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.
Airborne and ground-based observations of a weekend effect in ozone, precursors, and oxidation products in the California South Coast Air Basin
[1] Airborne and ground-based measurements during the CalNex (California Research at the Nexus of Air Quality and Climate Change) field study in May/June 2010 show a weekend effect in ozone in the South Coast Air Basin (SoCAB) consistent with previous observations. The well-known and much-studied weekend ozone effect has been attributed to weekend reductions in nitrogen oxide (NOx = NO + NO2) emissions, which affect ozone levels via two processes: (1) reduced ozone loss by titration and (2) enhanced photochemical production of ozone due to an increased ratio of non-methane volatile organic compounds (VOCs) to NOx. In accord with previous assessments, the 2010 airborne and ground-based data show an average decrease in NOx of 46 ± 11% and 34 ± 4%, respectively, and an average increase in VOC/NOxratio of 48 ± 8% and 43 ± 22%, respectively, on weekends. This work extends current understanding of the weekend ozone effect in the SoCAB by identifying its major causes and quantifying their relative importance from the available CalNex data. Increased weekend production of a VOC-NOxoxidation product, peroxyacetyl nitrate, compared to a radical termination product, nitric acid, indicates a significant contribution from increased photochemical production on weekends. Weekday-to-weekend differences in the products of NOx oxidation show 45 ± 13% and 42 ± 12% more extensive photochemical processing and, when compared with odd oxygen (Ox = O3 + NO2), 51 ± 14% and 22 ± 17% greater ozone production efficiency on weekends in the airborne and ground-based data, respectively, indicating that both contribute to higher weekend ozone levels in the SoCAB.
Measurement of gaseous and particulate nitrates in the atmosphere
Abstract Gaseous and particulate nitrates are simultaneously sampled on a train consisting of a Millipore FHLP filter and a Toyo 51A filter impregnated with NaCl, extracted from the filters and colorimetrically determined. The interferences of NO 2 , of a mixture of NO 2 and O 3 , of PAN and of organic nitrate were examined and found to be negligible in most of the measurements. The field study indicated that the inorganic gaseous nitrate concentration was significantly correlated with the oxidant level, whereas the concentration of particulate nitrate had no correlation with the oxidant level.