Monitoring of Atmospheric Hydrogen Peroxide in Houston Using Long Path-Length Laser-Based Absorption Spectroscopy

Wednesday, 17 December 2014
Nancy P Sanchez1, Yingchun Cao2, Wenzhe Jiang2, Frank Tittel2 and Robert J Griffin1, (1)Rice University, Civil and Environmental Engineering, Houston, TX, United States, (2)Rice University, Electrical and Computer Engineering, Houston, TX, United States
Hydrogen peroxide (H2O2) is a relevant atmospheric species mainly formed by recombination of hydroperoxyl radicals. H2O2 participates in the formation of sulfate aerosol by in-cloud oxidation of S(IV) to S(VI) and has been associated with the generation of multi-functional water soluble organic compounds in atmospheric particulate matter. Furthermore, H2O2 plays an important role in the oxidative capacity of the atmosphere as it acts as a reservoir for HOx radicals (OH and HO2). Particular conditions in the Houston area (e.g. extensive presence of petrochemical industry and high ozone and humidity levels) indicate the potential relevance of this species at this location. Despite its atmospheric relevance, no reports on the levels of H2O2 in Houston have been presented previously in the scientific literature. Determination of atmospheric H2O2 usually has been conducted based on transfer of the gas-phase H2O2 to the liquid phase prior to quantification by techniques such as fluorescence spectroscopy. Although these methods allow detection of H2O2 at the sub-ppb level, they present some limitations including the interference from other atmospheric constituents and potential sampling artifacts. In this study, a high sensitivity sensor based on long-path absorption spectroscopy using a distributed-feedback quantum cascade laser was developed and used to conduct direct gas-phase H2O2 monitoring in Houston. The sensor, which targets a strong H2O2 absorption line (~7.73 µm) with no interference from other atmospheric species, was deployed at a ground level monitoring station near the University of Houston main campus during summer 2014. The performance of this novel sensor was evaluated by side-by-side comparison with a fluorescence-based instrument typically used for atmospheric monitoring of H2O2. H2O2 levels were determined, and time series of H2O2 mixing ratios were generated allowing insight into the dynamics, trends, and atmospheric inter-relations of H2O2 in the Houston area.