Collaborative Research: Novel constraints on air-sea gas exchange and deep ocean ventilation from high-precision noble gas isotope measurements in seawater

合作研究：海水中高精度稀有气体同位素测量对海气交换和深海通风的新限制

• 批准号: 1923915
• 负责人: Peter Barry
• 金额: $ 54.83万
• 依托单位: Woods Hole Oceanographic Institution
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-09-01 至 2024-02-29
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1923915&HistoricalAwards=false
• 关键词: Collaborative; Research; Novel; constraints; air

The proposed work brings together the fields of chemical oceanography, ocean modeling, and solid Earth geochemistry to develop the stable isotope composition of heavy noble gases dissolved in seawater as novel physical tracers of air-sea gas exchange. Noble gases represent ideal tools for quantifying physical processes due to the fact that they are chemically inert. Because argon (Ar), krypton (Kr), and xenon (Xe) isotope ratios have distinct solubility and diffusivity ratios, as recently quantified in laboratory experiments, they complement existing bulk noble gas measurements in seawater by adding new constraints with unique sensitivities. Precise constraints on air-sea exchange of inert gases are paramount to properly quantifying production, consumption, and physical transport of biogeochemically important gases (such as carbon dioxide and oxygen) as well as ventilation age tracers (such as sulfur hexafluoride and CFCs). Additionally, global circulation models (GCMs) routinely underestimate deep-ocean ventilation compared to noble gas observations. Introducing these new isotopic constraints into model simulations will help identify physical processes related to deep-water formation that require improvement in future GCM development. Because the overturning circulation is closely tied to projections of future climate, by both the transports of radiative gases and heat into the deep ocean, there is broad international interest in improving future model projections. Therefore, adding high-precision noble gas isotope measurements to the existing body of research on inert gases in seawater will provide valuable new constraints for both the marine biogeochemistry and physical oceanography communities. Education and training of a graduate student and postdoctoral scholar will contribute to the human resource base of the United States. The proposed work will develop high-precision Ar, Kr, and Xe stable isotope ratios in seawater as new oceanographic tracers. Along with a 2018 pilot study, the proposed measurements represent the first high- precision Kr and Xe isotope ratio analyses in seawater. A key goal of this project is to test two specific hypotheses for the observed undersaturation of Ar, Kr, and Xe throughout the deep ocean: (1) rapid cooling-induced gas uptake by the surface ocean during deep-water formation with insufficient time for equilibration before sinking, or (2) subsurface cooling caused by melting of glacial ice, leading to the dissolution of air bubbles trapped in ice. Whereas both of these non-mutually exclusive processes produce similar patterns of heavy noble gas undersaturation, the isotope ratios of these gases are well suited to distinguish the relative importance of each process. Specifically, theoretical predictions suggest a decrease in heavy-to-light isotope ratios from the kinetic fractionation associated with rapid surface ocean gas uptake, but an increase in these ratios from the input of gravitationally enriched glacial meltwater. Other goals include: (a) comparing observations to model simulations to identify successes and shortcomings of GCM representations of deep-water formation processes, and (b) a year-long time series of surface-ocean observations from the SIO pier to test models of isotopic fractionation associated with bubble injection and upwelling, with implications for the saturation of biogeochemically important gases. This work will improve upon a recent method for dissolved noble gas isotopic analysis by increasing sample sizes and refining purification techniques to achieve a 60% improvement in precision.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

拟议的工作将化学海洋学、海洋建模和固体地球化学领域结合在一起，开发溶解在海水中的重惰性气体的稳定同位素组成，作为空气-海洋气体交换的新型物理示踪剂。由于惰性气体具有化学惰性，因此它们是量化物理过程的理想工具。正如最近在实验室实验中量化的那样，由于氩 (Ar)、氪 (Kr) 和氙 (Xe) 同位素比率具有不同的溶解度和扩散率比率，因此它们通过添加具有独特灵敏度的新约束来补充海水中现有的大量惰性气体测量。对惰性气体的海海交换的精确限制对于正确量化生物地球化学重要气体（例如二氧化碳和氧气）以及通风年龄示踪剂（例如六氟化硫和氟氯化碳）的生产、消耗和物理运输至关重要。此外，与惰性气体观测相比，全球环流模型（GCM）通常会低估深海通风。将这些新的同位素约束引入模型模拟将有助于识别与深水形成相关的物理过程，这些过程需要在未来的 GCM 开发中进行改进。由于翻转环流通过将辐射气体和热量输送到深海而与未来气候的预测密切相关，因此国际社会对改进未来模型预测有着广泛的兴趣。因此，在现有的海水惰性气体研究体系中增加高精度惰性气体同位素测量将为海洋生物地球化学和物理海洋学界提供有价值的新约束。研究生和博士后学者的教育和培训将为美国的人力资源基础做出贡献。拟议的工作将开发海水中高精度的 Ar、Kr 和 Xe 稳定同位素比率，作为新的海洋示踪剂。连同 2018 年的一项试点研究，拟议的测量代表了海水中首次高精度 Kr 和 Xe 同位素比分析。该项目的一个关键目标是测试在整个深海中观察到的 Ar、Kr 和 Xe 欠饱和度的两个具体假设：(1) 在深水形成过程中，快速冷却导致表层海洋吸收气体，而没有足够的时间下沉前的平衡，或（2）冰川融化引起的地下冷却，导致冰中捕获的气泡溶解。尽管这两种非互斥过程都会产生类似的重稀有气体欠饱和模式，但这些气体的同位素比率非常适合区分每种过程的相对重要性。具体来说，理论预测表明，由于与表面海洋气体快速吸收相关的动力学分馏，重同位素与轻同位素的比率会降低，但由于重力富集的冰川融水的输入，这些比率会增加。其他目标包括：（a）将观测结果与模型模拟进行比较，以确定 GCM 表示深水形成过程的成功和缺点，以及（b）从 SIO 码头进行长达一年的海表观测时间序列，以测试与气泡注入和上升流相关的同位素分馏，对生物地球化学重要气体的饱和度有影响。这项工作将通过增加样本量和改进纯化技术来改进最近的溶解惰性气体同位素分析方法，以实现精度提高 60%。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力评估进行评估，被认为值得支持。优点和更广泛的影响审查标准。

项目成果

The triple argon isotope composition of groundwater on ten-thousand-year timescales

万年时间尺度地下水的三重氩同位素组成

• DOI: 10.1016/j.chemgeo.2021.120458
• 发表时间: 2021-11
• 期刊: Chemical Geology
• 影响因子: 3.9
• 作者: Seltzer, Alan M.;Krantz, John A.;Ng, Jessica;Danskin, Wesley R.;Bekaert, David V.;Barry, Peter H.;Kimbrough, David L.;Kulongoski, Justin T.;Severinghaus, Jeffrey P.
• 通讯作者: Severinghaus, Jeffrey P.

Solubility Equilibrium Isotope Effects of Noble Gases in Water: Theory and Observations

稀有气体在水中的溶解度平衡同位素效应：理论与观察

• DOI: 10.1021/acs.jpcb.3c05651
• 发表时间: 2023-11
• 期刊: The Journal of Physical Chemistry B
• 作者: Seltzer, Alan M.;Shackleton, Sarah A.;Bourg, Ian C.
• 通讯作者: Bourg, Ian C.

Widespread six degrees Celsius cooling on land during the Last Glacial Maximum

末次盛冰期陆地上普遍降温六摄氏度

• DOI: 10.1038/s41586-021-03467-6
• 发表时间: 2021-05
• 期刊: Nature
• 影响因子: 64.8
• 作者: Seltzer, Alan M.;Ng, Jessica;Aeschbach, Werner;Kipfer, Rolf;Kulongoski, Justin T.;Severinghaus, Jeffrey P.;Stute, Martin
• 通讯作者: Stute, Martin

A unified method for measuring noble gas isotope ratios in air, water, and volcanic gases via dynamic mass spectrometry

通过动态质谱测量空气、水和火山气体中稀有气体同位素比率的统一方法

• DOI: 10.1016/j.ijms.2022.116873
• 发表时间: 2022-08
• 期刊: International Journal of Mass Spectrometry
• 影响因子: 1.8
• 作者: Seltzer, Alan M.;Bekaert, David V.
• 通讯作者: Bekaert, David V.

Groundwater residence time estimates obscured by anthropogenic carbonate

地下水停留时间估计被人为碳酸盐掩盖

• DOI: 10.1126/sciadv.abf3503
• 发表时间: 2021-04
• 期刊: Science Advances
• 影响因子: 13.6
• 作者: Seltzer AM;Bekaert DV;Barry PH;Durkin KE;Mace EK;Aalseth CE;Zappala JC;Mueller P;Jurgens B;Kulongoski JT
• 通讯作者: Kulongoski JT