Toward real-time measurement of atmospheric mercury concentrations using cavity ring-down spectroscopy

Abstract

Abstract. Cavity ring-down spectroscopy (CRDS) is a direct absorption technique that utilizes path lengths up to multiple kilometers in a compact absorption cell and has a significantly higher sensitivity than conventional absorption spectroscopy. This tool opens new prospects for study of gaseous elemental mercury (Hg0) because of its high temporal resolution and reduced sample volume requirements (<0.5 l of sample air). We developed a new sensor based on CRDS for measurement of (Hg0) mass concentration. Sensor characteristics include sub-ng m−3 detection limit and high temporal resolution using a frequency-doubled, tuneable dye laser emitting pulses at ~253.65 nm with a pulse repetition frequency of 50 Hz. The dye laser incorporates a unique piezo element attached to its tuning grating allowing it to tune the laser on and off the Hg0 absorption line on a pulse-to-pulse basis to facilitate differential absorption measurements. Hg0 absorption measurements with this CRDS laboratory prototype are highly linearly related to Hg0 concentrations determined by a Tekran 2537B analyzer over an Hg0 concentration range from 0.2 ng m−3 to 573 ng m−3, implying excellent linearity of both instruments. The current CRDS instrument has a sensitivity of 0.10 ng Hg0 m−3 at 10-s time resolution. Ambient-air tests showed that background Hg0 levels can be detected at low temporal resolution (i.e., 1 s), but also highlight a need for high-frequency (i.e., pulse-to-pulse) differential on/off-line tuning of the laser wavelength to account for instabilities of the CRDS system and variable background absorption interferences. Future applications may include ambient Hg0 flux measurements with eddy covariance techniques, which require measurements of Hg0 concentrations with sub-ng m−3 sensitivity and sub-second time resolution.