Brian W. Lafranchi

Observational insights into aerosol formation from isoprene.

Atmospheric photooxidation of isoprene is an important source of secondary organic aerosol (SOA) and there is increasing evidence that anthropogenic oxidant emissions can enhance this SOA formation. In this work, we use ambient observations of organosulfates formed from isoprene epoxydiols (IEPOX) and methacrylic acid epoxide (MAE) and a broad suite of chemical measurements to investigate the relative importance of nitrogen oxide (NO/NO2) and hydroperoxyl (HO2) SOA formation pathways from isoprene at a forested site in California. In contrast to IEPOX, the calculated production rate of MAE was observed to be independent of temperature. This is the result of the very fast thermolysis of MPAN at high temperatures that affects the distribution of the MPAN reservoir (MPAN / MPA radical) reducing the fraction that can react with OH to form MAE and subsequently SOA (F(MAE formation)). The strong temperature dependence of F(MAE formation) helps to explain our observations of similar concentrations of IEPOX-derived organosulfates (IEPOX-OS; ~1 ng m(-3)) and MAE-derived organosulfates (MAE-OS; ~1 ng m(-3)) under cooler conditions (lower isoprene concentrations) and much higher IEPOX-OS (~20 ng m(-3)) relative to MAE-OS (<0.0005 ng m(-3)) at higher temperatures (higher isoprene concentrations). A kinetic model of IEPOX and MAE loss showed that MAE forms 10-100 times more ring-opening products than IEPOX and that both are strongly dependent on aerosol water content when aerosol pH is constant. However, the higher fraction of MAE ring opening products does not compensate for the lower MAE production under warmer conditions (higher isoprene concentrations) resulting in lower formation of MAE-derived products relative to IEPOX at the surface. In regions of high NOx, high isoprene emissions and strong vertical mixing the slower MPAN thermolysis rate aloft could increase the fraction of MPAN that forms MAE resulting in a vertically varying isoprene SOA source.

Measurement of atmospheric nitrous acid at Bodgett Forest during BEARPEX2007

Nitrous acid (HONO) is an important precursor of the hydroxyl radical (OH) in the lower troposphere. Understanding HONO chemistry, particularly its sources and contribution to HOx (=OH+HO2) production, is very important for understanding atmospheric oxidation processes. A highly sensitive instrument for detecting atmospheric HONO based on wet chemistry followed by liquid waveguide long path absorption photometry was deployed in the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) at Blodgett Forest, California in late summer 2007. The median diurnal variation shows minimum HONO levels of about 20– 30 pptv during the day and maximum levels of about 60– 70 pptv at night, a diurnal pattern quite different from the results at various other forested sites. Measured HONO/NO 2 ratios for a 24-h period ranged from 0.05 to 0.13 with a mean ratio of 0.07. Speciation of reactive nitrogen compounds (NOy) indicates that HONO accounted for only ∼3% of total NOy. However, due to the fast HONO loss through phoCorrespondence to: X. Ren (xren@rsmas.miami.edu) tolysis, a strong HONO source (1.59 ppbv day −1) existed in this environment in order to sustain the observed HONO levels, indicating the significant role of HONO in NO y cycling. The wet chemistry HONO measurements were compared to the HONO measurements made with a Chemical Ionization Mass Spectrometer (CIMS) over a three-day period. Good agreement was obtained between the measurements from the two different techniques. Using the expansive suite of photochemical and meteorological measurements, the contribution of HONO photolysis to HOx budget was calculated to be relatively small (6%) compared to results from other forested sites. The lower HONO mixing ratio and thus its smaller contribution to HOx production are attributed to the unique meteorological conditions and low acid precipitation at Blodgett Forest. Further studies of HONO in this kind of environment are needed to test this hypothesis and to improve our understanding of atmospheric oxidation and nitrogen budget. Published by Copernicus Publications on behalf of the European Geosciences Union. 6284 X. Ren et al.: Measurement of atmospheric nitrous acid at Bodgett Forest