Re-evaluation of carbonic acid dissociation constants across conditions and the implications for ocean acidification
Re-evaluation of carbonic acid dissociation constants across conditions and the implications for ocean acidification
复制标题
重新评估不同条件下的碳酸解离常数及其对海洋酸化的影响
DOI：
10.1016/j.marchem.2023.104247
复制
发表时间：
2023
期刊：
影响因子：
3
通讯作者：
Moon, Ji-Young
中科院分区：
文献类型：
--
作者：
Woosley, Ryan J.;Moon, Ji-Young
随着海洋酸化威胁的日益加剧以及海洋在全球碳循环中的重要作用，需要高精度、准确度和可比性的无机碳系统参数测定。热力学关系使系统能够使用直接测量和计算的组合来完全约束。然而，由于解离常数的许多公式（超过120种可能的组合），计算变得复杂。为了解决这些重要的不确定性和可比性问题，我们评估了各种常数组合及其与温度（−1.9-40 °C），实际盐度（15-39）和pCO 2（150-1200 μatm）范围内直接测量的（不）一致性。结果表明，计算和测量之间的差异显着大于测量的不确定性，这意味着经常说的范式，一个只需要测量两个参数和其他可以计算不适用于气候质量海洋酸化研究。计算pH值的不确定性妨碍了从总碱度（TA）和溶解无机碳（DIC）计算气候质量pH值，而应直接测量。然而，气候质量TA和DIC通常可以分别使用测量的pH值和DIC或TA来计算。计算结果明显偏向于中高pCO 2值（2500 -800 μatm），这意味着模型低估了未来的海洋酸化。解离常数的不确定性导致文石饱和层深度的显著不确定性（在南大洋>500米），在研究碳酸钙循环时必须考虑到这一点。需要显着改善的热力学常数的精度，以提高pH值计算。
With the increasing threat of ocean acidification and the important role of the oceans in the global carbon cycle, highly precise, accurate, and intercomparable determination of inorganic carbon system parameters is required. Thermodynamic relationships enable the system to be fully constrained using a combination of direct measurements and calculations. However, calculations are complicated by many formulations for dissociation constants (over 120 possible combinations). To address these important issues of uncertainty and comparability, we evaluated the various combinations of constants and their (dis)agreement with direct measurements over a range of temperature (−1.9–40 °C), practical salinity (15–39) and pCO2(150–1200 μatm). The results demonstrate that differences between the calculations and measurements are significantly larger than measurement uncertainties, meaning the oft-stated paradigm that one only needs to measure two parameters and the others can be calculated does not apply for climate quality ocean acidification research. The uncertainties in calculated pHtprevent climate quality pHtfrom being calculated from total alkalinity (TA) and dissolved inorganic carbon (DIC) and should be directly measured instead. However, climate quality TA and DIC can often be calculated using measured pH and DIC or TA respectively. Calculations are notably biased at medium-to-high pCO2values (∼500–800 μatm) implying models underestimate future ocean acidification. Uncertainty in the dissociation constants leads to significant uncertainty in the depth of the aragonite saturation horizon (>500 m in the Southern Ocean) and must be considered when studying calcium carbonate cycling. Significant improvements in the precision of the thermodynamic constants are required to improve pHtcalculations.
登录
查看更多内容
用于分光光度法测量海水 pH 值的纯化间甲酚紫的一致性和稳定性
影响因子：
3
作者：
Takeshita, Yuichiro;Warren, Joseph K.;Liu, Xuewu;Spaulding, Reggie S.;Byrne, Robert H.;Carter, Brendan R.;DeGrandpre, Michael D.;Murata, Akihiko;Watanabe, Shu-ichi
通讯作者：
Watanabe, Shu-ichi
DOI：
10.1016/s0967-0637(99)00031-x
发表时间：
1999-11-01
影响因子：
2.4
作者：
Byrne, RH;McElligott, S;Millero, FJ
通讯作者：
Millero, FJ
咸水 pH 测量计量学 — 第 1 部分：将 TRIS 缓冲液的电化学 pHT 测量扩展到盐度 5 — 20
影响因子：
3.7
作者：
Müller, Jens D.;Bastkowski, Frank;Sander, Beatrice;Seitz, Steffen;Turner, David R.;Dickson, Andrew G.;Rehder, Gregor
通讯作者：
Rehder, Gregor
影响因子：
5.2
作者：
J. Waters;F. Millero;C. Sabine
通讯作者：
J. Waters;F. Millero;C. Sabine
影响因子：
3
作者：
R. Wanninkhof;E. Lewis;R. Feely;F. Millero
通讯作者：
R. Wanninkhof;E. Lewis;R. Feely;F. Millero