Effects of Natural Variability on the Use of Standard Deviation to Represent Measurement Uncertainties in Atmospheric Composition Studies
Measurement uncertainty is defined as a “non-negative parameter characterizing the dispersion of the quantity values being attributed to a measurand”. It is most common that the uncertainties of GAW hourly measurements, such as greenhouse gas measurements, are reported as standard deviations derived from individual sampling at a higher time resolution (e.g., 1 min). In contrast, the uncertainties of GAW measurements of reactive gases and aerosol properties are reported in percentiles covering the same probability. A quick look at hourly CO 2 data from Cape Grim, Australia yielded some interesting findings: the hourly standard deviation is, on average, more than a factor of 10 higher for the measurements under non-background conditions (over 50% observations), while the difference in average CO 2 amount fraction was less than 2 ppm. The dramatic contrast cannot be explained by the difference in measurement uncertainties, but can largely be attributed the natural variability, or episodic ambient CO 2 variation reflecting changes in meteorological conditions or emissions. These initial findings motivated a more in-depth analysis of the ground-based measurements of trace gases and aerosol properties. This analysis will be using continuous 1 min ground site observations to construct time averaged statistical indicators to evaluate whether the standard deviation is adequate to represent the dispersion, especially under marked influence by natural variability. The suitability of this representation can be determined by examining the difference between the standard deviation and percentiles encompassing the same probability. We will examine time intervals of 1 hour, 3 hours, and 24 hours, with the latter time intervals chosen to match those commonly used in model assessments. We will also investigate how natural variability can alter the probability distribution of the measurands and how adequate the quadrature propagation of uncertainties is under these conditions. The results will include several trace gases (e.g., CO 2 , CO, O 3 , and NO 2 ) with a range of measurement techniques (e.g., PANDORA, in situ), atmospheric lifetimes, and aerosol properties (e.g. scattering coefficient). The findings from this analysis should provide some useful feedback on the best practices for uncertainty reporting.