Chlorofluorocarbons as tracers of groundwater transport processes in a shallow, silty sand aquifer. Water Resources Research, v. 31, p. 425-434 https://doi.org/10.1029/94WR02528
  9. Dunkle, S.A., Plummer, L.N., Busenberg, E., Phillips, P.J., Denver, J.M., Hamilton, P.A., Michel, R.L., and Coplen, T.B. (1993) Chlorofluorocarbons ($CCl_{3}$F and $CCl_{2}$$F_{2}$) as dating tools and hydrologic tracers in shallow groundwater of the Delmarva Peninsula, Atlantic Coastal Plain, United States. Water Resources Research, v. 29, p. 3837-3860 https://doi.org/10.1029/93WR02073
  10. Ekwurzel, B., Schlosser, P., Smethie Jr., W.M., Plummer, L.N., Busenberg, E., Michel, R.L., Weppernig, R. and Stute, M. (1994) Dating of shallow groundwater: Comparison of the transient tracers $^{3}$H/$^{3}$He, chlorofluorocarbons, and $^{85}$Kr. Water Resources Research, v. 30, p. 1693-1708 https://doi.org/10.1029/94WR00156
  11. Happell, J. D., Price, R. M., Top, Z. and Swart, P. K. (2003) Evidence for the removal of CFC-11, CFC-12, and CFC-113 at the groundwater-surface water interface in the Everglades. Journal of Hydrology, v. 279, p. 94-105 https://doi.org/10.1016/S0022-1694(03)00169-0
  12. Hohener , P., Werner, D., Balsiger, C., and Pasteris G. (2003) Worldwide Occurrence and Fate of Chlorofluorocarbons in Groundwater. Critical Reviews in Environmental Science and Technology, v. 33, p. 1-29 https://doi.org/10.1080/10643380390814433
  13. Kim, J., Oh, S., Cho, H., Park, M., Kim, K., and Elkins, J. W. (2001) Background monitoring and long-range transport of atmospheric CFC-11 and CFC-12 at Kosan, Korea. Environmental Monitoring and Assessment, v. 79, p. 47-56 https://doi.org/10.1023/A:1020081723955
  14. Koh, D.C., Chang, H.W., Lee, K.S., Ko, K.S., Kim, Y. and Park, W.-B. (2005) Hydrogeochemistry and environmental isotopes of groundwater in Jeju volcanic island, Korea: implications for nitrate contamination. Hydrological Processes, v. 19, p. 2225-2245 https://doi.org/10.1002/hyp.5672
  15. Koh, D.C. and Kim, Y. (2004) Characterization of groundwater flow and quality using multi-tracers in Jeju Island. Proceedings of Korean Society Soil Groundwater Environment, fall conference
  16. Koh, D.C. and Lee, D.H. (2003) Evaluation of groundwater sampling techniques for analysis of chlorofluorocarbons. Journal of Korean Society Soil Groundwater Environment, v. 8, p. 1-8
  17. Koh, D.C., Plummer, L.N., Solomon, D.K., Busenberg, E., Kim, Y.J., and Chang, H.W. (2006) Application of environmental tracers to mixing, evolution, and nitrate contamination of groundwater in Jeju Island, Korea. Journal of Hydrology, v. 327, p. 258-275 https://doi.org/10.1016/j.jhydrol.2005.11.021
  18. Plummer, L.N., Busenberg, E., Bohlke, J.K., Nelms, D.L., Michel, R.L., and Schlosser, P. (2001) Groundwater residence times in Shenandoah National Park, Blue Ridge Mountains, Virginia, USA: a multi-tracer approach. Chemical Geology, v. 179, p. 93-111 https://doi.org/10.1016/S0009-2541(01)00317-5
  19. Plummer, L.N., Busenberg, E., Drenkard, S., Schlosser, P., Ekwurzel, B., Weppernig, R., McConnell, J.B. and Michel, R.L. (1998) Flow of river water into a Karstic limestone aquifer. 2. Dating the young fraction in groundwater mixtures in the Upper Floridan Aquifer near Valdosta, Georgia. Applied Geochemistry, v. 13, p. 1017-1043 https://doi.org/10.1016/S0883-2927(98)00032-8
  20. Reilly, T.E., Plummer, L.N., Phillips, P.J. and Busenberg, E. (1994) The use of simulation and multiple environmental tracers to quantify groundwater flow in a shallow aquifer. Water Resources Research, v. 30, p. 421-433 https://doi.org/10.1029/93WR02655
  21. Snyder, J.L. (2004) Environmental applications of gas chromatography: In Modern Practice of Gas Chromatography, 4th Ed., Grob, R.L., Barry, E.F. (eds), John Wiley & Sons, p. 769-881
  22. Szabo, Z., Rice, D.E., Plummer, L.N., Busenberg, E., Drenkard, S., and Schlosser, P. (1996) Age-dating of shallow groundwater with chlorofluorocarbons, tritium/helium 3, and flow path analysis, southern New Jersey coastal plain. Water Resources Research, v. 32, p. 1023-1038 https://doi.org/10.1029/96WR00068
  23. Warner, M.J. and Weiss, R.F. (1985) Solubilities of chlorofluorocarbons 11 and 12 in water and seawater. DeepSea Research, v. 32, p. 1485-1497