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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.

Satellite retrievals of carbon monoxide (CO) are routinely assimilated in atmospheric chemistry models to improve air quality forecasts, produce reanalyzes and to estimate emissions. This study applies the quantile‐conserving ensemble filter framework, a novel assimilation algorithm that can deal with non‐Gaussian and modestly nonlinear distributions. Instead of assuming normal distributions like the Ensemble Adjustments Kalman Filter (EAKF), we now apply a bounded normal rank histogram (BNRH) distribution for the prior. The goal is to efficiently estimate bounded quantities such as CO atmospheric mixing ratios and emission fluxes while maintaining the good performance achieved by the EAKF. We contrast assimilating meteorological and MOPITT (Measurement of Pollution in the Troposphere) observations for May 2018. We evaluate the results with the fourth deployment of the NASA Atmospheric Tomography Mission (ATom‐4) airborne field campaign. We also compare simulations with CO tropospheric columns from the network for the detection of atmospheric composition change and surface in‐situ observations from NOAA carbon cycle greenhouse gases. While the differences remain small, the BNRH approach clearly works better than the EAKF in comparison to all observation data sets. Plain Language Summary: The MOPITT instrument on the NASA/Terra satellite can detect carbon monoxide (CO) pollution in the lower and mid‐tropospheric atmosphere but cannot accurately differentiate small changes in the altitude of pollution plumes. Such satellite observations are assimilated in numerical model predictions to improve the spatial and temporal distribution of CO in the atmosphere and to estimate emission fluxes. We present a novel method that does not require assumptions about the model and the observations, leading to a more efficient and accurate assimilation of the satellite observations. Key Points: A novel non Gaussian and nonlinear ensemble data assimilation (DA) framework is applied to MOPITT joint state/flux optimizationThe new method performs better than the Ensemble Adjustment Kalman Filter in comparison to independent observationsMOPITT observations indicate that CAMS‐GLOB‐ANT_v5.3 emission fluxes are underestimated across the mid‐latitudes in May 2018 [ABSTRACT FROM AUTHOR]

Airborne estimates of greenhouse gas emissions are becoming more prevalent with the advent of rapid commercial development of trace gas instrumentation featuring increased measurement accuracy, precision, and frequency, and the swelling interest in the verification of current emission inventories. Multiple airborne studies have indicated that emission inventories may underestimate some hydrocarbon emission sources in US oil-and gas-producing basins. Consequently, a proper assessment of the accuracy of these airborne methods is crucial to interpreting the meaning of such discrepancies. We present a new method of sampling surface sources of any trace gas for which fast and precise measurements can be made and apply it to methane, ethane, and carbon dioxide on spatial scales of ĝ1/4 1000ĝ€m, where consecutive loops are flown around a targeted source region at multiple altitudes. Using Reynolds decomposition for the scalar concentrations, along with Gauss's theorem, we show that the method accurately accounts for the smaller-scale turbulent dispersion of the local plume, which is often ignored in other average mass balance methods. With the help of large eddy simulations (LES) we further show how the circling radius can be optimized for the micrometeorological conditions encountered during any flight. Furthermore, by sampling controlled releases of methane and ethane on the ground we can ascertain that the accuracy of the method, in appropriate meteorological conditions, is often better than 10ĝ€%, with limits of detection below 5ĝ€kgĝ€hĝ'1 for both methane and ethane. Because of the FAA-mandated minimum flight safe altitude of 150ĝ€m, placement of the aircraft is critical to preventing a large portion of the emission plume from flowing underneath the lowest aircraft sampling altitude, which is generally the leading source of uncertainty in these measurements. Finally, we show how the accuracy of the method is strongly dependent on the number of sampling loops and/or time spent sampling the source plume.

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]

The Ozarks Isoprene Experiment (OZIE) was conducted in July 1998 in Missouri, Illinois, Indiana, and Oklahoma. OZIE was designed to investigate the presumed strong isoprene emission rates from the Missouri Ozarks, where there is a high density of oak trees that are efficient isoprene emitters. Ground, balloon, and aircraft measurements were taken over a three-week study period; 0-D and 3-D chemical models were subsequently used to better understand the observed isoprene emissions from the Ozarks and to investigate their potential regional-scale impacts. Leaf-level measurements for two oak tree species yielded normalized average isoprene emission capacities of 66 mgC g-1 h-1, in good agreement with values used in current biogenic emissions models. However, the emission capacities exhibited a temperature dependence that is not captured by commonly used biogenic emission models. Isoprene mixing ratios measured aloft from tethered balloon systems were used to estimate isoprene fluxes. These measurement-derived fluxes agreed with BEIS3 estimates within the relatively large uncertainties in the estimates. Ground-level isoprene mixing ratios exhibited substantial spatial heterogeneity, ranging from

A tethered balloon-sampling platform was used to study biogenic volatile organic compounds (BVOCs) in the atmospheric boundary layer in three distinct moist tropical forest ecoregions, as well as an extensive pasture area, in Amazonia. Approximately 2440 soundings, including as many as four VOC samples collected simultaneously at various altitudes, were made at each site. Concentrations in the mixed layer increased during morning hours and were relatively constant midday through afternoon. Since most important meteorological and chemical parameters were very similar among the sites during the measurement periods, a BVOC canopy emission model was used with a model of the chemistry of the boundary layer to reproduce the atmospheric concentrations observed. The simulations indicated significantly different midday landscape isoprene and α-pinene emission rates for the three forest ecoregions (2200, 5300, 9800 μg m-2h-1 isoprene and 90, 120, and 180 μg m-2 h-1 x-pinene for the three moist forest ecoregions studied, respectively). The differences in emissions among the ecoregions may be attributed to the species composition, which were markedly different and in which the percentage of isoprene and terpene emitting species also differed significantly. © 2004 Blackwell Publishing Ltd.

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]

To understand the Korean Peninsula's carbon dioxide (CO 2) emissions and sinks as well as those of the surrounding region, we used 70 flask-air samples collected during May 2014 to August 2016 at Anmyeondo (AMY; 36.53 ∘ N, 126.32 ∘ E; 46 m a.s.l.) World Meteorological Organization (WMO) Global Atmosphere Watch (GAW) station, located on the west coast of South Korea, for analysis of observed 14 C in atmospheric CO 2 as a tracer of fossil fuel CO 2 contribution (Cff). Observed 14 C / C ratios in CO 2 (reported as Δ values) at AMY varied from -59.5 ‰ to 23.1 ‰, with a measurement uncertainty of ±1.8 ‰. The derived mean value Cff of (9.7±7.8) µ mol mol -1 (1σ) is greater than that found in earlier observations from Tae-Ahn Peninsula (TAP; 36.73 ∘ N, 126.13 ∘ E; 20 m a.s.l., 28 km away from AMY) of (4.4±5.7) µ mol mol -1 from 2004 to 2010. The enhancement above background mole fractions of sulfur hexafluoride (Δx(SF6)) and carbon monoxide (Δx(CO)) correlate strongly with Cff (r>0.7) and appear to be good proxies for fossil fuel CO 2 at regional and continental scales. Samples originating from the Asian continent had greater Δx(CO) : Cff(RCO) values, (29±8) to (36±2) nmol µ mol -1 , than in Korean Peninsula local air ((8±2) nmol µ mol -1). Air masses originating in China showed (1.6±0.4) to (2.0±0.1) times greater RCO than a bottom-up inventory, suggesting that China's CO emissions are underestimated in the inventory, while observed RSF6 values are 2–3 times greater than inventories for both China and South Korea. However, RCO values derived from both inventories and observations have decreased relative to previous studies, indicating that combustion efficiency is increasing in both China and South Korea. [ABSTRACT FROM AUTHOR]

Novel aerial methane (CH4) detection technologies were used in this study to identify anomalously high-emitting oil and gas (O&G) facilities and to guide ground-based "leak detection and repair" (LDAR) teams. This approach has the potential to enable a rapid and effective inspection of O&G facilities under voluntary or regulatory LDAR programs to identify and mitigate anomalously large CH4 emissions from a disproportionately small number of facilities. This is the first study of which the authors are aware to deploy, evaluate, and compare the CH4 detection volumes and cost-effectiveness of aerially guided and purely ground-based LDAR techniques. Two aerial methods, the Kairos Aerospace infrared CH4 column imaging and the Scientific Aviation in situ aircraft CH4 mole fraction measurements, were tested during a 2-week period in the Fayetteville Shale region contemporaneously with conventional ground-based LDAR. We show that aerially guided LDAR can be at least as cost-effective as ground-based LDAR, but several variable parameters were identified that strongly affect cost-effectiveness and which require field research and improvements beyond this pilot study. These parameters include (i) CH4 minimum dectectable limit of aerial technologies, (ii) emission rate size distributions of sources, (iii) remote distinction of fixable versus nonfixable CH4 sources ("leaks" vs. CH4 emissions occurring by design), and (iv) the fraction of fixable sources to total CH4 emissions. Suggestions for future study design are provided. Implications: Mitigation of methane leaks from existing oil and gas operations currently relies on on-site inspections of all applicable facilities at a prescribed frequency. This approach is labor- and cost-intensive, especially because a majority of oil and gas-related methane emissions originate from a disproportionately small number of facilities and components. We show for the first time in real-world conditions how aerial methane measurements can identify anomalously high-emitting facilities to enable a rapid, focused, and directed ground inspection of these facilities. The aerially guided approach can be more cost-effective than current practices, especially when implementing the aircraft deployment improvements discussed here. [ABSTRACT FROM AUTHOR]