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

More Information

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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