Influencing Factors of Dissolved Organic Carbon Isotope Determination in Water Samples of a Karst Area by Wet Oxidation Method

YANG Hui; WU Xia; YU Jianguo; TANG Wei; LAN Gaoyong

doi:10.15898/j.ykcs.202405130108

Rock and Mineral Analysis > 2024 > 43(6): 914-927. > DOI: 10.15898/j.ykcs.202405130108

YANG Hui，WU Xia，YU Jianguo，et al. Influencing Factors of Dissolved Organic Carbon Isotope Determination in Water Samples of a Karst Area by Wet Oxidation Method[J]. Rock and Mineral Analysis，2024，43（6）：914−927. DOI: 10.15898/j.ykcs.202405130108

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Influencing Factors of Dissolved Organic Carbon Isotope Determination in Water Samples of a Karst Area by Wet Oxidation Method

YANG Hui^{1, 2,},
WU Xia^{1, 2, ,},
YU Jianguo^{1, 2},
TANG Wei^{1, 2},
LAN Gaoyong^{1, 2}

1.
Institute of Karst Geology, Chinese Academy of Geological Sciences; Key Laboratory of Karst Dynamics, Ministry of National Resources & Guangxi Autonomous; Region/International Research Center on Karst under the Auspices of UNESCO, Guilin 541004, China
2.
Pingguo Guangxi, Karst Ecosystem, National Observation and Research Station, Pingguo, Guangxi 531406, China

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Received Date: May 12, 2024
Revised Date: September 27, 2024
Accepted Date: October 10, 2024
Available Online: October 28, 2024
Published Date: October 28, 2024

Abstract

HIGHLIGHTS
(1) Phosphoric acid was added to the water sample in a karst area for acidification, and sweeping for an appropriate period; the test accuracy was better than 0.40‰ for the sample with DOC content greater than 2mg/L.

(2) The pressure of the sample gas in the equilibrium headspace vial plays a significant role in enhancing the intensity of the δ¹³_DOC signal and reducing the bias of the testing results.

(3) The blank peak area, a significant factor produced by low-background pure water, is crucial in affecting the testing results of water samples with low DOC content.

ABSTRACT

Due to the high content of HCO₃ ⁻ , low content of DOC and complex composition in the karst water, the current wet oxidation method for the determination of δ¹³C_DOC needs to be improved. The study examined the impact of different pure waters, headspace bottle atmospheric equilibrium methods, DOC content, and the removal of bicarbonate (HCO₃ ⁻ ) in water on δ¹³C_DOC values. The experimental results show significant differences in the ⁴⁴CO₂ peak areas produced by different blank pure waters, with the most prominent peak area being 3.8 times the smallest. Using a gas-tight syringe for atmospheric equilibrium enhances the sample signal strength and ensures the optimal internal precision of the sample test results. Acidifying the water samples to pH<3 with phosphoric acid eliminates the influence of HCO₃ ⁻ in karst waters. A nitrogen-blowing apparatus at a 250mL/min flow rate for 5−10min removes the free CO₂ present after acidification. Under the above experimental conditions, the deviation between the test results and the calibrated reference values for karst water samples with DOC content greater than 2mg/L is better than 0.40‰ after blank correction. The difference in the measured results of δ¹³C_DOC in karst water samples measured by the wet oxidation method compared to the total organic carbon analyzer-stable isotope mass spectrometer online method was less than 0.30‰. The BRIEF REPORT is available for this paper at http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202405130108.
- dissolved organic carbon,
- HCO₃ ⁻,
- wet oxidation method,
- isotope mass spectrometry; blank sample
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