Stanley Rachel H. R.

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Stanley
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Rachel H. R.
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0000-0003-4860-2476

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

2009-05-29 , Stanley, Rachel H. R. , Baschek, Burkard , Lott, Dempsey E. , Jenkins, William J.

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 two-stage 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 20Ne/22Ne, ±2.0‰ for 84Kr/86Kr, ±2.5‰ for 84Kr/82Kr, ±0.9‰ for 132Xe/129Xe, and ±1.3‰ for 132Xe/136Xe. 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 3He/4He with precisions of ±0.1% for air standards and ±0.14% for water samples.

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The 3He flux gauge in the Sargasso Sea : a determination of physical nutrient fluxes to the euphotic zone at the Bermuda Atlantic Time-series Site

2015-09-04 , Stanley, Rachel H. R. , Jenkins, William J. , Doney, Scott C. , Lott, Dempsey E.

Significant rates of primary production occur in the oligotrophic ocean, without any measurable nutrients present in the mixed layer, fueling a scientific paradox that has lasted for decades. Here, we provide a new determination of the annual mean physical supply of nitrate to the euphotic zone in the western subtropical North Atlantic. We combine a 3-year time series of measurements of tritiugenic 3He from 2003 to 2006 in the surface ocean at the Bermuda Atlantic Time-series Study (BATS) site with a sophisticated noble gas calibrated air–sea gas exchange model to constrain the 3He flux across the sea–air interface, which must closely mirror the upward 3He flux into the euphotic zone. The product of the 3He flux and the observed subsurface nitrate–3He relationship provides an estimate of the minimum rate of new production in the BATS region. We also apply the gas model to an earlier time series of 3He measurements at BATS in order to recalculate new production fluxes for the 1985 to 1988 time period. The observations, despite an almost 3-fold difference in the nitrate–3He relationship, yield a roughly consistent estimate of nitrate flux. In particular, the nitrate flux from 2003 to 2006 is estimated to be 0.65 ± 0.14 mol m−2 yr−1, which is ~40 % smaller than the calculated flux for the period from 1985 to 1988. The difference in nitrate flux between the time periods may be signifying a real difference in new production resulting from changes in subtropical mode water formation. Overall, the nitrate flux is larger than most estimates of export fluxes or net community production fluxes made locally for the BATS site, which is likely a reflection of the larger spatial scale covered by the 3He technique and potentially also by the decoupling of 3He and nitrate during the obduction of water masses from the main thermocline into the upper ocean. The upward nitrate flux is certainly large enough to support observed rates of primary production at BATS and more generally in the oligotrophic subtropical ocean.

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Quantifying seasonal air-sea gas exchange processes using noble gas time-series : a design experiment

2006-03 , Stanley, Rachel H. R. , Jenkins, William J. , Doney, Scott C.

A multi-year time-series of measurements of five noble gases (He, Ne, Ar, Kr, and Xe) at a subtropical ocean location may allow quantification of air-sea gas exchange parameters with tighter constraints than is currently available by other methods. We have demonstrated this using a one-dimensional upper ocean model forced by 6-hourly NCEP reanalysis winds and heat flux for the Sargasso Sea near Bermuda. We performed ensemble model runs to characterize the response of the modeled noble gas saturation anomalies to a range of air-sea gas exchange parameters. We then used inverse calculations to quantify the sensitivity of the parameters to hypothetical observations. These calculations show that with currently achievable measurement accuracies, noble gas concentrations in the Sargasso Sea could be used to constrain the magnitude of equilibrium gas exchange to ±11%, the magnitude of the total air injection flux to ±14%, and the magnitude of net photosynthetic oxygen production to ±1.5 mol O2 m−2 y−1. Additionally, we can use noble gases to quantify the relative contributions of bubbles that are partially dissolved to bubbles that are completely dissolved. These constraints are based on idealized assumptions and may not fully account for some of the uncertainties in the meteorological data, in lateral transport processes, and in the solubilities of the noble gases. As a limited demonstration, we applied this approach to a time series of He, Ne, Ar, and O2 measurements from the Sargasso Sea from 1985 to 1988 (data from Spitzer, 1989). Due to the limited number of gases measured and the lower accuracy of those measurements, the constraints in this example application are weaker than could be achieved with current capabilities.

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Apparent oxygen utilization rates calculated from tritium and helium-3 profiles at the Bermuda Atlantic Time-series Study site

2012-06-04 , Stanley, Rachel H. R. , Doney, Scott C. , Jenkins, William J. , Lott, Dempsey E.

We present three years of Apparent Oxygen Utilization Rates (AOUR) estimated from oxygen and tracer data collected over the ocean thermocline at monthly resolution between 2003 and 2006 at the Bermuda Atlantic Time-series Study (BATS) site. We estimate water ages by calculating a transit time distribution from tritium and helium-3 data. The vertically integrated AOUR over the upper 500 m, which is a regional estimate of export, during the three years is 3.1 ± 0.5 mol O2 m−2 yr−1. This is comparable to previous AOUR-based estimates of export production at the BATS site but is several times larger than export estimates derived from sediment traps or 234Th fluxes. We compare AOUR determined in this study to AOUR measured in the 1980s and show AOUR is significantly greater today than decades earlier because of changes in AOU, rather than changes in ventilation rates. The changes in AOU are likely a methodological artefact associated with problems with early oxygen measurements.

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

2009-11-19 , Stanley, Rachel H. R. , Jenkins, William J. , Lott, Dempsey E. , Doney, Scott C.

Air-sea gas exchange is an important part of the biogeochemical cycles of many climatically and biologically relevant gases including CO2, O2, 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 one-dimensional 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 1σ 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.

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Dissolved gases in the deep North Atlantic track ocean ventilation processes

2023-03-14 , Seltzer, Alan M. , Nicholson, David P. , Smethie, William M. , Tyne, Rebecca L. , Le Roy, Emilie , Stanley, Rachel H. R. , Stute, Martin , Barry, Peter H. , McPaul, Katelyn , Davidson, Perrin W. , Chang, Bonnie X. , Rafter, Patrick A. , Lethaby, Paul , Johnson, Rod J. , Khatiwala, Samar , Jenkins, William J.

Gas exchange between the atmosphere and ocean interior profoundly impacts global climate and biogeochemistry. However, our understanding of the relevant physical processes remains limited by a scarcity of direct observations. Dissolved noble gases in the deep ocean are powerful tracers of physical air-sea interaction due to their chemical and biological inertness, yet their isotope ratios have remained underexplored. Here, we present high-precision noble gas isotope and elemental ratios from the deep North Atlantic (~32°N, 64°W) to evaluate gas exchange parameterizations using an ocean circulation model. The unprecedented precision of these data reveal deep-ocean undersaturation of heavy noble gases and isotopes resulting from cooling-driven air-to-sea gas transport associated with deep convection in the northern high latitudes. Our data also imply an underappreciated and large role for bubble-mediated gas exchange in the global air-sea transfer of sparingly soluble gases, including O, N, and SF. Using noble gases to validate the physical representation of air-sea gas exchange in a model also provides a unique opportunity to distinguish physical from biogeochemical signals. As a case study, we compare dissolved N/Ar measurements in the deep North Atlantic to physics-only model predictions, revealing excess N from benthic denitrification in older deep waters (below 2.9 km). These data indicate that the rate of fixed N removal in the deep Northeastern Atlantic is at least three times higher than the global deep-ocean mean, suggesting tight coupling with organic carbon export and raising potential future implications for the marine N cycle.

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