The development of in situ detection technology and device for dissolved methane and carbon dioxide in deep sea
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摘要:
甲烷、二氧化碳的地质和生物地球化学循环对海洋环境和全球气候变化有着重要影响，其在深海环境中通常以气泡或流体的形式向四周扩散，甲烷还是探测海底天然气水合物资源的重要指标之一。目前，国内外研究团队提出了各种背景下原位探测海洋溶解甲烷、二氧化碳的新技术、新方法，以促进对海洋碳循环的研究。简述了基于电化学技术、光学技术、质谱技术和生物传感技术等对海洋溶解甲烷、二氧化碳进行原位探测的最新进展，系统介绍了各传感器的工作原理和性能，分析其应用价值和前景，并在此基础上对未来的研究方向提出一些建议。
Abstract:The geological and biogeochemical cycle of methane and carbon dioxide in the ocean has an important impact on the marine environment and global climate change. In many deep-sea environments, methane and carbon dioxide usually diffuse in the form of bubbles or fluids, Methane is also one of the important indicators to detect the resources of natural gas hydrates. At present, in order to promote the study of marine carbon cycle and flux, research groups at home and abroad have proposed new technologies and methods for in-situ detection of dissolved methane and carbon dioxide in the ocean under various backgrounds. In this paper, the latest progress of in situ detection of dissolved methane and carbon dioxide in the ocean based on electrochemical, optical, mass spectrometry and biosensor technologies is reviewed, the working principle and performance of each sensor are introduced systematically, the application value and prospect of it are analyzed, and some suggestions for future research are put forward.
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表 1 基于膜脱气和半导体气敏材料的电化学传感器比较
Table 1. The comparison of electrochemical sensors based on porous film and semiconductor gas sensing materials
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表 2 基于光学技术的原位传感器比较
Table 2. The comparison of in situ sensors based on optical technology
仪器名称 检测原理 分析气体种类 测量范围/
(nmol/L)检出限/
(nmol/L)精度 响应时间/h 工作水深/m 功率 参考文献 Hydro CTM TDLAS CH4 0～56 700 <1 nmol/L 17～30 6 000 600 mA，12 V [25-27] NDIR CO2 0～200 000 <33.4 nmol/L 60 6 000 350 mA，12 V [26,28] 深水气体分析仪 OA-ICOS CH4
CO2
δ13
0.7～1 418.5
5 000～1 670 0000.001 nmol/L 33.4 nmol/L 1‰ 300 2 500 80 W，
115/230 V[30] 深海原位分析仪 OA-ICOS CH4
δ13
0.8‰ 3 000 120 VAC [22] 深海激光光谱仪 OA-ICOS CH4
δ13
CO2
δ13
0.8‰
0.7‰3 000 70 W，24 V [31] Sub-Ocean OFCEAS CH4 0.1～106 0.035 30 4 000 50 W，24 V [32] 原位CH4
分析系统CRDS CH4 0.000 56 nmol/L 12 W，24 V [35] IR-ATR光谱仪 ATR CH4
CO21 100 [40] CH4传感器 SPR CH4 1～300 3～7 (6～7)×10−6 RIU/(nmol/L) 60 [42-44] 片状CH4传感器 马赫-曾德尔干涉 CH4 49 3.48×10−2
rad/(nmol/L)120 [41,46] DORISS 拉曼光谱 CH4
CO24×106
1075～20 4 000 [48-51] RiP 拉曼光谱 CH4
CO2106 6 000 [53-58]
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表 3 基于质谱分析原理的原位传感器比较
Table 3. The comparison of in situ sensors based on mass spectrometry
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