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The atmospheric history of molecular hydrogen (H2) from 1852 to 2003 was reconstructed from measurements of firn air collected at Megadunes, Antarctica. The reconstruction shows that H2 levels in the southern hemisphere were roughly constant near 330 parts per billion (ppb; nmol H2 mol-1 air) during the mid to late 1800s. Over the twentieth century, H2 levels rose by about 70% to 550 ppb. The reconstruction shows good agreement with the H2 atmospheric history based on firn air measurements from the South Pole. The broad trends in atmospheric H2 over the twentieth century can be explained by increased methane oxidation and anthropogenic emissions. The H2 rise shows no evidence of deceleration during the last quarter of the twentieth century despite an expected reduction in automotive emissions following more stringent regulations. During the late twentieth century, atmospheric CO levels decreased due to a reduction in automotive emissions. It is surprising that atmospheric H2 did not respond similarly as automotive exhaust is thought to be the dominant source of anthropogenic H2. The monotonic late twentieth century rise in H2 levels is consistent with late twentieth-century flask air measurements from high southern latitudes. An additional unknown source of H2 is needed to explain twentieth-century trends in atmospheric H2 and to resolve the discrepancy between bottom-up and top-down estimates of the anthropogenic source term. The firn air-based atmospheric history of H2 provides a baseline from which to assess human impact on the H2 cycle over the last 150 y and validate models that will be used to project future trends in atmospheric composition as H2 becomes a more common energy source.

Hydrogen (H2) is a promising low-carbon alternative to fossil fuels for many applications. However, significant gaps in our understanding of the atmospheric H2 budget limit our ability to predict the impacts of greater H2 usage. Here we use NOAA H 2 dry air mole fraction observations from air samples collected from ground-based and ship platforms during 2010–2019 to evaluate the representation of H 2 in the NOAA GFDL-AM4.1 atmospheric chemistry-climate model. We find that the base model configuration captures the observed interhemispheric gradient well but underestimates the surface concentration of H2 by about 10 ppb. Additionally, the model fails to reproduce the 1–2 ppb yr -1 mean increase in surface H 2 observed at background stations. We show that the cause is most likely an underestimation of current anthropogenic emissions, including potential leakages from H 2 -producing facilities. We also show that changes in soil moisture, soil temperature, and snow cover have most likely caused an increase in the magnitude of the soil sink, the most important removal mechanism for atmospheric H2 , especially in the Northern Hemisphere. However, there remains uncertainty due to fundamental gaps in our understanding of H 2 soil removal, such as the minimum moisture required for H 2 soil uptake, for which we performed extensive sensitivity analyses. Finally, we show that the observed meridional gradient of the H2 mixing ratio and its seasonality can provide important constraints to test and refine parameterizations of the H2 soil sink. [ABSTRACT FROM AUTHOR]

The NOAA Global Monitoring Laboratory measures atmospheric hydrogen (H2) in grab-samples collected weekly as flask pairs at over 50 sites in the Global Cooperative Air Sampling Network. These NOAA H2 measurements from 2009 to 2021 are publicly available. Measurements representative of background air sampling show higher H2 in recent years at all latitudes. The marine boundary layer (MBL) global mean H2 was 20.2 ±0.2 ppb higher in 2021 compared to 2010. A 10 ppb or more increase over the 2010-2021 average annual cycle was detected in 2016 for MBL zonal means in the tropics and in the Southern Hemisphere. Carbon monoxide measurements in the same air samples suggest large biomass burning events in different regions likely contributed to the observed interannual variability at different latitudes. A major focus in recent years involved the adoption of the World Meteorological Organization Global Atmospheric Watch (WMO GAW) H2 mole fraction X2009 calibration scale, developed and maintained by the Max-Planck Institute for Biogeochemistry (MPI-BGC), Jena, Germany. GML maintains eight H2 primary calibration standards to propagate the MPI scale. These are gravimetric hydrogen-in-air mixtures in electropolished stainless steel cylinders (Essex Industries, st. Louis, MO) which are stable for H2. These mixtures were calibrated at the MPI-BGC, the WMO Central Calibration Laboratory (CCL) for H2, in late 2020 and span the range 250-700 ppb. We have used the CCL assignments to propagate the MPI X2009 H2 calibration scale to NOAA air measurements performed using Gas Chromatography-Helium Pulse Discharge Detector instruments since 2009. To propagate the scale, NOAA uses a hierarchy of secondary and tertiary standards, which are high pressure tanks with whole air mixtures calibrated against the primary and secondary standards respectively. NOAA secondary and tertiary standards are stored in aluminum cylinders, which have a tendency to grow H2 over time. We fit the calibration histories of these standards with 0-2nd order polynomial functions of time and use the time-dependent mole fraction assignments on the MPI X2009 to reprocess all tank air and flask air measurement records. The robustness of the scale propagation over multiple years is evaluated with the regular analysis of target air cylinders and with long-term same air measurement comparison efforts with WMO GAW partner laboratories. Long-term calibrated, globally distributed and freely accessible measurements of H2 and other gasses and isotopes continue to be essential to track and interpret regional and global changes in the atmosphere composition. The adoption of the MPI X2009 H2 calibration scale and subsequent reprocessing of NOAA atmospheric data constitute a significant improvement in the NOAA H2 measurement records. [ABSTRACT FROM AUTHOR]

Since 1999, Environment and Climate Change Canada (ECCC) has been coordinating a multi-laboratory comparison of measurements of long-lived greenhouse gases in whole air samples collected at the Global Atmosphere Watch (GAW) Alert Observatory located in the Canadian High Arctic (82 ∘ 28 ′ N, 62 ∘ 30 ′ W). In this paper, we evaluate the measurement agreement of atmospheric CO 2 , CH 4 , N 2 O, SF 6 , and stable isotopes of CO 2 (δ13 C, δ18 O) between leading laboratories from seven independent international institutions. The measure of success is linked to target goals for network compatibility outlined by the World Meteorological Organization's (WMO) GAW greenhouse gas measurement community. Overall, based on ∼ 8000 discrete flask samples, we find that the co-located atmospheric CO 2 and CH 4 measurement records from Alert by CSIRO, MPI-BGC, SIO, UHEI-IUP, and ECCC versus NOAA (the designated reference laboratory) are generally consistent with the WMO compatibility goals of ± 0.1 ppm CO 2 and ± 2 ppb CH 4 over the 17-year period (1999–2016), although there are periods where differences exceed target levels and persist as systematic bias for months or years. Consistency with the WMO goals for N 2 O, SF 6 , and stable isotopes of CO 2 (δ13 C, δ18 O) has not been demonstrated. Additional analysis of co-located comparison measurements between CSIRO and SIO versus NOAA or INSTAAR (for the isotopes of CO 2) at other geographical sites suggests that the findings at Alert for CO 2 , CH 4 , N 2 O, and δ13 C–CO 2 could be extended across the CSIRO, SIO, and NOAA observing networks. The primary approach to estimate an overall measurement agreement level was carried out by pooling the differences of all individual laboratories versus the designated reference laboratory and determining the 95th percentile range of these data points. Using this approach over the entire data record, our best estimate of the measurement agreement range is -0.51 to + 0.53 ppm for CO 2 , -0.09 ‰ to + 0.07 ‰ for δ13 C, -0.50 ‰ to + 0.58 ‰ for δ18 O, -4.86 to + 6.16 ppb for CH 4 , -0.75 to + 1.20 ppb for N 2 O, and -0.14 to + 0.09 ppt for SF 6. A secondary approach of using the average of 2 standard deviations of the means for all flask samples taken in each individual sampling episode provided similar results. These upper and lower limits represent our best estimate of the measurement agreement at the 95 % confidence level for these individual laboratories, providing more confidence for using these datasets in various scientific applications (e.g., long-term trend analysis). [ABSTRACT FROM AUTHOR]

Historical atmospheric H 2 levels were reconstructed using firn air measurements from two sites in Greenland (NEEM and Summit) and two sites in Antarctica (South Pole and Megadunes). A joint reconstruction based on the two Antarctic sites yields H 2 levels monotonically increasing from about 330 ppb in 1900 to 550 ppb in the late 1990s, leveling off thereafter. These results are similar to individual reconstructions published previously (Patterson et al., 2020, 2021). Interpretation of the Greenland firn air measurements is complicated by challenges in modeling enrichment induced by pore close-off at these sites. We used observations of neon enrichment at NEEM and Summit to tune the parameterization of enrichment induced by pore close-off in our firn air model. The joint reconstruction from the Greenland data shows H 2 levels rising 30 % between 1950 and the late 1980s, reaching a maximum of 530 ppb. After 1990, reconstructed atmospheric H 2 levels over Greenland are roughly constant, with a small decline of 3 % over the next 25 years. The reconstruction shows good agreement with the available flask measurements of H 2 at high northern latitudes. [ABSTRACT FROM AUTHOR]

Hydrogen (H2) is being considered for many applications as an alternative to fossil fuels. Robust assessment of the climate implications of increased H2 usage in the global economy is partly hindered by uncertainties in its biogeochemical cycle. Here we use NOAA H2 dry air mole fraction observations from air samples collected from ground-based and ship platforms from 2010 to 2019 to evaluate the representation of H2 in the NOAA GFDL-AM4.1 atmospheric chemistry-climate model. We find that the model captures the observed interhemispheric gradient well but underestimates the surface concentration of H2 by about 10 ppbv. Observations show a 1–2 ppbv/year mean increase in surface H2 at background stations, while the simulated H2 exhibits no significant change over the 2010–2019 period. We show that this model bias is primarily driven by the estimated decrease of anthropogenic emissions, mostly from transportation, and that including leakage from H2-producing facilities can improve the simulated trend. We find that changes in soil moisture, soil temperature, and snow cover likely increase the magnitude and modify spatial distribution of the soil sink, the most important removal mechanism for atmospheric H2. However, the magnitude and even the sign of such changes is uncertain due to fundamental gaps in our understanding of H2 soil removal, such as the minimum soil moisture for H2 soil uptake. We show that the observed meridional gradient of H2 mixing ratio and its seasonality provide important constraints to test and refine parameterizations of H2 soil removal. [ABSTRACT FROM AUTHOR]

Historical hemispheric atmospheric H2 levels since 1930 were reconstructed using the UCI_2 firn air model and firn air measurements from three sites in Greenland: (NEEM, Summit, and Tunu) and two sites in Antarctica (South Pole and Megadunes). A joint reconstruction based on the two Antarctic sites yields H2 levels monotonically increasing from about 350 ppb in 1900 to 550 ppb in the late 1990's, levelling off thereafter. These results are similar to individual reconstructions published previously (Patterson et al., 2020; 2021). Reconstruction of the Greenland data is complicated by a systematic bias between Tunu and the other sites. The Tunu reconstruction shows substantially lower historical H2 levels than the other two sites, a difference we attribute to possible bias in the calibration of the Tunu measurements. All three reconstructions show a late 20th century maximum in H2 levels over Greenland. A joint reconstruction of the Greenland data shows H2 levels rising 40% from 1930-1990, reaching a maximum of 550 ppb. After 1990, reconstructed atmospheric H2 decrease by 6% over the next 20 years. The reconstruction deviates by at most 4% from the few available surface air measurements of atmospheric H2 levels over Greenland from 1998-2004. However, the longer instrumental records from sampling sites outside of Greenland show a more rapid decrease and stabilization after 1990 compared to the reconstruction. We explore the possibility that this difference is an artefact caused by the firn air model underestimating pore close-off induced enrichment, evidenced by a mismatch between measured and modelled Ne in firn air. We developed new parameterizations which more accurately capture pore close-off induced enrichment at the Greenland sites. Incorporating those 30 parameterizations into the UCI_2 model yields reconstructions with lower H2 levels throughout the mid-late 20th century and more stable H2 levels during the 1990's, in better agreement with the flask measurements. [ABSTRACT FROM AUTHOR]

The atmospheric history of molecular hydrogen (H2) from 1852 to 2003 was reconstructed from measurements of firn air collected at Megadunes, Antarctica. The reconstruction shows that H2 levels in the southern hemisphere were roughly constant near 330 parts per billion (ppb; nmol H2 mol-1 air) during the mid to late 1800s. Over the twentieth century, H2 levels rose by about 70% to 550 ppb. The reconstruction shows good agreement with the H2 atmospheric history based on firn air measurements from the South Pole. The broad trends in atmospheric H2 over the twentieth century can be explained by increased methane oxidation and anthropogenic emissions. The H2 rise shows no evidence of deceleration during the last quarter of the twentieth century despite an expected reduction in automotive emissions following more stringent regulations. During the late twentieth century, atmospheric CO levels decreased due to a reduction in automotive emissions. It is surprising that atmospheric H2 did not respond similarly as automotive exhaust is thought to be the dominant source of anthropogenic H2. The monotonic late twentieth century rise in H2 levels is consistent with late twentieth-century flask air measurements from high southern latitudes. An additional unknown source of H2 is needed to explain twentieth-century trends in atmospheric H2 and to resolve the discrepancy between bottom-up and top-down estimates of the anthropogenic source term. The firn air-based atmospheric history of H2 provides a baseline from which to assess human impact on the H2 cycle over the last 150 y and validate models that will be used to project future trends in atmospheric composition as H2 becomes a more common energy source. [ABSTRACT FROM AUTHOR]

The NOAA Global Monitoring Laboratory serves as the WMO/GAW Central Calibration Laboratory (CCL) for CO2 and is responsible for maintaining the WMO/GAW mole fraction scale used as a reference within the WMO/GAW program. The current WMO-CO2-X2007 scale is embodied by 15 aluminum cylinders containing natural air, with CO2 mole fractions determined using the NOAA manometer from 1995 to 2006. We have made two minor corrections to historical manometric records: fixing an error in the applied second virial coefficient of CO2, and accounting for loss of a small amount of CO2 to materials in the manometer during the measurement process. By incorporating these corrections, extending the measurement records of the original 15 primary standards through 2015, and adding four new primary standards to the suite, we define a new scale, identified as WMO-CO2-X2019. The new scale is 0.18 µmol mol-1 (ppm) greater than the previous scale at 400 ppm CO2. While this difference is small in relative terms (0.045%), it is significant in terms of atmospheric monitoring. All measurements of tertiary-level standards will be reprocessed to WMO-CO2-X2019. The new scale is more internally consistent than WMO-CO2-X2007 owing to revisions in propagation, and should result in an overall improvement in atmospheric data records traceable to the CCL. [ABSTRACT FROM AUTHOR]

Atmospheric flask samples are either collected at atmospheric pressure by simply opening a valve of a pre-evacuated flask, or pressurized with the help of a pump to a few bar above ambient providing large air samples for analysis. Under humid conditions, there is a risk that water vapour in the sample leads to condensation on the walls of the flask, notably at higher than ambient sampling pressures. Liquid water in sample flasks is known to affect the CO2 mixing ratios and also alters the isotopic composition of oxygen (17O and 18O) in CO2 via isotopic equilibration. Hence, for accurate determination of CO2 mole fractions and its stable isotopic composition, it is vital to dry the air samples to a sufficiently low dew point before they are pressurized in flasks to avoid condensation. Moreover, the drying system itself should not influence the mixing ratio and the isotopic composition of CO2, nor of the other constituents under study. For the "Airborne Stable Isotopes of Carbon from the Amazon" (ASICA) project focusing on accurate measurements of CO2 and its singly-substituted stable isotopologues over the Amazon, an air drying system was needed capable of removing water vapour from air sampled at a dew point better than −2 °C, high flow rates up to 12 L/min, and without the need for electrical power. Since to date, no commercial air drying device is available that meets these requirements, we designed and built our own consumable-free, power-free, and portable drying system based on multi-tube Nafion™ gas sample driers (Perma Pure, Lakewood, USA). The required dry purge air is provided by feeding the exhaust flow of the flasks sampling system through a dry molecular sieve (type 3A) cartridge. In this study we describe the systematic evaluation of our Nafion-based air sample dryer with emphasis on its performance concerning the measurements of atmospheric CO2 mole fractions and the three singly-substituted isotopologues of CO2 (16O13C16O, 16O12C17O and 16O12C18O), as well as the trace gas species CH4, CO, N2O, and SF6. Experimental results simulating extreme tropical conditions (saturated air at 33 °C) indicated that the response of the air dryer is almost instantaneous and that approximately 85 L of air, containing up to 4 % water vapour, can be processed staying below a −2 °C dew point temperature (at 275 kPa). We estimated that least 8 flasks can be sampled (at an overpressure of 275 kPa) with a water vapour content below −2 °C dew point temperature during a typical flight sampling up to 5 km altitude over the Amazon, whereas the remaining samples would stay well below 5 °C dew point temperature (at 275 kPa). The performance of the air dryer on measurements of CO2, CH4, CO, N2O, and SF6, and the CO2 isotopologues 16O13C16O and 16O12C18O was tested in the laboratory simulating real sampling conditions by compressing humidified air from a calibrated cylinder, after being dried by the air dryer, into sample flasks. We found that the mole fraction and the isotopic composition difference between the different test conditions (including the dryer) and the base condition (dry air, without dryer) remained well within or very close to, in the case of N2O, the WMO recommended compatibility goals for independent measurement programs, proving that the test condition induced no significant bias on the sample measurements. [ABSTRACT FROM AUTHOR]

We have explored a one-step method for gravimetric preparation of CO2-in-air standards in aluminum cylinders. We consider both adsorption to stainless steel surfaces used in the transfer of highly-pure CO2, and adsorption of CO2 to cylinder walls. We demonstrate that CO2-in-air standards can be prepared with relatively low uncertainty (~ 0.04 %, ~ 95 % Confidence Level) by introducing aliquots whose masses are know to high precision, and by using well-characterized cylinders. Five gravimetric standards, prepared over the nominal range 350 to 490 μmol mol-1 (parts per million, ppm), showed excellent internal consistency, with residuals from a linear fit equal to 0.05 ppm. This work compliments efforts to maintain the World Meteorological Organization, Global Atmosphere Watch, mole fraction scale for carbon dioxide, widely used for atmospheric monitoring. This gravimetric technique could be extended to other atmospheric trace gases, depending on the vapor pressure of the gas. [ABSTRACT FROM AUTHOR]

We have developed a method to calculate the fractional distribution of CO2 across all of its component isotopologues based on measured δ13C and δ18O values. The fractional distribution can be used with known total CO2 to calculate each component isotopologue individually, in units of mole fraction. The technique is applicable to any molecule where isotopologue-specific values are desired. We used it with a new CO2 calibration system to account for isotopic differences among the primary CO2 standards that define the WMO X2007 CO2 in air calibration scale and between the primary standards and standards in subsequent levels of the calibration hierarchy. The new calibration system uses multiple laser spectroscopic techniques to measure amount of substance fractions (in mole fraction units) of the three major CO2 isotopologues (16O12C16O, 16O13C16O, and 18O12C16O) individually. The three measured values are then combined into total CO2 (accounting for the rare unmeasured isotopologues), δ13C, and δ18O values. The new calibration system significantly improves our ability to transfer the WMO CO2 calibration scale with low uncertainty through our role as the World Meteorological Organization Global Atmosphere Watch Central Calibration Laboratory for CO2. Our current estimates for reproducibility of the new calibration system are ±0.01 μmol mol-1 CO2, ±0.2 ‰ δ13C, and ±0.2 ‰ δ18O, all at 68 % confidence interval (CI). [ABSTRACT FROM AUTHOR]

Atmospheric flask samples are either collected at atmospheric pressure by simply opening a valve of a pre-evacuated flask, or pressurized with the help of a pump to a few bar above ambient providing large air samples for analysis. Under humid conditions, there is a risk that water vapour in the sample leads to condensation on the walls of the flask, notably at higher than ambient sampling pressures. Liquid water in sample flasks is known to affect the CO2 mixing ratios and also alters the isotopic composition of oxygen (17O and 18O) in CO2 via isotopic equilibration. Hence, for accurate determination of CO2 mole fractions and its stable isotopic composition, it is vital to dry the air samples to a sufficiently low dew point before they are pressurized in flasks to avoid condensation. Moreover, the drying system itself should not influence the mixing ratio and the isotopic composition of CO2, nor of the other constituents under study. For the "Airborne Stable Isotopes of Carbon from the Amazon" (ASICA) project focusing on accurate measurements of CO2 and its singly-substituted stable isotopologues over the Amazon, an air drying system was needed capable of removing water vapour from air sampled at a dew point better than −2 °C, high flow rates up to 12 L/min, and without the need for electrical power. Since to date, no commercial air drying device is available that meets these requirements, we designed and built our own consumable-free, power-free, and portable drying system based on multi-tube Nafion™ gas sample driers (Perma Pure, Lakewood, USA). The required dry purge air is provided by feeding the exhaust flow of the flasks sampling system through a dry molecular sieve (type 3A) cartridge. In this study we describe the systematic evaluation of our Nafion-based air sample dryer with emphasis on its performance concerning the measurements of atmospheric CO2 mole fractions and the three singly-substituted isotopologues of CO2 (16O13C16O, 16O12C17O and 16O12C18O), as well as the trace gas species CH4, CO, N2O, and SF6. Experimental results simulating extreme tropical conditions (saturated air at 33 °C) indicated that the response of the air dryer is almost instantaneous and that approximately 85 L of air, containing up to 4 % water vapour, can be processed staying below a −2 °C dew point temperature (at 275 kPa). We estimated that least 8 flasks can be sampled (at an overpressure of 275 kPa) with a water vapour content below −2 °C dew point temperature during a typical flight sampling up to 5 km altitude over the Amazon, whereas the remaining samples would stay well below 5 °C dew point temperature (at 275 kPa). The performance of the air dryer on measurements of CO2, CH4, CO, N2O, and SF6, and the CO2 isotopologues 16O13C16O and 16O12C18O was tested in the laboratory simulating real sampling conditions by compressing humidified air from a calibrated cylinder, after being dried by the air dryer, into sample flasks. We found that the mole fraction and the isotopic composition difference between the different test conditions (including the dryer) and the base condition (dry air, without dryer) remained well within or very close to, in the case of N2O, the WMO recommended compatibility goals for independent measurement programs, proving that the test condition induced no significant bias on the sample measurements. [ABSTRACT FROM AUTHOR]