E. C. Browne

Evidence for NOx Control over Nighttime SOA Formation

Nighttime Sources Organic aerosols account for about half of the total mass of small (submicrometer) particles in the troposphere, and most of them are believed to form through the oxidation of volatile molecules, rather than being emitted directly from specific sources. These particles have important roles in many atmospheric processes, and therefore a better understanding of their complex composition and chemistry is desirable. Rollins et al. (p. 1210) report on measurements of particulate organic nitrates, an important class of organic aerosols that form at night. However, they also found that high concentrations of organic molecules can suppress the growth of organic nitrate particles. These observations should help improve efforts to reduce organic aerosol pollution. The growth of particulate organic nitrates can account for much of the nighttime increase in organic aerosol mass. Laboratory studies have established a number of chemical pathways by which nitrogen oxides (NOx) affect atmospheric organic aerosol (OA) production. However, these effects have not been directly observed in ambient OA. We report measurements of particulate organic nitrates in Bakersfield, California, the nighttime formation of which increases with NOx and is suppressed by high concentrations of organic molecules that rapidly react with nitrate radical (NO3)—evidence that multigenerational chemistry is responsible for organic nitrate aerosol production. This class of molecules represents about a third of the nighttime increase in OA, suggesting that most nighttime secondary OA is due to the NO3 product of anthropogenic NOx emissions. Consequently, reductions in NOx emissions should reduce the concentration of organic aerosol in Bakersfield and the surrounding region.

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

Evidence for a nitrous acid (HONO) reservoir at the ground surface in Bakersfield, CA, during CalNex 2010

Measurements of HONO(g) and particulate nitrite (NO2−(p)) were made with a modified Ambient Ion Monitor–Ion Chromatography (AIM-IC) instrument during California at the Nexus of Air Quality and Climate 2010 in Bakersfield, CA (CalNex-San Joaquin Valley (SJV)). Observations of gas and particulate matter (PM2.5) water-soluble composition showed accumulation of both species at night, followed by loss the next day. Intercomparison with a Stripping Coil-UV/Vis Absorption Photometer (SC-AP) demonstrated excellent agreement with the AIM-IC HONO(g) measurement (slope = 0.957, R2 = 0.86), and the particulate nitrite observations were validated to be free of known interferences for wet chemical instrumentation. The accumulation of nitrite into particulate matter was found to be enhanced when gaseous mixing ratios of HONO(g) were highest. Reactive uptake of HONO(g) on to lofted dust and the ground surface, forming a reservoir, is a potential mechanism to explain these observations. The AIM-IC HONO(g) measurements were parameterized in a chemical model to calculate the ground surface daytime HONO(g) source strength at 4.5 m above the surface, found to be on the order of 1.27 ppb h−1, to determine the relative importance of a surface reservoir. If all deposited nighttime HONO(g) is reemitted the following day, up to 30% of the daytime HONO(g) source at CalNex-SJV may be accounted for. The observations of HONO(g) and NO2−(p) in Bakersfield, during CalNex, suggest a surface sink and source of HONO(g). Extension of currently accepted unknown daytime HONO(g) source reactions to include a potential surface HONO(g) reservoir should therefore be sound, but quantitation of the relative contributions of each surface source toward daytime HONO(g) production remains to be resolved.

Observations of total RONO 2 over the boreal forest: NO x sinks and HNO 3 sources

In contrast with the textbook view of remote chemistry where HNO_3 formation is the primary sink of nitrogen oxides, recent theoretical analyses show that formation of RONO_2 (ΣANs) from isoprene and other terpene precursors is the primary net chemical loss of nitrogen oxides over the remote continents where the concentration of nitrogen oxides is low. This then increases the prominence of questions concerning the chemical lifetime and ultimate fate of ΣANs. We present observations of nitrogen oxides and organic molecules collected over the Canadian boreal forest during the summer which show that ΣANs account for ~20% of total oxidized nitrogen and that their instantaneous production rate is larger than that of HNO3. This confirms the primary role of reactions producing ΣANs as a control over the lifetime of NO_x (NO_x = NO + NO_2) in remote, continental environments. However, HNO_3 is generally present in larger concentrations than ΣANs indicating that the atmospheric lifetime of ΣANs is shorter than the HNO_3 lifetime. We investigate a range of proposed loss mechanisms that would explain the inferred lifetime of ΣANs finding that in combination with deposition, two processes are consistent with the observations: (1) rapid ozonolysis of isoprene nitrates where at least ~40% of the ozonolysis products release NO_x from the carbon backbone and/or (2) hydrolysis of particulate organic nitrates with HNO_3 as a product. Implications of these ideas for our understanding of NO_x and NO_y budget in remote and rural locations are discussed.

An Atmospheric Constraint on the NO2 Dependence of Daytime Near-Surface Nitrous Acid (HONO)

Recent observations suggest a large and unknown daytime source of nitrous acid (HONO) to the atmosphere. Multiple mechanisms have been proposed, many of which involve chemistry that reduces nitrogen dioxide (NO2) on some time scale. To examine the NO2 dependence of the daytime HONO source, we compare weekday and weekend measurements of NO2 and HONO in two U.S. cities. We find that daytime HONO does not increase proportionally to increases in same-day NO2, i.e., the local NO2 concentration at that time and several hours earlier. We discuss various published HONO formation pathways in the context of this constraint.

Rapid heterogeneous oxidation of organic coatings on submicron aerosols

Laboratory studies have found that heterogeneous oxidation can affect the composition and loading of atmospheric organic aerosol particles over time scales of several days, but most studies have examined pure organic particles only. In this study, in order to probe the reactivity of organic species confined near the particle surface, the rates and products of the OH-initiated oxidation of pure squalane particles are compared to oxidation of thin coatings of squalane on ammonium sulfate particles. The squalane reaction rate constant shows a linear dependence on the organic surface area-to-volume ratio, with rate constants for coated particles up to 10 times larger than for pure particles. Changes in the carbon oxidation state and fraction of particulate carbon remaining show similar enhancements, implying that heterogeneous oxidation may exhibit a stronger effect on the loadings and properties of organic aerosol than previously estimated from laboratory studies.

Laser Ablation-Aerosol Mass Spectrometry-Chemical Ionization Mass Spectrometry for Ambient Surface Imaging

Mass spectrometry imaging is becoming an increasingly common analytical technique due to its ability to provide spatially resolved chemical information. Here, we report a novel imaging approach combining laser ablation with two mass spectrometric techniques, aerosol mass spectrometry and chemical ionization mass spectrometry, separately and in parallel. Both mass spectrometric methods provide the fast response, rapid data acquisition, low detection limits, and high-resolution peak separation desirable for imaging complex samples. Additionally, the two techniques provide complementary information with aerosol mass spectrometry providing near universal detection of all aerosol molecules and chemical ionization mass spectrometry with a heated inlet providing molecular-level detail of both gases and aerosols. The two techniques operate with atmospheric pressure interfaces and require no matrix addition for ionization, allowing for samples to be investigated in their native state under ambient pressure conditions. We demonstrate the ability of laser ablation-aerosol mass spectrometry-chemical ionization mass spectrometry (LA-AMS-CIMS) to create 2D images of both standard compounds and complex mixtures. The results suggest that LA-AMS-CIMS, particularly when combined with advanced data analysis methods, could have broad applications in mass spectrometry imaging applications.

CCN closure and composition analysis of droplet-forming aerosol

Cloud condensation nuclei, aerosol chemical composition, and aerosol size measurements were determined at a field site subject to a variety of aerosol sources. A pumped counterflow virtual impactor was utilized to directly determine the chemical composition of the droplet activating aerosol.