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| The Experimental Research on In-Situ Detection for Dissolved CO2 in
Seawater Based on Tunable Diode Laser Absorption Spectroscopy |
| DU Bao-lu, LI Meng, GUO Jin-jia*, ZHANG Zhi-hao, YE Wang-quan, ZHENG Rong-er |
College of Information Science & Engineering, Ocean University of China, Qingdao 266100, China
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Abstract The exchange flux of CO2 between the ocean and the atmosphere is an important indicator for studying the carbon cycle and the ocean acidification issue. The estimation of CO2 flux mainly depends on the detection of CO2 in seawater. As a widely used gas detection technology, Tunable Diode Laser Absorption Spectroscopy (TDLAS) has advantages in environmental adaptability, selectivity and good sensitivity, and thus it is potential in the in-situ detection for dissolved gas in seawater. In order to verify the feasibility of applying TDLAS technology to the in-situ detection for dissolved CO2 in the seawater, this paper integrates the permeable membrane which realizes gas-water separation with the TDLAS gas detection prototype developed in the laboratory to realize the in-situ detection for CO2 in seawater. The whole prototype is designed as a sealed cabin. The prototype’s material is aluminum alloy which has good tightness, pressure and corrosion resistance. The laser source uses a DFB laser with a central wavenumber of 4 990 cm-1, and its wavenumber is scanned from 4 992 to 4 994.5 cm-1 over time, which can contain two absorption lines of CO2 at 4 992.51 and 4 993.74 cm-1. The permeable membrane’s material uses Teflon AF-2400 X with excellent pressure resistance and air permeability. Considering of requirements of high detection sensitivity and fast response rate for the prototype in underwater, the prototype uses a miniaturized Herriott-type multi-reflection cavity with good absorption characteristics. The cavity can achieve an effective optical path of 8 meters and a gas sampling volume of only 24 mL. A calibration experiment was done in the laboratory to reduce the influence of the prototype error on the measured value. Five different concentration (202.8×10-6, 503×10-6, 802×10-6, 1 006×10-6, 2 019×10-6) standard CO2 gases were measured by the prototype. The linear correlation (R2) is 99.95% between measured values, and actual values and the prototype has a maximum relatively error ≤8%. The prototype was used to continuously measure the standard CO2 gas with a concentration of 802×10-6 for 30 minutes to evaluate the stability of the prototype for a long time working. The average measured value is 802.6×10-6, and the fluctuation range is only 10×10-6. The accuracy of the prototype is about 0.5%, which can fulfill the requirement of in-situ dissolved gas detection in seawater. A test was done in an offshore pier with a depth of 3 meters. The prototype successfully obtained the typical absorption spectrum and concentration results of dissolved CO2 in water for the whole 24 hours. The test verifies the long-lasting stability and robustness of the prototype. Through a shipborne adaptability test of five areas with different depths in the East China Sea, the typical absorption spectrum of dissolved CO2 was successfully obtained, which proved the adaptability of the TDLAS detection prototype combined with permeable membrane degassing technology within 30 meters depth of seawater.
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Received: 2021-01-11
Accepted: 2021-03-11
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Corresponding Authors:
GUO Jin-jia
E-mail: opticsc@ouc.edu.cn
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