The distribution of helium isotopes in the upper kilometer of the water column along the GP15 section in the central Pacific reflects the large-scale patterns of upwelling hydrothermal 3He in the tropics and sub-polar gyre, tracing two important pathways whereby bottom water exits from the deep Pacific. Heavy noble gas saturation anomalies, particularly in the upper two hundred meters of the water column, are more strongly increased by seasonal radiative heating, while lighter noble gas saturation anomalies are increased more by air injection processes. A similar, seasonally persistent radiative heating feature was observed in the Equatorial Undercurrent, and appears to be replicated in climate system model simulations. The origin of this feature, however, remains a mystery. A heuristic component model explains the noble gas saturation anomaly distributions, separating the influences of air injection, barometric pressure and radiative heating/cooling. Results show cohesive spatial patterns consistent with where water masses originate, their circulation, and gas exchange dynamics in relation to their formation regions. Using this model, we diagnose the distribution of "non-atmospheric" 4He in shallow waters, which parallels the helium isotope anomaly and silica distributions.

We observed large water column anomalies in helium isotopes and trace metal concentrations above the Loihi Seamount. The He-3/He-4 of the added helium was 27.3 times the atmospheric ratio, clearly marking its origin to a primitive mantle plume. The dissolved iron to He-3 ratio (dFe:He-3) exported to surrounding waters was 9.3 +/- 0.3 x 10(6). We observed the Loihi He-3 and dFe "signal" at a depth of 1100 m at several stations within similar to 100 - 1000 km of Loihi, which exhibited a distal dFe:He-3 ratio of similar to 4 x 10(6), about half the proximal ratio. These ratios were remarkably similar to those observed over and near the Southern East Pacific Rise (SEPR) despite greatly contrasting geochemical and volcanic-tectonic origins. In contrast, the proximal and distal dMn:He-3 ratios were both similar to 1 x 10(6), less than half of that observed at the SEPR. Dissolved methane was minimally enriched in waters above Loihi Seamount and was distally absent. Using an idealized regional-scale model we replicated the historically observed regional He-3 distribution, requiring a hydrothermal 3He source from Loihi of 10.4 +/- 4.2 mola(-1), similar to 2% of the global abyssal hydrothermal He-3 flux. From this we compute a corresponding dFe flux of similar to 40 Mmola(-1). Global circulation model simulations suggest that the Loihi-influenced waters eventually upwell along the west coast of North America, also extending into the shallow northwest Pacific, making it a possibly important determinant of marine primary production in the subpolar North Pacific. (c) 2020 Elsevier B.V. All rights reserved.

We have determined the concentrations of atmospheric helium, neon, argon, krypton, and xenon in distilled water and seawater equilibrated with moist marine air at one atmosphere over a temperature range from near freezing point to approximately 35 degrees C and a salinity range of zero to roughly 39.5 PSS78. In all, we made 74 sets of noble gas measurements at 34 distinct temperature and salinity combinations. The experiments included 35 replicate pairs of samples drawn from 35 separate equilibrations, which in turn had three pairs of repeat equilibrations run at close to identical temperatures. We fit the results to an eight-parameter function similar to one commonly used to compute solubility equilibrium concentrations of these gases for environmental waters. Based on an estimate of analytical accuracy, reproducibility of the comparison with secondary atmospheric standards, replicate sample reproducibility, and reproducibility of the repeat equilibrations, we estimate this function to predict equilibrium concentrations at a particular temperature and salinity within this range to overall precisions 0.10% or better. This includes the regression statistics associated with interpolation and analytical errors for fitting the 8-parameter smoothing function. There is an overall systematic uncertainty of 0.15% for all gases, based on our confidence in and experience with the integrity and cross-calibration of our air standards over recent years. Because our methods are calibrated using assumed and explicit atmospheric abundances of these noble gases, any subsequent uncertainties in atmospheric abundances cancel out in the determination, particularly when the oceanographic measurements utilize marine air as a primary standard. Furthermore, measurement at ambient atmospheric abundances avoids any potential co-solvency induced biases introduced by using similar to 1 atm pure noble gases, as has been done in most previous studies. We compare these determinations to those made by others in the past and find modest but significant systematic differences with those results.

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.

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 >4000km 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 2000km 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 107mol/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.

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.

Abstract. 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.

We present the distributions of helium isotopes (in the form of helium isotope ratio anomaly relative to the atmospheric ratio) and tritium along two sections occupied in the subtropical North Atlantic as part of the first U.S. GEOTRACES survey (GEOTRACES GA03). The general distributions of these isotopes are consistent with the continuing penetration and evolution of bomb-produced tritium and its daughter isotope 3He in the main thermocline and along the western boundary current system. We combine these two distributions to compute a tritium–3He age, which is related to the elapsed time since the water was at the ocean surface. Although it is an indicator biased by the effects of mixing and influenced by the time history and spatial distribution of bomb tritium delivery to the ocean surface, it still remains a useful measure of ventilation time-scales. Aside from the continued propagation of the tritium–3He transient into the ocean interior, there are three notable features of interest in these distributions. The first is the clear signature of upwelling in the water column near the coast of Mauritania, characterized by the upward bowing of isochrones in the thermocline and discernable 3He excess at the ocean surface. A simple 3He mass balance calculation suggests an upwelling flux of order 1.8×106m3s−1 (1.8Sv) along the Mauritanian coast. The second is a mid-depth (~1500–2000m) core of ventilated waters centered over the Mid-Atlantic Ridge, an anticyclonic circulation of waters likely originating in the Labrador Sea. The third notable feature is a volcanic 3He plume at about 3500m depth emanating from the TAG Hydrothermal Area that is detectable as much as 500km away on each side of the Mid-Atlantic Ridge. We estimate a 3He:heat ratio of ~7×10–18molJ−1 and a 3He flux from the TAG site of ~15mmoly−1. Since 3He is a conserved tracer in the absence of measureable tritium, the correlation of volcanic 3He with other hydrothermally influenced TEIs (e.g., Fe) can be used as a dilution tracer as probe of non-conservative behavior in the water column. Also, since the regional and global fluxes of volcanic 3He are known, the correlations can be used as a regional/global flux gauge for hydrothermal input of those TEIs.

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.

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.

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.

We present and discuss the distribution of (3)He and its relationship to nutrients in two eddies (cyclone C1 and anticyclone A4) with a view towards examining eddy-related mechanisms whereby nutrients are transported from the upper 200-300 m into the euphotic zone of the Sargasso Sea. The different behavior of these tracers in the euphotic zone results in changes in their distributions and relationships that may provide important clues as to the nature of physical and biological processes involved.The cyclonic eddy (C1) is characterized by substantial (3)He excesses within the euphotic zone. The distribution of this excess (3)He is strongly suggestive of both past and recent ongoing deep-water injection into the euphotic zone. Crude mass balance calculations suggest that ail average of approximately 1.4 +/- 0.7mol m(-2) of nitrate has been introduced into the euphotic zone of eddy C1, consistent with the integrated apparent oxygen utilization anomaly in the aphotic zone below. The (3)He-NO(3) relationship within the eddy deviates substantially from the linear thermocline trend, suggestive of incomplete drawdown of nutrients and/or substantial mixing between euphotic and aphotic zone waters.Anticyclone (A4) displays a simpler (3)He-NO(3) relationship, but is relatively impoverished in euphotic zone excess (3)He. We suggest that because of the relatively strong upwelling and lateral divergence of water the residence time of upwelled (3)He is relatively short within the euphotic zone of this eddy. An estimate of the recently upwelled nutrient inventory, based on the excess (3)He observed in A4's lower euphotic zone, is stoichiometrically consistent with the oxygen maximum observed in the euphotic zone. (C) 2008 Elsevier Ltd. All rights reserved.