Cavity ring-down spectroscopy sensor development for high-time-resolution measurements of gaseous elemental mercury in ambient air

Abstract

Abstract. We describe further development of a previous laboratory prototype pulsed cavity ring-down spectroscopy (CRDS) sensor into a field-deployable system for high-time-resolution, continuous, and automated measurement of gaseous elemental mercury (GEM) concentrations in ambient air. We employed an external, isotopically enriched Hg cell for automated locking and stabilization of the laser wavelength on the GEM peak absorption during measurements. Further, we describe implementation of differential absorption measurements via a piezoelectric tuning element for pulse-by-pulse tuning of the laser wavelength onto and off of the GEM absorption line. This allowed us to continuously correct (at 25 Hz) for system baseline extinction losses unrelated to GEM absorption. Extensive measurement and calibration data obtained with the system were based on spike addition in both GEM-free air and ambient air. Challenges and interferences that occurred during measurements (particularly in ambient air) are discussed including temperature and ozone (O3) concentration fluctuations, and steps taken to reduce these. CRDS data were highly linear (r2 ≥ 0.98) with data from a commercial Tekran 2537 Hg analyzer across a wide range of GEM concentrations (0 to 127 ng m−3) in Hg-free and ambient air. Measurements during periods of stable background GEM concentrations provided a conservative instrument sensitivity estimate of 0.35 ng m−3 for the CRDS system when time averaged for 5 min. This sensitivity, along with concentration patterns observed in ambient air (with the CRDS system and verified with the Tekran analyzer), showed that the sensor was capable of characterizing GEM fluctuations in ambient air. The value of fast-response GEM measurements was shown by a series of GEM spike additions – highlighting that high-temporal-resolution measurement allowed for detailed characterization of fast concentration fluctuations not possible with traditional analyzers.