Comparison and calibration of methods for ambient reactive mercury quantification.

Gaseous oxidized mercury (GOM) is the dominant form of atmospheric mercury (Hg) deposited and sequestered within ecosystems. Thus, accurate, calibrated measurements of GOM are needed. Here, two active membrane-based collection systems (RMAS) were used to determine GOM and particulate-bound Hg (PBM), as well as reactive Hg (RM = GOM + PBM), and compared with two dual-channel systems (DCS) and a Tekran 2537/1130 speciation system. The DCS measured operationally defined GOM by difference, using concentrations of gaseous elemental Hg (GEM) and total gaseous Hg. One DCS was linked to a custom-built, automated calibration system that permeated GEM, HgBr2, or HgCl2. The five systems were co-located for one-year to develop a dataset that would allow for understanding limitations of each system, and assessing measurement accuracy and long-term precision of the calibrator. The Tekran system measured ~14.5 % of the GOM measured by the other systems. The USU and UNR DCS and RMAS were significantly correlated, but the DCS was 50 and 30 % higher, respectively, than the RMAS. The calibrator performed consistently in the field and lab, and the DCS fully recovered GOM injected by the calibrator. Since the uncalibrated DCS measured the same concentrations as the calibrated DCS, they are both accurate methods for measuring RM and/or GOM. Some loss occurred from the RMAS membranes. SYNOPSIS: Accurate and calibrated measurements of atmospheric reactive mercury using membranes and two dual-channel systems.