Portable chamber system for measuring chloroform fluxes from terrestrial environments--methodological challenges

This study describes a system designed to measure chloroform flux from terrestrial systems, providing a reliable first assessment of the spatial variability of flux over an area. The study takes into account that the variability of ambient air concentrations is unknown. It includes quality assurance procedures, sensitivity assessments, and testing of materials used to ensure that the flux equation used to extrapolate from concentrations to fluxes is sound and that the system does not act as a sink or a source of chloroform. The results show that many materials and components commonly used in sampling systems designed for CO2, CH4, and N2O emit chloroform and other volatile chlorinated compounds (VOCls) and are thus unsuitable in systems designed for studies of such compounds. To handle the above-mentioned challenges, we designed a system with a non-steady-state chamber and a closed-loop air-circulation unit returning scrubbed air to the chamber. Based on empirical observations, the concentration increase during a deployment was assumed to be linear. Four samples were collected consecutively and a line was fitted to the measured concentrations. The slope of the fitted line and the y-axis intercept were input variables in the equation used to transform concentration change data to flux estimates. The soundness of the flux equation and the underlying assumptions were tested and found to be reliable by comparing modeled and measured concentrations. Fluxes of chloroform in a forest clear-cut on the east coast of Vancouver Island, BC, during the year were found to vary from -130 to 620 ng m(-2) h(-1). The study shows that the method can reliably detect differences of approximately 50 ng m(-2) h(-1) in chloroform fluxes. The statistical power of the method is still comparatively strong down to differences of 35 ng m(-2) h(-1), but for smaller differences, the results should be interpreted with caution.