Calibration of atmospheric hydrogen measurements

Abstract

Abstract. Interest in atmospheric hydrogen (H2) has been growing in recent years with the prospect of H2 being a potential alternative to fossil fuels as an energy carrier. This has intensified research for a quantitative understanding of the atmospheric hydrogen cycle and its total budget, including the expansion of the global atmospheric measurement network. However, inconsistencies in published observational data constitute a major limitation in exploring such data sets. The discrepancies can be mainly attributed to difficulties in the calibration of the measurements. In this study various factors that may interfere with accurate quantification of atmospheric H2 were investigated including drifts of standard gases in high pressure cylinders. As an experimental basis a procedure to generate precise mixtures of H2 within the atmospheric concentration range was established. Application of this method has enabled a thorough linearity characterization of the commonly used GC-HgO reduction detector. We discovered that the detector response was sensitive to the composition of the matrix gas. Addressing these systematic errors, a new calibration scale has been generated defined by thirteen standards with dry air mole fractions ranging from 139–1226 nmol mol−1. This new scale has been accepted as the official World Meteorological Organisation's (WMO) Global Atmospheric Watch (GAW) H2 mole fraction scale.