Comparison of Solidification Pre-treatment Methods for the Determination of δ13C of Dissolved Organic Carbon: Alkaline Persulfate Oxidation-Carbonate Precipitation vs. Freeze Drying

용존유기탄소의 δ13C : 분석시 고형화 전처리 방법 비교 알칼린 과황산칼륨산화 탄산침전과 동결건조

  • Jeon, Byeong-Jun (Department of Rural & Biosystems Engineering, Chonnam National University) ;
  • Park, Hyun-Jin (Department of Rural & Biosystems Engineering, Chonnam National University) ;
  • Choi, Woo-Jung (Department of Rural & Biosystems Engineering, Chonnam National University) ;
  • Park, Yong-Se (National Instrumentation Center for Environmental Management, Seoul National University) ;
  • Lee, Sang-Mo (National Instrumentation Center for Environmental Management, Seoul National University) ;
  • Yoon, Kwang-Sik (Department of Rural & Biosystems Engineering, Chonnam National University)
  • 전병준 (전남대학교 지역.바이오시스템공학과) ;
  • 박현진 (전남대학교 지역.바이오시스템공학과) ;
  • 최우정 (전남대학교 지역.바이오시스템공학과) ;
  • 박용세 (서울대학교 농생명과학공동기기원) ;
  • 이상모 (서울대학교 농생명과학공동기기원) ;
  • 윤광식 (전남대학교 지역.바이오시스템공학과)
  • Received : 2017.04.25
  • Accepted : 2017.06.07
  • Published : 2017.06.30


BACKGROUND: The carbon (C) isotope ratio (${\delta}^{13}C$) of dissolved organic C (DOC) is an indicator of water pollution source. In this study, the potential use of two pre-treatments for the ${\delta}^{13}C$ analysis, alkaline persulfate oxidation coupled with carbonate precipitation (precipitation) and freeze drying (drying), were compared to suggest a more feasible pre-treatment method. METHODS AND RESULTS: Two reference materials with different ${\delta}^{13}C$ values were used for the experiments; chemical grade glucose ($-12.0{\pm}0.02$‰) and pig manure compost extract ($-23.3{\pm}0.04$‰). In the precipitation method, the measured ${\delta}^{13}C$ values were consistently lower than the theoretically calculated values as dissolved $CO_2$ could not be removed due to the alkaline property of the reagents and the dissolution of air $CO_2$ into the alkaline solution. The drying method also resulted in more negative ${\delta}^{13}C$ than the calculated ${\delta}^{13}C$; however, the difference was systematic ($3.9{\pm}0.3$‰) and there was a strong correlation (${\delta}^{13}C_{calculated}=0.87{\times}{\delta}^{13}C_{measured}-0.624$, $r^2=0.98$) between the calculated and measured ${\delta}^{13}C$. Calibration of ${\delta}^{13}C$ using the relationship between the calculated and the measured ${\delta}^{13}C$ values produced reliable and accurate ${\delta}^{13}C$ values. CONCLUSION: Our results suggest that the drying method is more accurate pre-treatment method to minimize the influence of air $CO_2$ compared to the precipitation method for the determination of ${\delta}^{13}C$ of DOC.


Carbon isotope ratio;Dissolved organic carbon;Freeze drying;Stable isotope ratio mass spectrometer;Strontium carbonate precipitation


  1. Yoo, S. H., Ro, H. M., & Choi, W. J. (2012). Soil and water qualities affected by six decades of agricultural paradigm shifts in Korea. Proceedings of Korean Academy of Science, 51(1), 127-157.
  2. Yu, K., Gan, Y., Zhou, A., Han, L., & Liu, Y. (2015). A persulfate oxidation method for stable isotope analysis of dissolved organic carbon and the influence of inorganic ions on the results. International Journal of Mass Spectrometry, 392(1), 63-68.
  3. Zhou, J., Wu, Y., Zhang, J., Kang, Q., & Liu, Z. (2006). Carbon and nitrogen composition and stable isotope as potential indicators of source and fate of organic matter in the salt marsh of the Changjiang Estuary, China. Chemosphere, 65(2), 310-317.
  4. Amiotte-suchet, P., Linglois, N., Leveque, J., & Andreux, F. (2007). $^{13}C$ composition of dissolved ogranic carbon in upland forested catchments of the morvan mountains (France): Influence of coniferous and deciduous vegetation. Journal of Hydrology, 335(3&4), 354-363.
  5. Cabrera, M. L., & Beare, M. H. (1993). Alkaline persulfate oxidation for determining total nitrogen in microbial biomass extracts. Soil Science Society of America Journal, 57(4), 1007-1012.
  6. Choi, W. J., Kwak, J. H., Lim, S. S., Park, H. J., Chang, S. X., Lee, S. M., Arshad, M. A., Yun, S. I., & Kim, H. Y. (2017). Synthetic fertilizer and livestock manure differently affect ${\delta}^{15}N$ in the agricultural landscape: A review. Agriculture Ecosystems & Environment, 237(1), 1-15.
  7. Choi, W. J., & Lee, K. H. (2012). A short overview on linking annual tree ring carbon isotopes to historical changes in atmospheric environment. Forest Science & Technology, 8(2), 61-66.
  8. Dungait, J. A. J., Bol, R., Lopez-Capel, E., Bull, I. D., Chadwick, D., Amelung, W., Granger, S. J., Manning, D. A. C., & Evershed, R. P. (2010). Applications of stable isotope ratio masss spectrometry in cattle dung carbon cycling studies. Rapid Communications in Mass Spectrometry, 24(5), 495-500.
  9. Harris, D., Porter, L. K., & Paul, E. A. (1997). Continuous flow isotope ratio mass spectrometry of carbon dioxide trapped as strontium carbonate. Communications in Soil Science and Plant Analysis, 28(9&10), 747-757.
  10. Kirkels, F. M. S. A., Cerli, C., Federherr, E., Gao, J., Kalbitz, K. (2014). A novel high-temperature combustion based system for stable isotope analysis of dissolved organic carbon in aqueous samples. II: optimization and assessment of analytical performance. Rapid Communications in Mass Spectrometry, 28(23), 2574-2586.
  11. Lambert, T., Pierson-Wickmann A. C., Gruau, G., Thibault, J. N., & Jaffrezic, A. (2011). Carbon isotopes as tracers of dissolved organic carbon sources and water pathways in headwater catchments. Journal of Hydrology, 402(3&4), 228-238.
  12. Nitschelm, J. J., Luscher, A., Hartwig, U. A., & van Kessel, C. (1997). Using stable isotopes to determine soil carbon input differences under ambient and elevated atmospheric $CO_2$ conditions. Global Change Biology, 3(5), 411-416.
  13. Ongley, E. D., Xiaolan, Z., & Tao, Y. (2010). Current status of agricultural and rural non-point source pollution assessment in China. Environmental Pollution, 158(5), 1159-1168.
  14. Parker, S. R., Poulson, S. R., Smith, M. G., Weyer, C. L., & Bates, K. M. (2010). Temporal variability in the concentration and stable carbon isotope composition of dissolved inorganic and organic carbon in two Montana, USA rivers. Aquatic Geochemistry, 16(1), 61-84.
  15. Sun, B., Zhang, L., Yang, L., Zhang, F., Norse, D., & Zhu, Z. (2012). Agricultural non-point source pollution in China: causes and mitigation measures. AMBIO, 41(4) 370-379.
  16. Tu, C. L., Liu, C. Q., Lu, X. H., Yuan, J., & Lang, Y. C. (2011). Sources of dissolved organic carbon in forest soils: evidences from the differences of organic carbon concentration and isotope composition studies. Environmental Earth Sciences, 63(4), 723-730.
  17. Van Geldern, R., Verma, M. P., Carvalho, M. C., Grassa, F., Delgado-Huertas, A., Monvoisin, G., & Barth, J. A. C. (2013). Stable carbon isotope analysis of dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC) in natural waters-Results from a worldwide proficiency test. Rapid Communications in Mass Spectrometry, 27(18), 2099-2107.
  18. Yanagi, Y., Hirooka, H., Oishi, K., Choumei, Y., Hata, H., Arai, M., Kitagawa, M., Gotoh, T., Inada, S., & Kumagai, H. (2012). Stable carbon and nitrogen isotope analysis as a toll for inferring beef cattle feeding systems in Japan. Food Chemistry, 134(1), 502-506.