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Hamme, RC, Severinghaus JP.  2007.  Trace gas disequilibria during deep-water formation. Deep-Sea Research Part I-Oceanographic Research Papers. 54:939-950.   10.1016/j.dsr.2007.03.008   AbstractWebsite

We present high-precision measurements by a new isotope dilution technique of a suite of inert gases in the North Pacific. Remarkably smooth gradients in Ar, Kr and Xe from near equilibrium in intermediate waters to several percent undersaturated in deep waters were observed. The general pattern in the deepest waters was that Ar, Kr and Xe were undersaturated (Ar least and Xe most), while N-2 was close to equilibrium, and Ne was supersaturated. We propose that this pattern was produced by the interaction between the different physical properties of the gases (solubility and the temperature dependence of solubility) with the rapid cooling and high wind speeds that characterize deep-water formation regions. In a simple model of deep-water formation by convection, the saturations of the more temperature-sensitive gases were quickly driven down by rapid cooling and could not reequilibrate with the atmosphere before the end of the winter. In contrast, the gas exchange rate of the more bubble-sensitive gases (Ne and N-2) was able to meet or exceed the drawdown by cooling. Our simple convection model demonstrates that the heavier noble gases (Ar, Kr and Xe) are sensitive on seasonal timescales to the competing effects of cooling and air-sea gas exchange that are also important to setting the concentration Of CO2 in newly formed waters. (c) 2007 Elsevier Ltd. All rights reserved.

Hamme, RC, Emerson SR, Severinghaus JP, Long MC, Yashayaev I.  2017.  Using noble gas measurements to derive air-sea process information and predict physical gas saturations. Geophysical Research Letters. 44:9901-9909.   10.1002/2017gl075123   AbstractWebsite

Dissolved gas distributions are important because they influence oceanic habitats and Earth's climate, yet competing controls by biology and physics make gas distributions challenging to predict. Bubble-mediated gas exchange, temperature change, and varying atmospheric pressure all push gases away from equilibrium. Here we use new noble gas measurements from the Labrador Sea to demonstrate a technique to quantify physical processes. Our analysis shows that water-mass formation can be represented by a quasi steady state in which bubble fluxes and cooling push gases away from equilibrium balanced by diffusive gas exchange forcing gases toward equilibrium. We quantify the rates of these physical processes from our measurements, allowing direct comparison to gas exchange parameterizations, and predict the physically driven saturation of other gases. This technique produces predictions that reasonably match N-2/Ar observations and demonstrates that physical processes should force SF6 to be approximate to 6% more supersaturated than CFC-11 and CFC-12, impacting ventilation age calculations. Plain Language Summary Gases dissolved in the ocean are important because they influence oceanic habitats and Earth's climate. Physics and biology combine to control the amounts of gases like carbon dioxide, oxygen, and nitrogen in the ocean. Our research seeks to disentangle and quantify the competing effects of physics and biology on dissolved gases. We present very precise measurements of dissolved noble gas concentrations (neon, argon, and krypton) in the Labrador Sea, one of the few places on Earth where the surface and deep ocean communicate with each other. Because noble gases have no biological function, responding only to physical processes in the ocean, we use these measurements to discover the amounts of physical processes that affect gases during the winter at this site, like rapid cooling of the water or bubbles injected by breaking waves. From these amounts of physical processes, we calculate the concentrations of nitrogen and chlorofluorocarbons if only physical processes affected these gases. Our work will allow oceanographers to better estimate the rate that bioavailable nutrients are being removed from the ocean (a process that biologically creates nitrogen gas) and to better determine how the ocean moves from observations of changing chlorofluorocarbons in the ocean.