EVALUATION OF NOy AND NITRIC ACID MEASUREMENT METHODS AND COLLECTION OF AMBIENT DATA
California has an ambient air quality standard for nitrogen dioxide (NO2), and oxides of nitrogen are also critical participants in atmospheric photochemistry to form ozone. Ambient air quality monitoring networks use chemiluminescent analyzers that alternately measure NO and all nitrogenous species that are converted to NO by a heated catalyst. The difference is defined as NO2. In the atmosphere these nitrogenous species (NOy) consist of, in addition to NO and NO2, nitrogenous acids (nitric and nitrous), ammonia (NH3), and organic nitrates. Dual converter NOx analyzers were used during SCOS97-NARSTO to measure NOy and nitric acid. These instruments were refurbished by replacing or reactivating their reduction converters and thoroughly evaluating their efficiency to convert nitrogen-containing species. These instruments are equipped with dual converters with one channel fitted with a NaCl-coated fabric denuder to selectively remove nitric acid (NOy*). Since the instrument automatically cycles between the two channels, the difference is a measure of nitric acid. A pair of collocated analyzers was set up at the CE-CERT laboratory in Riverside and a single analyzer was installed in Azusa at the monitoring site operated by the South Coast Air Quality Management District (SCAQMD). Data collection started April and October 2000, respectively, for the Riverside and Azusa measurement sites. Data were compiled and validated until April 2001. NOy values at Riverside ranged up to 300 ppb, and values at Azusa reached up to 500 ppb. The Azusa NOy and NOx reported by the SCAQMD compared quite closely. Since it was not possible to have both analyzers sample the same span gas, the significance of differences between the two approaches could not be evaluated. The diurnal pattern of nitric acid was observable nearly every day during the smog season. The concentrations at Riverside ranged up to 6 ppb in the summer. Despite the measurement period at Azusa not including the summer smog season, nitric acid concentrations as high as 8 ppb were observed. A thermoevolution denuder (TED) to measure nitric acid was evaluated under laboratory conditions. This device uses a special ceramic fabric denuder coated with sodium chloride to selectively remove nitric acid. Since this fabric strongly adsorbs microwave radiation at the same wavelength as that for cooking, the fabric can be heated rapidly and controllably to high iv temperatures using a standard microwave oven. This heating will decompose the collected sodium nitrate to NOx. While this design allowed the denuder to adsorb nitric acid, the amount recovered was low and variable. We found that the denuder was not evenly heated, and the amount recovered when drops of dilute nitric acid were placed on the denuder depended on the location on the denuder that was used. It was likely that the microwave oven, which was a consumer product, was not designed to produce a uniform microwave field. We concluded that additional research was needed before the system was ready to evaluate with other methods of measuring nitric acid. This report included the initial year of NOy and nitric acid data. We continued to maintain the NOy analyzers and added NO2/PAN gas chromatographs at both sites. These chromatographs separate NO2 and quantify the amount using luminol detection. This selective method of measuring NO2 will be used to quantify the amount of NO2 contained in the NOy. Under additional funding these instruments will be maintained until October 2002. The results from this period will be the subject of a final report for the second period of funding.
Trends in ozone, its precursors, and related secondary oxidation products in Los Angeles, California: A synthesis of measurements from 1960 to 2010
Decreases in ozone (O3) observed in California's South Coast Air Basin (SoCAB) over the past five decades have resulted from decreases in local emissions of its precursors, nitrogen oxides (NOx = NO + NO2) and volatile organic compounds (VOCs). Ozone precursors have been characterized in the SoCAB with measurements dating back to 1960. Here we compile an extensive historical data set using measurements in the SoCAB between 1960 and 2010. Faster rates of decrease have occurred in abundances of VOCs (−7.3 ± 0.7% yr−1) than in NOx (−2.6 ± 0.3% yr−1), which have resulted in a decrease in VOC/NOx ratio (−4.8 ± 0.9% yr−1) over time. Trends in the NOx oxidation products peroxyacetyl nitrate (PAN) and nitric acid (HNO3), measured in the SoCAB since 1973, show changes in ozone production chemistry resulting from changes in precursor emissions. Decreases in abundances of PAN (−9.3 ± 1.1% yr−1) and HNO3 (−3.0 ± 0.8% yr−1) reflect trends in VOC and NOx precursors. Enhancement ratios of O3 to (PAN + HNO3) show no detectable trend in ozone production efficiency, while a positive trend in the oxidized fraction of total reactive nitrogen (+2.2 ± 0.5% yr−1) suggests that atmospheric oxidation rates of NOx have increased over time as a result of the emissions changes. Changes in NOx oxidation pathways have increasingly favored production of HNO3, a radical termination product associated with quenching the ozone formation cycle.
Simultaneous nitric acid, particulate nitrate and acidity measurements in ambient air
Abstract A laboratory and field study was conducted to evaluate measurement methods for atmospheric nitric acid and to elucidate the formation of artifact particulate nitrate on filter media. Nitric acid collection with nylon and NaCl-impregnated filters was compared employing Teflon pre-filters to remove atmospheric particulate matter. The two collection procedures provided > 97% collection of nitric acid at the levels expected under ambient conditions. At higher levels, the efficiency of the nylon filters decreased. Nylon filters supplied by Millipore and Ghia Corporations were shown to be equally effective. Clean Teflon pre-filters permitted passage of > 98% of the HNO 3 to the collection filters. However, atmospheric particulate matter on the pre-filters retained HNO 3 . Ammonium nitrate on otherwise clean pre-filters caused positive error in HNO 3 measurement (and a corresponding loss of particulate nitrate) when clean air was passed through the sample. Dissociation to NH 3 and HNO 3 is a likely source of these errors. A lower limit of 22 (ppb) 2 is obtained for the NH 4 NO 3 dissociation constant at 21°C. Atmospheric sampling was done in Pittsburg, California. On average, results with the two HNO 3 collection procedures agreed within 3% for levels in the range 0.3–1.5 ppb. Levels of HNO 3 and NH 3 were below those needed for saturation with respect to NH 4 NO 3 formation. A glass fiber filter was shown to serve as a total inorganic nitrate sampler, collecting both particulate nitrate and HNO 3 .