Past studies of noble gas concentrations in the deep ocean have revealed widespread, several percent undersaturation of Ar, Kr, and Xe. However, the physical explanation for these disequilibria remains unclear. To gain insight into undersaturation set by deep‐water formation, we measured heavy noble gas isotope and elemental ratios from the deep North Pacific using a new analytical technique. To our knowledge, these are the first high‐precision seawater profiles of38Ar/36Ar and Kr and Xe isotope ratios. To interpret isotopic disequilibria, we carried out a suite of laboratory experiments to measure solubility fractionation factors in seawater. In the deep North Pacific, we find undersaturation of heavy‐to‐light Ar and Kr isotope ratios, suggesting an important role for rapid cooling‐driven, diffusive air‐to‐sea gas transport in setting the deep‐ocean undersaturation of heavy noble gases. These isotope ratios represent promising new constraints for quantifying physical air‐sea gas exchange processes, complementing noble gas concentration measurements.
- PAR ID:
- 10438206
- Date Published:
- Journal Name:
- Proceedings of the National Academy of Sciences
- Volume:
- 120
- Issue:
- 11
- ISSN:
- 0027-8424
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
Abstract -
Rationale Noble gases are widely used as physically based climate proxies, notably in dissolved water samples as tracers of past recharge temperature in groundwater and air–sea gas exchange processes in seawater. Recent advances in measuring large‐volume samples of dissolved noble gas isotopic ratios at high precision have expanded the range of climate parameters that can be interpreted.
Methods We build on prior methods for measuring noble gas stable isotopes at high precision with a new large‐volume equilibration (LVE) method wherein sample gases are equilibrated in the sample flask between the dissolved phase and the headspace. The original dissolved gas composition is determined by measuring the headspace gases and correcting for the equilibrium dissolved gas content of the discarded water using known solubilities and fractionation factors. We evaluate the accuracy and precision of this method with air‐equilibrated water standards of known noble gas composition.
Results Replicate air‐equilibrated water standards and field measurements demonstrate that the LVE method achieves comparable precision to prior methods, with major advantages of measuring the Ne content as a constraint on excess air and allowing for long‐term sample storage. Isotope ratios measured with the LVE method in replicate samples were consistent between two laboratories, and LVE elemental noble gas abundances agreed closely with replicate samples measured using established copper‐tube methods and static noble gas mass spectrometry.
Conclusions The new LVE method enables reconstruction of past water table depths at ±1 m precision along with excess air, recharge temperature, and age and hydrogeochemical indicators. It has wide application to investigating climate signals and physical gas exchange processes in groundwater and seawater.
-
Abstract Here we use high-precision carbon isotope data (δ13C-CO2) to show atmospheric CO2during Marine Isotope Stage 4 (MIS 4, ~70.5-59 ka) was controlled by a succession of millennial-scale processes. Enriched δ13C-CO2during peak glaciation suggests increased ocean carbon storage. Variations in δ13C-CO2in early MIS 4 suggest multiple processes were active during CO2drawdown, potentially including decreased land carbon and decreased Southern Ocean air-sea gas exchange superposed on increased ocean carbon storage. CO2remained low during MIS 4 while δ13C-CO2fluctuations suggest changes in Southern Ocean and North Atlantic air-sea gas exchange. A 7 ppm increase in CO2at the onset of Dansgaard-Oeschger event 19 (72.1 ka) and 27 ppm increase in CO2during late MIS 4 (Heinrich Stadial 6, ~63.5-60 ka) involved additions of isotopically light carbon to the atmosphere. The terrestrial biosphere and Southern Ocean air-sea gas exchange are possible sources, with the latter event also involving decreased ocean carbon storage.
-
Abstract The noble gas signature of incoming Pacific Bottom Water (PBW), when compared to North Atlantic Deep Water, indicates the addition of 450 ± 70 GT a−1glacial melt water to form AABW and subsequently PBW. The downstream evolution of this signature between the southern (20°S to equator) and northern (25°–45°N) bottom waters indicates a decrease in sea level pressure around Antarctica over the past two millennia. Vertical profiles of noble gases in the deep Pacific show exponential relationships with depth with scale heights identical to temperature and salinity. Unlike the other noble gases, helium isotopes show evidence of mid‐depth injection of non‐atmospheric helium. Using observed deviations from exponential behavior, we quantify its magnitude and isotope ratio. There is a clear latitude trend in the isotope ratio of this added helium that decreases from a high exceeding 9 RA(atmospheric3He/4He ratio) in the south to around 8 RAnear the equator. North of 30–40°N, it systematically decreases northward to a low of ∼2 RAnorth of 50°N. This decline results from a combination of northward decline in seafloor spreading, release of radiogenic helium from increased sediment thickness, and the possible emission of radiogenic helium through cold seeps along the Alaskan and North American margins. Finally, we derive an improved method of computing the excess helium isotope concentrations and that the distributions of bottom water3HeXS/4HeXSare consistent with what is known about bottom water flow patterns and the input of low3He/4He sedimentary helium.
-
Abstract Seasonal formation of Dense Shelf Water (DSW) in the Ross Sea is a direct precursor to Antarctic Bottom Water, which fills the deep ocean with atmospheric gases in what composes the southern limb of the solubility pump. Measurements of seawater noble gas concentrations during katabatic wind events in two Ross Sea polynyas reveal the physical processes that determine the boundary value properties for DSW. This decomposition reveals 5–6 g kg−1of glacial meltwater in DSW and sea‐ice production rates of up to 14 m yr−1within the Terra Nova Bay polynya. Despite winds upwards of 35 m s−1during the observations, air bubble injection had a minimal contribution to gas exchange, accounting for less than 0.01 μmols kg−1of argon in seawater. This suggests the slurry of frazil ice and seawater at the polynya surface inhibits air‐sea exchange. Most noteworthy is the revelation that sea‐ice formation and glacial melt contribute significantly to the ventilation of DSW, restoring 10% of the gas deficit for krypton, 24% for argon, and 131% for neon, while diffusive gas exchange contributes the remainder. These measurements reveal a cryogenic component to the solubility pump and demonstrate that while sea ice blocks air‐sea exchange, sea ice formation and glacial melt partially offset this effect via addition of gases. While polynyas are a small surface area, they represent an important ventilation site within the southern‐overturning cell, suggesting that ice processes both enhance and hinder the solubility pump.