Atmospheric H₂ observations from the NOAA Cooperative Global Air Sampling Network

Abstract

The NOAA Global Monitoring Laboratory (GML) measures atmospheric hydrogen (H2) in grab samples collected weekly as flask pairs at over 50 sites in the Cooperative Global Air Sampling Network. Measurements representative of background air sampling show higher H2 in recent years at all latitudes. The marine boundary layer (MBL) global mean H2 was 552.8 ppb in 2021, 20.2 ± 0.2 ppb higher 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. The NOAA H2 measurements from 2009 to 2021 are now based on the World Meteorological Organization Global Atmospheric Watch (WMO GAW) H2 mole fraction 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 WMO 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 WMO H2 calibration scale to NOAA air measurements performed using gas chromatography and helium pulse discharge detector instruments since 2009. To propagate the scale, NOAA uses a hierarchy of secondary and tertiary standards, which consist of high-pressure whole-air mixtures in aluminum cylinders, calibrated against the primary and secondary standards, respectively. Hydrogen at the parts per billion level has a tendency to increase in aluminum cylinders over time. We fit the calibration histories of these standards with zero-, first-, or second-order polynomial functions of time and use the time-dependent mole fraction assignments on the WMO scale to reprocess all tank air and flask air H2 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 gases and isotopes continue to be essential to track and interpret regional and global changes in the atmosphere composition. The adoption of the WMO H2 calibration scale and subsequent reprocessing of NOAA atmospheric data constitute a significant improvement in the NOAA H2 measurement records.