skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: A method for resolving changes in atmospheric He ∕ N<sub>2</sub> as an indicator of fossil fuel extraction and stratospheric circulation
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
Award ID(s):
1940361
PAR ID:
10301097
Author(s) / Creator(s):
; ; ;
Date Published:
Journal Name:
Atmospheric Measurement Techniques
Volume:
14
Issue:
3
ISSN:
1867-8548
Page Range / eLocation ID:
2515 to 2527
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Chen, Huilin (Ed.)
    Abstract. Tropospheric helium variations are tightly linked to CO2 due to the co-emission of He and CO2 from natural-gasburning. Recently, Birner et al. (2022a) showed that the global consumption of natural gas has measurably increased the He content of theatmosphere. Like CO2, He is also predicted to exhibit complex spatial and temporal variability on shorter timescales, butmeasurements of these short-term variations are lacking. Here, we present the development of an improved gas delivery and purification system for thesemi-continuous mass spectrometric measurement of the atmospheric He-to-nitrogen ratio (He/N2). The method replaces the chemicalgetter used previously by Birner et al. (2021, 2022a) to preconcentrate He in an air stream with a cryogenic trap which can be more simplyregenerated by heating and which improves the precision of the measurement to 22 per meg (i.e., 0.022 ‰) in10 min (1σ). Using this “cryo-enrichment” method, we measured the He/N2 ratios in ambient air at La Jolla (California,USA) over 5 weeks in 2022. During this period, He/N2 was strongly correlated with atmospheric CO2 concentrations, as expectedfrom anthropogenic emissions, with a diurnal cycle of 450–500 per meg (max–min) caused by the sea–land breeze pattern of local winds,which modulates the influence of local pollution sources. 
    more » « less
  2. Abstract The noble gas signature of incoming Pacific Bottom Water (PBW), when compared to North Atlantic Deep Water, indicates the addition of 450 ± 70 GT a−1glacial melt water to form AABW and subsequently PBW. The downstream evolution of this signature between the southern (20°S to equator) and northern (25°–45°N) bottom waters indicates a decrease in sea level pressure around Antarctica over the past two millennia. Vertical profiles of noble gases in the deep Pacific show exponential relationships with depth with scale heights identical to temperature and salinity. Unlike the other noble gases, helium isotopes show evidence of mid‐depth injection of non‐atmospheric helium. Using observed deviations from exponential behavior, we quantify its magnitude and isotope ratio. There is a clear latitude trend in the isotope ratio of this added helium that decreases from a high exceeding 9 RA(atmospheric3He/4He ratio) in the south to around 8 RAnear the equator. North of 30–40°N, it systematically decreases northward to a low of ∼2 RAnorth of 50°N. This decline results from a combination of northward decline in seafloor spreading, release of radiogenic helium from increased sediment thickness, and the possible emission of radiogenic helium through cold seeps along the Alaskan and North American margins. Finally, we derive an improved method of computing the excess helium isotope concentrations and that the distributions of bottom water3HeXS/4HeXSare consistent with what is known about bottom water flow patterns and the input of low3He/4He sedimentary helium. 
    more » « less
  3. Abstract. Chlorine-initiated oxidation of n-alkanes (C8−12) under high-nitrogen oxide conditions was investigated. Observed secondary organic aerosol yields (0.16 to 1.65) are higher than those for OH-initiated oxidation of C8−12 alkanes (0.04 to 0.35). A high-resolution time-of-flight chemical ionization mass spectrometer coupled to a Filter Inlet for Gases and AEROsols (FIGAERO–CIMS) was used to characterize the gas- and particle-phase molecular composition. Chlorinated organics were observed, which likely originated from chlorine addition to the double bond present on the heterogeneously produced dihydrofurans. A two-dimensional thermogram representation was developed to visualize the composition and relative volatility of organic aerosol components using unit-mass resolution data. Evidence of oligomer formation and thermal decomposition was observed. Aerosol yield and oligomer formation were suppressed under humid conditions (35% to 67% RH) relative to dry conditions (under 5% RH). The temperature at peak desorption signal, Tmax, a proxy for aerosol volatility, was shown to change with aerosol filter loading, which should be constrained when evaluating aerosol volatilities using the FIGAERO–CIMS. Results suggest that long-chain anthropogenic alkanes could contribute significantly to ambient aerosol loading over their atmospheric lifetime. 
    more » « less
  4. Abstract. Trichodesmium species, as a group of photosynthetic N2 fixers(diazotrophs), play an important role in the marine biogeochemical cycles ofnitrogen and carbon, especially in oligotrophic waters. How ongoing oceanwarming may interact with light availability to affect Trichodesmium is not yet clear. Wegrew Trichodesmium erythraeum IMS 101 at three temperature levels of 23, 27, and 31∘C undergrowth-limiting and growth-saturating light levels of 50 and 160 µmol quanta m−2 s−1, respectively, for at least 10 generations and thenmeasured physiological performance, including the specific growth rate, N2fixation rate, and photosynthesis. Light availability significantly modulatedthe growth response of Trichodesmium to temperature, with the specific growth ratepeaking at ∼27∘C under the light-saturatingconditions, while growth of light-limited cultures was non-responsive acrossthe tested temperatures (23, 27, and 31∘C). Short-term thermalresponses for N2 fixation indicated that both high growth temperatureand light intensity increased the optimum temperature (Topt) forN2 fixation and decreased its susceptibility to supra-optimaltemperatures (deactivation energy – Eh). Simultaneously, alllight-limited cultures with low Topt and high Eh were unable tosustain N2 fixation during short-term exposure to high temperatures (33–34∘C) that are not lethal for the cells grown underlight-saturating conditions. Our results imply that Trichodesmium spp. growing under lowlight levels while distributed deep in the euphotic zone or under cloudyweather conditions might be less sensitive to long-term temperature changesthat occur on the timescale of multiple generations but are more susceptible toabrupt (less than one generation time span) temperature changes, such asthose induced by cyclones and heat waves. 
    more » « less
  5. Abstract As the spatial dimension is lowered, locally stabilizing interactions are reduced, leading to the emergence of strongly fluctuating phases of matter without classical analogues. Here we report on the experimental observation of a one dimensional quantum liquid of 4 He using nanoengineering by confining it within a porous material preplated with a noble gas to enhance dimensional reduction. The resulting excitations of the confined 4 He are qualitatively different than bulk superfluid helium, and can be analyzed in terms of a mobile impurity allowing for the characterization of the emergent quantum liquid beyond the Luttinger liquid paradigm. The low dimensional helium system offers the possibility of tuning via pressure—from weakly interacting, all the way to the super Tonks-Girardeau gas of strongly interacting hard-core particles. 
    more » « less