Sulfur dioxide (SO2) is an important precursor for the formation of atmospheric sulfate aerosol and acid rain. We present an instrument using Broadband Cavity-Enhanced Absorption Spectroscopy (BBCEAS) for the measurement of SO2 with a minimum limit of detection of 0.75 ppbv (3-σ) using the spectral range 305.5–312 nm and an averaging time of 5 min. The instrument consists of high-reflectivity mirrors (0.9985 at 310 nm) and a deep UV light source (Light Emitting Diode). The effective absorption path length of the instrument is 610 m with a 0.966 m base length. Published reference absorption cross sections were used to fit and retrieve the SO2 concentrations and were compared to fluorescence standard measurements for SO2. The comparison was well correlated, R2 = 0.9998 with a correlation slope of 1.04. Interferences for fluorescence measurements were tested and the BBCEAS showed no interference, while ambient measurements responded similarly to standard measurement techniques.
Often only small amounts of sample are available for spectroscopic analytical determinations. This work investigates the enhancement of signal in columns packed with silica particles. We propose that silica particles cause the light to scatter through the column, effectively increasing optical path length. Packed columns are shown to be effective with fluorescence spectroscopy, but results were inconclusive with absorbance spectroscopy.
The Wasatch Front in Utah, USA is currently a non-attainment area for ozone according to the Environmental Protection Agency’s (EPA) National Ambient Air Quality Standards (NAAQS). Nitrogen oxides (NOx = NO2 + NO) and volatile organic compounds (VOCs) in the presence of sunlight lead to ozone formation in the troposphere. When the rate of oxidant production, defined as the sum of O3 and NO2, is faster than the rate of NOx production, a region is said to be NOx-limited and ozone formation will be limited by the concentration of NOx species in the region. The inverse of this situation makes the region VOC-limited. Knowing if a region is NOx-limited or VOC-limited can aid in generating effective mitigation strategies. Understanding the background or regional contributions to ozone in a region, whether it be from the transport of precursors or of ozone, provides information about the lower limit for ozone concentrations that a region can obtain with regulation of local precursors. In this paper, measured oxidant and NOx concentrations are analyzed from 14 counties in the state of Utah to calculate the regional and local contributions to ozone for each region. This analysis is used to determine the nature of the atmosphere in each county by determining if the region is VOC- or NOx-limited. Furthermore, this analysis is performed for each county for the years 2012 and 2022 to determine if there has been a change in the oxidative nature and quantify the regional and local contributions to ozone over a 10-year period. All studied counties—except for Washington County—in Utah were found to be VOC-limited in 2012. This shifted in 2022 to most counties being either in a transitional state or being NOx-limited. Local contributions to ozone increased in two major counties, Cache and Salt Lake Counties, but decreased in Carbon, Davis, Duchesne, Uinta, Utah, Washington, and Weber Counties. Generally, the regional contributions to oxidant concentrations decreased across the state. A summertime spike in both regional and local contributions to oxidants was seen. Smoke from wildfires was seen to increase the regional contributions to oxidants and shift the local regime to be more NOx-limited.
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