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

Author Posting. © American Geophysical Union, 2009. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 10 (2009): Q05008, doi:10.1029/2009GC002429.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.We are grateful for support by the National Science Foundation Chemical Oceanography program (OCE-0221247), by the Department of Defense (graduate fellowship to RHRS), and by the Woods Hole Oceanographic Institution (postdoctoral fellowship for B.B.)

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

© The Author(s), 2012. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biogeosciences 9 (2012): 1969-1983, doi:10.5194/bg-9-1969-2012.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.Support from this work came from the National Science Foundation (OCE-0221247, OCE-0623034, and OCE-1029676) and from the WHOI Penzance Endowed Fund in Support of Assistant Scientists

The deep distributions of helium isotopes, radiocarbon, and noble gases along the U.S. GEOTRACES East Pacific Zonal Transect (GP16)

Author Posting. © The Author(s), 2017. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Marine Chemistry 201 (2018): 167-182, doi:10.1016/j.marchem.2017.03.009.We report the deep distributions of noble gases, helium isotopes, and radiocarbon measured during the U.S. GEOTRACES GP16 East Pacific Zonal Transect between 152 and 77°W at 12- 15°S in the South Pacific. The dominant feature is an intense tongue of hydrothermal effluent that extends more than 4,000 km westward from the East Pacific Rise (EPR) at ~2500m depth. The patterns reveal significant “downstream” variations in water mass structure, advection, and mixing that belie the simple perception of a continuous plume extending westward from the EPR. For example, one feature observed at 120°W, 14°S has tracer signatures that are consistent with a water mass originating from an area as much as 2,000 km south of this section, suggesting a quasi-permanent northward flow on the western flank of the EPR. Helium isotope variations in the plume show a uniquely high 3He/4He source in the tongue compared with typical mid-ocean ridge basalts (MORB), consistent with the anomalously high ratios observed in MORB glasses from the EPR segment just south of this transect. The water column data also reveal that the background 3He/4He east of the EPR is significantly lower than values characteristic of MORB, suggesting an additional, more geographically distributed radiogenic 4He flux of order 107 mol/y into the deep Pacific. In the western end of the section, incoming bottom waters have relatively less hydrothermal hydrothermal helium, more radiocarbon, and more oxygen, as well as negative saturation anomalies for the heavy noble gases (Ar, Kr, and Xe). During the basin-scale upwelling of this water, diapycnal mixing serves to erase these negative anomalies. The relative magnitudes of the increases for the heavy noble gases (Ar, Kr, and Xe) are quantitatively consistent with this process. This leads us to estimate the relatively smaller effects on He and Ne saturations, which range from near zero to 0.2% and 0.3% respectively. With this information, we are able to refine our estimates of the magnitude of 3He and 4He excesses and the absolute 3He/4He ratio of non-atmospheric helium introduced into deep Pacific waters.The work was funded under National Science Foundation grant number OCE-1232991 for WJJ and OCE-1130870 for CRG

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

Author Posting. © American Geophysical Union, 2009. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 114 (2009): C11020, doi:10.1029/2009JC005396.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.Funding from the National Science Foundation Chemical Oceanography program (OCE-0221247 and OCE-0623034)

Fragment Isospin as a Probe of Heavy-Ion Collisions

Isotope ratios of fragments produced at mid-rapidity in peripheral and central collisions of 114Cd ions with 92Mo and 98Mo target nuclei at E/A = 50 MeV are compared. Neutron-rich isotopes are preferentially produced in central collisions as compared to peripheral collisions. The influence of the size (A), density, N/Z, E*/A, and Eflow/A of the emitting source on the measured isotope ratios was explored by comparison with a statistical model (SMM). The mid-rapidity region associated with peripheral collisions does not appear to be neutron-enriched relative to central collisions.Comment: 12 pages including figure

Rapid helium isotopic variability in Mauna Kea shield lavas from the Hawaiian Scientific Drilling Project

Author Posting. © American Geophysical Union, 2004. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 5 (2004): Q04G14, doi:10.1029/2002GC000439.This paper presents new magmatic helium isotopic compositions in a suite of lavas from phase II of the Hawaiian Scientific Drilling Project (HSDP2) core, which sampled Mauna Kea volcano to a maximum depth of 3098 m below sea level. Most of the measurements were performed by in vacuo crushing of olivine phenocrysts, but include submarine pillow glasses from the 2200 to 2500 meter depth interval, and orthopyroxene phenocrysts from an intrusive at 1880 m. The magmatic 3He/4He ratios range from 6 to 24.7 times atmospheric (Ra), which significantly extends the range of values for Mauna Kea volcano. The 3He/4He ratios are lowest (i.e., close to MORB values of ∼8 Ra) near the top of the Mauna Kea section and rise slowly, to 10–12 Ra, at 1000 m below sea level, consistent with results from the HSDP1 core. At depths greater than 1000 m in the core, primarily in the submarine lavas, there are brief periods when the 3He/4He ratios are higher than 14.5 Ra, always returning to a baseline value. Twelve such excursions were identified in the core; all but one are in the submarine section, and most (7) are in the deepest section, at depths of 1950 to 3070 m. The baseline 3He/4He value rises from 10–12 Ra near 1000 m depth to 12–14 Ra at 3000 m. The helium spikes are found only in lavas that are older than 380 Ka in age, based on an age model derived from Ar-Ar data (W. D. Sharp et al., manuscript in preparation, 2003). Excluding the excursions defined by single lava flows (3) and intrusive units (3), the average spike duration is approximately 15 (±9) Ka (n = 6). The high 3He/4He spikes are interpreted as pulses of magma from the center of the actively upwelling Hawaiian hot spot. The short duration of the high 3He/4He excursions suggests that Mauna Kea was never directly over high the 3He/4He component of the plume (during the HSDP2 eruptive period), presumed to be the plume center. Assuming that the Mauna Kea helium spikes result from melting of heterogeneities within the plume, their short duration implies that the length scales of heterogeneities in the solid upwelling mantle are between 60 m and 12 km (for upwelling rates of 2 to 40 cm/yr). The high 3He/4He are associated with high 208Pb/204Pb, and relatively low 143Nd/144Nd, Zr/Nb, and SiO2. The correlations with major elements, trace elements and isotopes demonstrate that helium is coupled to the other geochemical variations, and that the Mauna Kea isotopic variability is caused by heterogeneities within the upwelling plume.This work was supported by EAR/NSF through the Continental Dynamics and Instrumentation and Facilities programs

W.H.O.I. Helium Isotope Laboratory data report no. 2 : Tritium and ³3He data from the beta triangle (All-107, Oct. 1979 and OC-78, March 1980)

The data incorporated in this report consists of 509 tritium and 467 helium isotope measurements made on samples collected on two cruises to the "Beta Triangle" area, an approximately 1000 km on a side triangle centered near 27.5°N, 33.5°W in the eastern subtropical Atlantic. The first cruise (AII-107, H. Stonunel, Chief Scientist) occurred in the auturrm of 1979, and consisted of the Triangle survey with a short meridional section along 38.5°W (approximately 6°N to 27°N) appended. The second cruise (OC-78, H. Stommel, L. Armi, co-Chief Scientists) occurred in March, 1980 and was an abbreviated subsampling of the triangle.Funding was provided by the National Science Foundation under grant Number OCE 79-19815

Monetary Policy and the Oil Futures Market

© The Author(s), 2015. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biogeosciences 12 (2015): 5199-5210, doi:10.5194/bg-12-5199-2015.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.This research was funded by the National Science Foundation (OCE-1434000 and OCE-221247)

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