Dempsey E. Lott

Noble gas constraints on air‐sea gas exchange and bubble fluxes

[1] Air-sea gas exchange is an important part of the biogeochemical cycles of many climatically and biologically relevant gases including CO2 ,O 2, dimethyl sulfide and CH4. Here we use a three year observational time series of five noble gases (He, Ne, Ar, Kr, and Xe) at the Bermuda Atlantic Time series Study (BATS) site in tandem with a onedimensional upper ocean model to develop an improved parameterization for air-sea gas exchange that explicitly includes separate components for diffusive gas exchange and bubble processes. Based on seasonal timescale noble gas data, this parameterization, which has a 1s uncertainty of ±14% for diffusive gas exchange and ±29% for bubble fluxes, is more tightly constrained than previous parameterizations. Although the magnitude of diffusive gas exchange is within errors of that of Wanninkhof (1992), a commonly used parameterization, we find that bubble-mediated exchange, which is not explicitly included by Wanninkhof (1992) or many other formulations, is significant even for soluble gases. If one uses observed saturation anomalies of Ar (a gas with similar characteristics to O2) and a parameterization of gas exchange to calculate gas exchange fluxes, then the calculated fluxes differ by � 240% if the parameterization presented here is used compared to using the Wanninkhof (1992) parameterization. If instead one includes the gas exchange parameterization in a model, then the calculated fluxes differ by � 35% between using this parameterization and that of Wanninkhof (1992). These differences suggest that the bubble component should be explicitly included in a range of marine biogeochemical calculations that incorporate air-sea gas fluxes.

Helium isotopic variability within single diamonds from the Orapa kimberlite pipe

Abstract The distribution and isotopic composition of helium has been measured in a suite of well-characterized one-carat diamonds from the Orapa kimberlite, Botswana. Crushing of the diamonds in vacuo indicates that most of the helium is contained by the matrix (generally greater than 90%), rather than by the inclusions. Step-heating experiments, performed on inclusion-free fragments remaining after crushing, indicate that the3He/4He ratio is variablewithin individual diamonds. The fragments, as small as 10 mg, were heated in two timed steps, both at 2000°C. In every case, lower3He/4He ratios are observed in the first graphitization step (0.05–3 × atmospheric), while the last heating step releases helium with systematically higher3He/4He ratio (30–80 × atmospheric). We suggest that this internal isotopic variability is the result of stepwise graphitization: the first heating step initiates graphitization, which nucleates around defects, and the second heating step graphitizes the relatively defect-free regions of the diamond. The3He/4He ratio measured, using the partial graphitization technique, differs by up to a factor of 100 within a single specimen. The inclusion-free fragments release small quantities of helium below 2000°C, which suggests that helium release is obtained only by graphitization. The3He contents of the monocrystalline diamonds are relatively constant (at ∼ 3 × 10−13 cm3 STP/gram) and indicate that most of the isotopic variability is due to radiogenic4He. The variations in4He content are either related to zoning of Th and U in the diamonds (i.e., in-situ decay), to zoning of inherited4He, or to implantation of α-particles from a Th and U rich environment (i.e., kimberlite). Because the Orapa diamonds were mined from roughly 40 m depth in the kimberlite, spallation reactions from cosmic ray interactions are not a significant source of3He. However, calculations based on the age of the kimberlite (90 m.y.) and reasonable Th and U abundances suggest that most of the3He in the Orapa diamonds could be produced by6Li(n, α)T in the diamond. Although this may not be true of all diamonds, nuclear reactions in the crust and mantle (including spallation reactions at the surface) can explain many of the high3He/4He ratios previously reported for diamonds.

A new automated method for measuring noble gases and their isotopic ratios in water samples

[1] A method is presented for precisely measuring all five noble gases and their isotopic ratios in water samples using multiple programmed multistage cryogenic traps in conjunction with quadrupole mass spectrometry and magnetic sector mass spectrometry. Multiple automated cryogenic traps, including a twostage cryotrap used for removal of water vapor, an activated charcoal cryotrap used for helium separation, and a stainless steel cryotrap used for neon, argon, krypton, and xenon separation, allow reproducible gas purification and separation. The precision of this method for gas standards is ±0.10% for He, ±0.14% for Ne, ±0.10% for Ar, ±0.14% for Kr, and ±0.17% for Xe. The precision of the isotopic ratios of the noble gases in gas standards are ±1.9% for 20 Ne/ 22 Ne, ±2.0% for 84 Kr/ 86 Kr, ±2.5% for 84 Kr/ 82 Kr, ±0.9% for 132 Xe/ 129 Xe, and ±1.3% for 132 Xe/ 136 Xe. The precision of this method for water samples, determined by measurement of duplicate pairs, is ±1% for He, ±0.9% for Ne, ±0.3% for Ar, ±0.3% for Kr, and ±0.2% for Xe. An attached magnetic sector mass spectrometer measures 3 He/ 4 He with precisions of ±0.1% for air standards and ±0.14% for water samples.

Continuous Measurements of Dissolved Ne, Ar, Kr, and Xe Ratios with a Field-deployable Gas Equilibration Mass Spectrometer

Noble gases dissolved in natural waters are useful tracers for quantifying physical processes. Here, we describe a field-deployable gas equilibration mass spectrometer (GEMS) that provides continuous, real-time measurements of Ne, Ar, Kr, and Xe mole ratios in natural waters. Gas is equilibrated with a membrane contactor cartridge and measured with a quadrupole mass spectrometer, after in-line purification with reactive metal alloy getters. We use an electron energy of 35 V for Ne to eliminate isobaric interferences, and a higher electron energy for the other gases to improve sensitivity. The precision is 0.7% or better and 1.0% or better for all mole ratios when the instrument is installed in a temperature-controlled environment and a variable-temperature environment, respectively. In the lab, the accuracy is 0.9% or better for all gas ratios using air as the only calibration standard. In the field (and/or at greater levels of disequilbrium), the accuracy is 0.7% or better for Ne/Kr, Ne/Ar, and Ar/Kr, and 2.5% or better for Ne/Xe, Ar/Xe, and Kr/Xe using air as the only calibration standard. The field accuracy improves to 0.6% or better for Ne/Xe, Ar/Xe, and Kr/Xe when the data is calibrated using discrete water samples run on a laboratory-based mass spectrometer. The e-folding response time is 90-410 s. This instrument enables the collection of a large number of continuous, high-precision and accuracy noble gas measurements at substantially reduced cost and labor compared to traditional methods.

Using Noble Gases to Compare Parameterizations of Air‐water Gas Exchange and to Constrain Oxygen Losses by Ebullition in a Shallow Aquatic Environment

Accurate determination of air-water gas exchange fluxes is critically important for calculating ecosystem metabolism rates from dissolved oxygen in shallow aquatic environments. We present a unique data set of the noble gases neon, argon, krypton, and xenon in a salt marsh pond to demonstrate how the dissolved noble gases can be used to quantify gas transfer processes and evaluate gas exchange parameterizations in shallow, near-shore environments. These noble gases are sensitive to a variety of physical processes, including bubbling. We thus additionally use this data set to demonstrate how dissolved noble gases can be used to assess the contribution of bubbling from the sediments (ebullition) to gas fluxes. We find that while literature gas exchange parameterizations do well in modeling more soluble gases, ebullition must be accounted for in order to correctly calculate fluxes of the lighter noble gases. In particular, for neon and argon, the ebullition flux is larger than the differences in the diffusive gas exchange flux estimated by four different wind speed-based parameterizations for gas exchange. We present an application of noble gas derived ebullition rates to improve estimates of oxygen metabolic fluxes in this shallow pond environment. Up to 21% of daily net oxygen production by photosynthesis may be lost from the pond via ebullition during some periods of biologically and physically produced supersaturation. Ebullition could be an important flux of oxygen and other gases that is measurable with noble gases in other shallow aquatic environments.