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A cavity ring-down spectroscopy system for high time resolution measurements of gaseous elemental mercury concentrations
AuthorPierce, Ashley M.
Natural Resources and Environmental Science
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The global cycling of mercury (Hg), a highly toxic environmental pollutant, currently has many unknowns. There are various sources of Hg to the atmosphere including both anthropogenic and natural sources. Processes involved in the global cycling of Hg include emissions from legacy Hg pools, deposition, re-emission, and chemical and physical transformation processes such as gas-phase oxidation and heterogeneous redox reactions. Gaseous elemental mercury (GEM) can represent >95% of Hg present in the atmosphere. GEM has a relatively long atmospheric lifetime, which allows it to be transported 1000s of km, effectively making it a global pollutant. Once deposited, Hg can be converted to methylmercury, a bioavailable form of Hg known to cause neurological damage in wildlife and humans. Current atmospheric Hg sensors require long analyzing periods for a single sample (minutes to hours), thus a faster-response sensor would improve characterization of surface-atmosphere exchange processes and atmospheric Hg dynamics. The goal of this thesis work was to develop a new, field-deployable sensor for high time resolution measurements of GEM in ambient air using pulsed cavity ring-down spectroscopy (CRDS). In this research, a CRDS system was developed using a pulsed laser (50 Hz pulse repetition rate) emitting wavelengths tunable between 215 and 280 nm (Hg absorbs at 253.65 nm), a high finesse 1-m-long cavity lined with two high reflectivity mirrors. Due to the long path length (~1 km) produced inside the short cavity, sample volumes could be kept small while measurement sensitivity remained high. By optimizing the CRDS setup and reducing interferences (e.g., ozone concentration fluctuations), the current CRDS sensor was deployed in the field to measure GEM concentrations in ambient air. The sensor was also used for the first-ever GEM flux measurements by the eddy covariance flux method. Results showed that fast GEM fluctuations could be detected by the CRDS sensor and the detection limit was improved compared to other CRDS systems. Limitations in sensitivity and long-term drifts in measurements, however, may limit the use of this system for measurement of sub-ambient levels of GEM or for long-term monitoring campaigns.