The Determination of Henry’s Law Constant of Carbon Dioxide in Stratified Seawater of the South China Sea's Shenhu Sea by D-value of Multi Balance Systems
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摘要: 海水中溶存CO2含量在一定程度上影响全球气候的变化，影响海洋生物的生长，控制海底碳酸盐岩的形成，是海洋环境、海底矿产资源以及海洋生物调查与评价的重要指标之一，对于海底矿产的勘探开发、海洋环境监测、海水及海底沉积物碳循环乃至全球碳循环的研究具有重要的学术价值。检测水中游离CO2通常采用滴定法或亨利法，滴定法适用于检测地下水中游离CO2的含量，目标通常为单个样品；亨利法更适用于海水中游离CO2含量的检测，尤其适用船载现场采自同一海域的批量同源海水样品，检测结果主要基于CO2在水中的理论亨利常数，但由于不同海水的温度、盐度、成分不同，其CO2的亨利常数并不相同，需要先行测定海水样品中CO2的亨利常数。本文依据质量守恒原理和CO2在海水中的溶解规律，设计了测定海水中CO2亨利常数的差量平衡法，预先构建多个不同质量、体积的气液平衡体系，再根据平衡体系间CO2物质的量的差值求算CO2亨利常数。应用差量平衡法测定了24个南海神狐海域分层海水样品中CO2的亨利常数值，并通过多体系转换重合实验验证了差量平衡法的科学性与可行性。Abstract: The concentration of dissolved carbon dioxide in seawater affects global climate change, the growth of marine organisms and controls the formation of submarine carbonates, it is one of the most important indices in the marine environment and mineral resource survey. It has important academic value for the exploration of seabed minerals, monitoring of marine environment, the study of carbon cycle in seabed sediments and even the global carbon cycle. Titration and Henrys are used to determine the concentration of dissolved carbon dioxide in seawater. The Henrys is more suitable for seawater, especially for a great deal of seawater samples collected from the same sea area on board ships, the results are mainly based on the theoretical Henry's constant of carbon dioxide in seawater, in fact, the Henry’s Law Constants of carbon dioxide in different seawater are different. In order to achieve higher measurement accuracy and precision, the Henry’s Law Constants of carbon dioxide in seawater have to be determined first. An experimental plan is designed and D-value of Multi Balance Systems is put forward in this article, which is used to determine the Henry’s Law Constants of carbon dioxide in seawater. D-value of Multi Balance Systems is based on the principle of mass conservation and the dissolution behavior of carbon dioxide in seawater. In D-value of Multi Balance Systems, multiple gas-liquid balance systems with different masses and volumes are constructed in advance, then the Henry’s Law Constant of carbon dioxide is derived on the basis of the different mass of carbon dioxide between the balance systems. The Henry's values of carbon dioxide in 24 stratified seawater samples from the South China Sea's Shenhu Sea are determined by D-value of Multi Balance Systems. At last the scientificalness and feasibility of D-value of Multi Balance Systems are proved by multiple system conversion coincidence experiments.
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图 1 CO2溶于海水的系列反应
Fig. 1 A series of chemical reactions where carbon dioxide dissolves in seawater
图 2 实验设计流程图
1气源 2原液桶 3真空单元-真空泵 4真空单元-隔水三角瓶 5-8平衡单元-定气标液配制器9-1平衡单元-恒温振荡箱 9-2平衡单元-恒温振荡箱控制器 10分析单元-CO2分析仪
Fig. 2 Schematic representation of experimental design process
1gas source 2 stock solution barrel 3 vacuum unit–vacuum pump 4 vacuum unit–waterproof conical flask 5-8 balance unit–calibrating standard solution prepare 9-1 balance unit–oscillator 9-2 balance unit–thermostatic oscillator controller 10 analytical unit–carbon dioxide analyzer
图 3 南海北部神狐海域分层海水样品采集位置图
Fig. 3 Site map of stratified seawater samples from the South China Sea's Shenhu Sea
图 4 平衡体系顶部混合气体中CO2含量测试曲线图
Fig. 4 Test curve of carbon dioxide in gas mixture in the top of balance system
图 5 神狐海域分层海水中CO2亨利常数以及基于多体系转换实验的相对标准偏差图
Fig. 5 Henry’s law constants of carbon dioxide of stratified seawater from the South China Sea's Shenhu Sea and RSD based on systems transformations
表 1 神狐海域分层海水样品CO2亨利常数实验数据表
Tab. 1 Experimental data table of Henry’s law constant of carbon dioxide in seawater in Shenhu area at various depths
样品编号 样品分层
水深（米）海水温度（℃） 海水盐度（‰） 海水中CO2
亨利常数（kpa）HSSH3-01 0 25.1 34.20 6.07111E-06 HSSH3-02 50 18.0 34.67 7.40505E-06 HSSH3-03 100 16.1 34.71 7.87081E-06 HSSH3-04 150 13.5 34.62 8.51811E-06 HSSH3-05 200 12.5 34.52 8.79949E-06 HSSH3-06 250 11.3 34.43 9.15568E-06 HSSH3-07 300 9.9 34.42 9.59864E-06 HSSH3-08 350 9.5 34.41 9.73095E-06 HSSH3-09 400 9.0 34.42 9.90009E-06 HSSH3-10 450 8.0 34.43 1.02514E-05 HSSH3-11 500 7.8 34.44 1.03238E-05 HSSH3-12 550 7.0 34.45 1.06210E-05 HSSH3-13 600 6.8 34.46 1.06972E-05 HSSH3-14 650 6.4 34.46 1.08520E-05 HSSH3-15 700 6.1 34.46 1.09702E-05 HSSH3-16 750 6.0 34.47 1.10100E-05 HSSH3-17 800 5.9 34.48 1.10500E-05 HSSH3-18 850 5.7 34.49 1.11306E-05 HSSH3-19 900 5.4 34.51 1.12532E-05 HSSH3-20 950 5.2 34.52 1.13359E-05 HSSH3-21 1000 5.0 34.52 1.14196E-05 HSSH3-22 1100 4.5 34.54 1.16325E-05 HSSH3-23 1200 3.9 34.58 1.18955E-05 HSSH3-24 2000 2.9 34.62 1.23529E-05 
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表 2 多体系转换重合验证实验数据表
Tab. 2 Experimental data table of the systems transformation coincidence experiment
样品编号 H（1-2-3体系）
（kpa）H（1-2-4体系）
（kpa）H（2-3-4体系）
（kpa）RstDev（max）
（‰）HSSH3-02 7.40290254E-06 7.40327279E-06 7.40356899E-06 −0.29 HSSH3-03 7.86821263E-06 7.86860617E-06 7.86892101E-06 −0.33 HSSH3-04 8.51881700E-06 8.51884256E-06 8.52603184E-06 0.93 HSSH3-05 8.79737812E-06 8.79781810E-06 8.79817008E-06 −0.24 HSSH3-06 9.15643992E-06 9.15646739E-06 9.15653148E-06 0.093 HSSH3-07 9.60244106E-06 9.60257544E-06 9.60286340E-06 0.44 HSSH3-09 9.89771398E-06 9.89820898E-06 9.89860499E-06 −0.24 HSSH3-11 1.03249356E-05 1.03254518E-05 1.03258648E-05 0.2 HSSH3-14 1.08477677E-05 1.08480933E-05 1.08485274E-05 −0.39 HSSH3-17 1.10523205E-05 1.10526520E-05 1.10530940E-05 0.28 HSSH3-18 1.11316240E-05 1.11316685E-05 1.11318244E-05 0.11 HSSH3-20 1.13341996E-05 1.13346531E-05 1.13353332E-05 −0.15 HSSH3-22 1.16335702E-05 1.16336167E-05 1.16337796E-05 0.11
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