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

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.