Real-time soil flux measurements and calculations with CRDS + Soil Flux Processor: comparison among flux algorithms and derivation of whole system error

Understanding chamber-based soil flux model fitting and measurement error is key to scaling soils GHG emissions and resolving the primary uncertainties in climate and management feedbacks at regional scales. One key challenge is the selection of the correct empirical model applied to soil flux rate analysis in chamber-based experiments. Another challenge is the characterization of error in the chamber measurement. Traditionally, most chamber-based N2O and CH4 measurements and model derivations have used discrete sampling for GC analysis, and have been conducted using extended chamber deployment periods (DP) which are expected to result in substantial alteration of the pre-deployment flux. The development of high-precision, high-frequency CRDS analyzers has advanced the science of soil flux analysis by facilitating much shorter DP and, in theory, less chamber-induced suppression of the soil-atmosphere diffusion gradient. As well, a new software tool developed by Picarro (the "Soil Flux Processor" or "SFP") links the power of Cavity Ring-Down Spectroscopy (CRDS) technology with an easy-to-use interface that features flexible sample-ID and run-schemes, and provides real-time monitoring of chamber accumulations and environmental conditions. The SFP also includes a sophisticated flux analysis interface which offers a user-defined model selection, including three predominant fit algorithms as default, and an open-code interface for user-composed algorithms. The SFP is designed to couple with the Picarro G2508 system, an analyzer which simplifies soils flux studies by simultaneously measuring primary GHG species -- N2O, CH4, CO2 and H2O. In this study, Picarro partners with the ARS USDA Soil & Water Management Research Unit (R. Venterea, St. Paul), to examine the degree to which the high-precision, high-frequency Picarro analyzer allows for much shorter DPs periods in chamber-based flux analysis, and, in theory, less chamber-induced suppression of the soil-atmosphere diffusion gradient. This study presents an initial review of the most accurate and precise flux-calculation scheme that are suitable for shorter deployment periods. This study also presents the unique derivation of whole-system chamber measurement error available in the SFP.