Trace gas emission in chambers: a non-steady-state diffusion model

Non-steady-state (NSS) chambers are widely used to measure trace gas emissions from the Earth's surface to the atmosphere. Unfortunately, traditional interpretations of time-dependent chamber concentrations often systematically underestimate predeployment exchange rates because they do not accurately represent the fundamental physics of diffusive soil gas transport that follows chamber deployment. To address this issue, we formally derived a time-dependent diffusion model applicable to NSS chamber observations and evaluated its performance using simulated chamber headspace C[O.sub.2] concentration data generated by an independent, three-dimensional, numerical diffusion model. Using nonlinear regression to estimate the model parameters, we compared the performance of the non-steady-state diffusive flux estimator (NDFE) to that of the linear, quadratic, and steady-state diffusion models that are widely cited in the literature, determined its sensitivity to violation of the primary assumptions on which it is based, and addressed some of the practicalities of its application. In sharp contrast to the other models, NDFE proved an accurate and robust estimator of trace gas emissions across a wide range of soil, chamber design, and deployment scenarios.