Deployment of a sequential two-photon laser induced fluorescence sensor for the detection of gaseous elemental mercury at ambient levels: fast, specific, ultrasensitive detection with parts-per-quadrillion sensitivity

Abstract

Abstract. The operation of a laser-based sensor for gas phase elemental mercury, Hg(0), is described. It utilizes sequential two photon laser excitation with detection of blue shifted laser induced fluorescence to provide a highly specific detection scheme that precludes detection of anything other than atomic mercury. It has high sensitivity, fast temporal resolution, and can be deployed for in-situ measurements in the open atmosphere with essentially no perturbation of the environment. An ambient sample can also be pulled through a fluorescence cell allowing standard addition calibrations of the concentration. No type of preconcentration is required and there appears to be no significant interferences from other atmospheric constituents including gas phase oxidized mercury species. As a consequence, is not necessary to remove RGM from the air sample. The instrument has been deployed as part of an instrument intercomparison and compares well with conventional instrumentation that utilizes preconcentration on gold followed by analysis using Cold Vapor Atomic Fluorescence Spectroscopy. Currently, the achievable detection sensitivity is ~ 15 pg m−3 (~ 5 × 104 atoms cm−3, ~ 2 ppq) at a sampling rate of 0.1Hz i.e. averaging 100 shots with a 10 Hz laser system. Preliminary results are described for a 50 Hz instrument that utilizes a modified excitation sequence and has monitored ambient elemental mercury with an effective sampling rate of 10 Hz. Additional work is required to produce the precision necessary to perform eddy correlation measurements. Addition of a pyrolysis channel should allow the measurement of Total Gaseous Mercury, and hence Reactive Gaseous Mercury (by difference) with good sensitivity and time resolution.