Internal consistency tests for evaluation of measurements of anthropogenic hydrocarbons in the troposphere

Measurements of tropospheric nonmethane hydrocarbons (NMHCs) made in continental North America should exhibit a common pattern determined by photochemical removal and dilution acting upon the typical North American urban emissions. We analyze 11 data sets collected in the United States in the context of this hypothesis, in most cases by analyzing the geometric mean and standard deviations of ratios of selected NMHCs. In the analysis we attribute deviations from the common pattern to plausible systematic and random experimental errors. In some cases the errors have been independently verified and the specific causes identified. Thus this common pattern provides a check for internal consistency in NMHC data sets. Specific tests are presented which should provide useful diagnostics for all data sets of anthropogenic NMHC measurements collected in the United States. Similar tests, based upon the perhaps different emission patterns of other regions, presumably could be developed. The specific tests include (1) a lower limit for ethane concentrations, (2) specific NMHCs that should be detected if any are, (3) the relatively constant mean ratios of the longer-lived NMHCs with similar atmospheric lifetimes, (4) the constant relative patterns of families of NMHCs, and (5) limits on the ambient variability of the NMHC ratios. Many experimental problems are identified in the literature and the Southern Oxidant Study data sets. The most important conclusion of this paper is that a rigorous field intercomparison of simultaneous measurements of ambient NMHCs by different techniques and researchers is of crucial importance to the field of atmospheric chemistry. The tests presented here are suggestive of errors but are not definitive; only a field intercomparison can resolve the uncertainties.