Gaining insights into the seawater carbonate system using discrete fCO2 measurements
Gaining insights into the seawater carbonate system using discrete fCO2 measurements
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使用离散 fCO2 测量深入了解海水碳酸盐系统
DOI：
10.1016/j.marchem.2022.104150
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发表时间：
2022
期刊：
影响因子：
3
通讯作者：
García-Ibáñez M
中科院分区：
文献类型：
--
作者：
García-Ibáñez M
了解海洋碳汇及其未来酸化引起的变化需要准确和精确的测量，并具有良好的时空覆盖。此外，深入了解海水碳酸盐系统的热力学是测量和计算变量之间相互转换的关键。为了深入了解海水碳酸盐系统中剩余的不一致性，我们评估了二氧化碳逸度（fCO 2），溶解无机碳（DIC），总碱度（TA）和pH值的离散水柱测量值，这些测量值来自GLODAP v2.2020中包含的大西洋，太平洋和南大洋的水文巡航（19，013个样本）。在94%的汇编数据集中，DIC和pH测量和计算的fCO 2之间的一致性优于± 3%，而当DIC和TA测量和计算的fCO 2时，88%的汇编数据集的一致性优于± 4%，高CO2水域的内部一致性较差。通过对测量和计算变量中所有可能的不确定性来源的考察，我们得出结论：海水碳酸盐体系群落需要（i）进一步完善海水碳酸盐体系的热力学模型，尤其是K2，包括有机化合物和其他酸碱体系对TA的影响; ㈡根据目前的技术和分析进展，更新海水碳酸盐系统测量的标准作业程序，特别注意发展最快的pH值方法; ㈢鼓励测量离散水柱fCO 2，以进一步检查海水碳酸盐系统的内部一致性，特别是考虑到基于传感器的海水测量的新时代;以及（iv）在全球海洋中遇到的各种数值范围内，开发用于测量fCO 2和pH值的海水标准物质，以及用于测量TA和DIC的海水标准物质。我们的结论还表明，需要重新评估GLODAP v2对pH值的调整，这是基于DIC和TA一致性检查，但不支持fCO 2和DIC一致性。
Understanding the ocean carbon sink and its future acidification-derived changes requires accurate and precise measurements with good spatiotemporal coverage. In addition, a deep knowledge of the thermodynamics of the seawater carbonate system is key to interconverting between measured and calculated variables. To gain insights into the remaining inconsistencies in the seawater carbonate system, we assess discrete water column measurements of carbon dioxide fugacity (fCO2), dissolved inorganic carbon (DIC), total alkalinity (TA), and pH measured with unpurified indicators, from hydrographic cruises in the Atlantic, Pacific, and Southern Oceans included in GLODAPv2.2020 (19,013 samples). An agreement of better than ± 3% betweenfCO2measured and calculated from DIC and pH is obtained for 94% of the compiled dataset, while when consideringfCO2measured and calculated from DIC and TA, the agreement is better than ± 4% for 88% of the compiled dataset, with a poorer internal consistency for high-CO2waters. Inspecting all likely sources of uncertainty from measured and calculated variables, we conclude that the seawater carbonate system community needs to (i) further refine the thermodynamic model of the seawater carbonate system, especially K2, including the impact of organic compounds and other acid-base systems on TA; (ii) update the standard operating procedures for the seawater carbonate system measurements following current technological and analytical advances, paying particular attention to the pH methodology that is the one that evolved the most; (iii) encourage measuring discrete water columnfCO2to further check the internal consistency of the seawater carbonate system, especially given the new era of sensor-based seawater measurements; and (iv) develop seawater Certified Reference Materials (CRMs) forfCO2and pH together with seawater CRMs for TA and DIC over the range of values encountered in the global ocean. Our conclusions also suggest the need for a re-evaluation of the adjustments applied by GLODAPv2 to pH, which were based on DIC and TA consistency checks but not supported byfCO2and DIC consistency.
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