Mercury vapor air–surface exchange measured by collocated micrometeorological and enclosure methods – Part I: Data comparability and method characteristics

Abstract. Reliable quantification of air–biosphere exchange flux of elemental mercury vapor (Hg⁰) is crucial for understanding the global biogeochemical cycle of mercury. However, there has not been a standard analytical protocol for flux quantification, and little attention has been devoted to characterize the temporal variability and comparability of fluxes measured by different methods. In this study, we deployed a collocated set of micrometeorological (MM) and dynamic flux chamber (DFC) measurement systems to quantify Hg⁰ flux over bare soil and low standing crop in an agricultural field. The techniques include relaxed eddy accumulation (REA), modified Bowen ratio (MBR), aerodynamic gradient (AGM) as well as dynamic flux chambers of traditional (TDFC) and novel (NDFC) designs. The five systems and their measured fluxes were cross-examined with respect to magnitude, temporal trend and correlation with environmental variables.

Fluxes measured by the MM and DFC methods showed distinct temporal trends. The former exhibited a highly dynamic temporal variability while the latter had much more gradual temporal features. The diurnal characteristics reflected the difference in the fundamental processes driving the measurements. The correlations between NDFC and TDFC fluxes and between MBR and AGM fluxes were significant (R>0.8, p<0.05), but the correlation between DFC and MM fluxes were from weak to moderate (R=0.1–0.5). Statistical analysis indicated that the median of turbulent fluxes estimated by the three independent MM techniques were not significantly different. Cumulative flux measured by TDFC is considerably lower (42% of AGM and 31% of MBR fluxes) while those measured by NDFC, AGM and MBR were similar (<10% difference). This suggests that incorporating an atmospheric turbulence property such as friction velocity for correcting the DFC-measured flux effectively bridged the gap between the Hg⁰ fluxes measured by enclosure and MM techniques. Cumulated flux measured by REA was ~60% higher than the gradient-based fluxes. Environmental factors have different degrees of impacts on the fluxes observed by different techniques, possibly caused by the underlying assumptions specific to each individual method. Recommendations regarding the application of flux quantification methods were made based on the data obtained in this study.