Sampling of nitrates in ambient air

Abstract

Methods for the measurement of nitric acid, particulate nitrate and total inorganic nitrate (i.e. HNO 3 plus particulate nitrate) are compared using atmospheric samples from the Los Angeles Basin. Nitric acid was measured by (1) the nitrate collected on nylon or NaCl-impregnated cellulose filters after removal of particulate matter with Teflon prefilters, (2) long-path Fourier transform infrared spectroscopy (FTIR) performed by a collaborating investigator, and (3) the difference between total inorganic nitrate (TIN) and particulate nitrate (PN). TIN was measured by the sum of the nitrate collected with a Teflon prefilter and nylon or NaCl-impregnated after-filter. PN was measured by the nitrate able to penetrate a diffusion dénuder coated to remove acidic gases (e.g. HNO 3). Losses of nitrate from Teflon prefilters were determined by comparing the nitrate retained by these filters to the nitrate penetrating the acid gas denuder. TIN and the nitrate collected with glass fiber filters were compared to assess the origin of the artifact particulate nitrate on the latter. Nitric acid measurements using nylon or NaCl-impregnated after-filters were substantially higher than those by the difference technique. This correlated with losses of nitrate from the Teflon prefilters, which exceeded 50 % at high ambient temperature and low relative humidity. Nitric acid by the difference method exceeded that by FTIR by, on average, 20 %. Thus errors inferred in HNO 3 measurements by comparison to the difference measurements are considered minimum values. The high values for HNO 3 by the difference method are consistent with the partial loss of PN in the acid gas denuder. However, no loss of 0.1 μm to 3 μm diameter NH 4NO 3 particles was observed. Thus, if significant, such loss is restricted to coarse particulate nitrate. Heating the filter samplers was shown to increase sampling errors. Nitrate results obtained in short-term, low volume sampling with Gelman A glass fiber filters approximated those with the TIN samplers. Accordingly, these glass fiber filters retained essentially all the gaseous nitric acid sampled.