skip to main content

Explore Research Products in the NSF-PAR

This content will become publicly available on November 16, 2024

Title: Solubility Equilibrium Isotope Effects of Noble Gases in Water: Theory and Observations
The abundance and isotopic composition of noble gases dissolved in water have many applications in the geosciences. In recent years, new analytical techniques have opened the door to the use of high-precision measurements of noble gas isotopes as tracers for groundwater hydrology, oceanography, mantle geochemistry, and paleoclimatology. These analytical advances have brought about new measurements of solubility equilibrium isotope effects (SEIEs) in water (i.e., the relative solubilities of noble gas isotopes) and their sensitivities to the temperature and salinity. Here, we carry out a suite of classical molecular dynamics (MD) simulations and employ the theoretical method of quantum correction to estimate SEIEs for comparison with experimental observations. We find that classical MD simulations can accurately predict SEIEs for the isotopes of Ar, Kr, and Xe to order 0.01‰, on the scale of analytical uncertainty. However, MD simulations consistently overpredict the SEIEs of Ne and He by up to 40% of observed values. We carry out sensitivity tests at different temperatures, salinities, and pressures and employ different sets of interatomic potential parameters and water models. For all noble gas isotopes, the TIP4P water model is found to reproduce observed SEIEs more accurately than the SPC/E and TIP4P/ice models. Classical MD simulations also accurately capture the sign and approximate magnitude of temperature and salinity sensitivities of SEIEs for heavy noble gases. We find that experimental and modeled SEIEs generally follow an inverse-square mass dependence, which implies that the mean-square force experienced by a noble gas atom within a solvation shell is similar for all noble gases. This inverse-square mass proportionality is nearly exact for Ar, Kr, and Xe isotopes, but He and Ne exhibit a slightly weaker mass dependence. We hypothesize that the apparent dichotomy between He–Ne and Ar–Kr–Xe SEIEs may result from atomic size differences, whereby the smaller noble gases are more likely to spontaneously fit within cavities of water without breaking water–water H-bonds, thereby experiencing softer collisions during translation within a solvation shell. We further speculate that the overprediction of simulated He and Ne SEIEs may result from the neglection of higher-order quantum corrections or the overly stiff representation of van der Waals repulsion by the widely used Lennard-Jones 6–12 potential model. We suggest that new measurements of SEIEs of heavy and light noble gases may represent a novel set of constraints with which to refine hydrophobic solvation theories and optimize the set of interatomic potential models used in MD simulations of water and noble gases.  more » « less
Award ID(s):
1923915
NSF-PAR ID:
10497332
Author(s) / Creator(s):
; ;
Publisher / Repository:
Journal of Physical Chemistry B
Date Published:
Journal Name:
The Journal of Physical Chemistry B
Volume:
127
Issue:
45
ISSN:
1520-6106
Page Range / eLocation ID:
9802 to 9812
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; ; ; ; ; ( , Journal of Geophysical Research: Oceans)
    Abstract

    Gas exchange at high wind speeds is not well understood—few studies have been conducted at wind speeds above 20 ms−1and significant disagreement exists between gas exchange models at high wind speeds. In this study, noble gases (He, Ne, Ar, Kr, and Xe) were measured in 35 experiments in the SUSTAIN wind‐wave tank where the wind speeds ranged from 20 to 50 m s−1and mechanical waves were generated as monochromatic or with a short‐crested JONSWAP frequency spectrum. Bubble size spectra were determined using shadowgraph imagery and wave statistics were measured using a wave wire array. The steady state saturation anomalies and gas fluxes initially increased as wind speeds increased but then leveled off, similar to prior studies of heat and momentum flux coefficients. Noble gas fluxes and steady state saturation anomalies are correlated most strongly with bubble volumes for the less soluble noble gases and with wind speed and wave Reynolds number for the more soluble noble gases. In the JONSWAP experiments, significant wave height was the most important predictor for gas steady state saturation anomalies with correlation coefficients of greater than 0.92 for He, Ne, and Ar (P < 0.05). Furthermore, invasion fluxes were larger than evasion fluxes when other conditions were similar. Taken together, these lab‐based experiments suggest more attention should be paid to parameterizations based on wave characteristics and bubbles and that current wind‐speed based gas exchange parameterizations should not be applied to conditions with very high wind speeds.

     
    more » « less
  2. ; ; ; ( , Geophysical Research Letters)
    Abstract

    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.

     
    more » « less
  3. ; ; ; ( , Atmospheric Measurement Techniques)
    null (Ed.)
    Abstract. The atmospheric He/N2 ratio is expected to increase due to the emission of He associated with fossil fuels and isexpected to also vary in both space and time due to gravitational separationin the stratosphere. These signals may be useful indicators of fossil fuelexploitation and variability in stratospheric circulation, but directmeasurements of He/N2 ratio are lacking on all timescales. Here wepresent a high-precision custom inlet system for mass spectrometers thatcontinuously stabilizes the flow of gas during sample–standard comparisonand removes all non-noble gases from the gas stream. This enablesunprecedented accuracy in measurement of relative changes in the helium molefraction, which can be directly related to the 4He/N2 ratio usingsupplementary measurements of O2/N2, Ar/N2 and CO2.Repeat measurements of the same combination of high-pressure tanks using ourinlet system achieves a He/N2 reproducibility of∼ 10 per meg (i.e., 0.001 %) in 6–8 h analyses. This compares to interannual changesof gravitational enrichment at ∼ 35 km in the midlatitudestratosphere of order 300–400 per meg and an annual tropospheric increasefrom human fossil fuel activity of less than ∼ 30 per meg yr−1 (bounded by previous work on helium isotopes). The gettering andflow-stabilizing inlet may also be used for the analysis of other noble-gasisotopes and could resolve previously unobserved seasonal cycles inKr/N2 and Xe/N2. 
    more » « less
  4. ; ; ; ; ; ; ( , Nature Communications)
    Abstract

    Constraining the magnitude of past hydrological change may improve understanding and predictions of future shifts in water availability. Here we demonstrate that water-table depth, a sensitive indicator of hydroclimate, can be quantitatively reconstructed using Kr and Xe isotopes in groundwater. We present the first-ever measurements of these dissolved noble gas isotopes in groundwater at high precision (≤0.005‰ amu−1; 1σ), which reveal depth-proportional signals set by gravitational settling in soil air at the time of recharge. Analyses of California groundwater successfully reproduce modern groundwater levels and indicate a 17.9 ± 1.3 m (±1 SE) decline in water-table depth in Southern California during the last deglaciation. This hydroclimatic transition from the wetter glacial period to more arid Holocene accompanies a surface warming of 6.2 ± 0.6 °C (±1 SE). This new hydroclimate proxy builds upon an existing paleo-temperature application of noble gases and may identify regions prone to future hydrological change.

     
    more » « less
  5. ; ; ; ( , Physical Chemistry Chemical Physics)
    The potential energy curves (PECs) for the homonuclear He–He, Ar–Ar, Cu–Cu, and Si–Si dimers, as well as heteronuclear Cu–He, Cu–Ar, Cu–Xe, Si–He, Si–Ar, and Si–Xe dimers, are obtained in quantum Monte Carlo (QMC) calculations. It is shown that the QMC method provides the PECs with an accuracy comparable with that of the state-of-the-art coupled cluster singles and doubles with perturbative triples corrections [CCSD(T)] calculations. The QMC data are approximated by the Morse long range (MLR) and (12-6) Lennard-Jones (LJ) potentials. The MLR and LJ potentials are used to calculate the deflection angles in binary collisions of corresponding atom pairs and transport coefficients of Cu and Si vapors and their mixtures with He, Ar, and Xe gases in the range of temperature from 100 K to 10 000 K. It is shown that the use of the LJ potentials introduces significant errors in the transport coefficients of high-temperature vapors and gas mixtures. The mixtures with heavy noble gases demonstrate anomalous behavior when the viscosity and thermal conductivity can be larger than that of the corresponding pure substances. In the mixtures with helium, the thermal diffusion factor is found to be unusually large. The calculated viscosity and diffusivity are used to determine parameters of the variable hard sphere and variable soft sphere molecular models as well as parameters of the power-law approximations for the transport coefficients. The results obtained in the present work include all information required for kinetic or continuum simulations of dilute Cu and Si vapors and their mixtures with He, Ar, and Xe gases. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email