Speciated particle-phase organic nitrates (pONs) were quantified using online chemical ionization MS during June and July of 2013 in rural Alabama as part of the Southern Oxidant and Aerosol Study. A large fraction of pONs is highly functionalized, possessing between six and eight oxygen atoms within each carbon number group, and is not the common first generation alkyl nitrates previously reported. Using calibrations for isoprene hydroxynitrates and the measured molecular compositions, we estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. Each of the isoprene-and monoterpenes-derived groups exhibited a strong diel trend consistent with the emission patterns of likely biogenic hydrocarbon precursors. An observationally constrained diel box model can replicate the observed pON assuming that pONs (i) are produced in the gas phase and rapidly establish gasparticle equilibrium and (ii) have a short particle-phase lifetime (∼2-4 h). Such dynamic behavior has significant implications for the production and phase partitioning of pONs, organic aerosol mass, and reactive nitrogen speciation in a forested environment. O rganic nitrates (ONs; ON = RONO 2 + RO 2 NO 2 ) are an important reservoir, if not sink, of atmospheric nitrogen oxides (NO x = NO + NO 2 ). ONs formed from isoprene oxidation alone are responsible for the export of 8-30% of anthropogenic NO x out of the US continental boundary layer (1, 2). Regional NO x budgets and tropospheric ozone (O 3 ) production are, therefore, particularly sensitive to uncertainties in the yields and fates of ON (3-6). The yields implemented in modeling studies are determined from laboratory experiments, in which only a few of the first generation gaseous ONs or the total gas-phase ONs and particle-phase organic nitrates (pONs) have been quantified, whereas production of highly functionalized ONs capable of strongly partitioning to the particle phase have been inferred (7-11) or directly measured in the gas phase (12). Addition of a nitrate (-ONO 2 ) functional group to a hydrocarbon is estimated to lower the equilibrium saturation vapor pressure by 2.5-3 orders of magnitude (13). Thus, ON formation can enhance particle-phase partitioning of semivolatile species in regions with elevated levels of nitrogen oxides, contributing to secondary organic aerosol (SOA) growth (8). However, highly time-resolved measurements of speciated ON in the particle phase have been lacking.We use a recently developed high-resolution time-of-flight chemical ionization mass spectrometer (HRToF-CIMS) using iodide-adduct ionization (14) with a filter inlet for gases and aerosols (FIGAERO) (15) that allows alternating in situ measurements of the molecular SignificanceWe present online field observations of the speciated molecular composition of organic nitrates in ambient atmospheric particles utilizing recently developed high-resolution MS-based instrumentation. We find that never-before-identified low-volatility organi...

Abstract. Isoprene hydroxynitrates (IN) are tracers of the photochemical oxidation of isoprene in high NOx environments. Production and loss of IN have a significant influence on the NOx cycle and tropospheric O3 chemistry. To better understand IN chemistry, a series of photochemical reaction chamber experiments was conducted to determine the IN yield from isoprene photooxidation at high NO concentrations (> 100 ppt). By combining experimental data and calculated isomer distributions, a total IN yield of 9(+4/−3) % was derived. The result was applied in a zero-dimensional model to simulate production and loss of ambient IN observed in a temperate forest atmosphere, during the Southern Oxidant and Aerosol Study (SOAS) field campaign, from 27 May to 11 July 2013. The 9 % yield was consistent with the observed IN/(MVK+MACR) ratios observed during SOAS. By comparing field observations with model simulations, we identified NO as the limiting factor for ambient IN production during SOAS, but vertical mixing at dawn might also contribute (~ 27 %) to IN dynamics. A close examination of isoprene's oxidation products indicates that its oxidation transitioned from a high-NO dominant chemical regime in the morning into a low-NO dominant regime in the afternoon. A significant amount of IN produced in the morning high NO regime could be oxidized in the low NO regime, and a possible reaction scheme was proposed.

Abstract. Measurements of an extensive range of nonmethane hydrocarbons (NMHCs) including alkanes, alkenes, and aromatics, and oxygenated volatile organic compounds (OVOCs) including alcohols, ketones, and aldehydes were conducted for several weeks during the summer of 1995 as part of the Southern Oxidants Study (SOS) at a rural experimental site (Youth, Inc.) 32 km southeast of Nashville, Tennessee, in the southeastern United States. These measurements were conducted to (1) determine the absolute magnitude and variability of oxygenated compounds found in a contemporary rural region; (2) assess the importance of the measured ambient levels of OVOCs on a photochemical reactivity basis relative to the more commonly determined NMHCs; and (3) to evaluate our ability to accurately measure oxygenates by the current techniques employed under a field study scenario. Several other physical (temperature, insolation, etc.), meteorological (wind velocity, wind direction, atmospheric structure, and boundary layer height), and chemical (criterion pollutants, NOx, SO2, CO, 03, etc.) parameters were measured concurrently with the NMHC and OVOC measurements. During the study period, OVOCs were consistently the dominant compounds present, and methanol and acetone had the highest mixing ratios. Although OVOCs made up the majority of the volatile organic compound component on a mass basis, a substantial sink for OH was isoprene and its immediate oxidation products, methacrolein and methyl vinyl ketone. In combination with CO and formaldehyde, these compounds comprised about 85% of the observed OH reactivity at the site. Acetaldehyde and methanol were responsible for an additional 10%, with the NMHCs and remaining OVOCs making up the final 5% of the measured OH reactivity at the site. These observed patterns reinforce recent studies which find OVOCs to be an important component of the rural troposphere.

Abstract. Isoprene and its oxidation products methyl vinyl ketone (MVK) and methacrolein (MACR) were measured over a 4 week period in July of 1995 at a rural/forest site near Nashville, Tennessee, as part of the 1995 Southern Oxidants Study (SOS) field intensive. High nighttime isoprene mixing ratios, measured during a 3 day period of stagnant high pressure, are reported. These high nighttime isoprene events are interpreted as a result of continuing emission of isoprene into a developing shallow nocturnal boundary layer in the early evening, followed by advective transport under the inversion to the measurement site. During some evenings, there is very rapid decay of isoprene just afl:er sunset. These events occurred when the product [O3]'[NO2] was relatively large, consistent with loss via reaction with NO3. A chemical box model showed that isoprene decays were consistent with the NO3 mechanism but only for relatively high NO• conditions. This study indicates that nighttime processing of isoprene can be important for forested regions susceptible to high-NO• transport events. We also find that this nighttime NO3 chemistry can lead to conditions where, at least at the surface, a significant fraction of the NOy is in the form of organic nitrates that are products of the NO3-isoprene reaction and that the NO3-isoprene reaction can be the dominant NO3 sink.

Abstract. Isoprene and its oxidation products, methyl vinyl ketone (MVK) and mcthacrolein (MACR), were measured in a semirural environment that was occasionally heavily impacted by urban emissions. At this site, isoprenc was the most important hydrocarbon in terms of koH' [hydrocarbon], but the aldehydes HCHO and CH3CHO also appear to be very important. The local isoprene photochemistry appears to be occasionally enhanced in NOx-rich urban plumes that are advected to the site over intermediate forested land. When 03 was being rapidly produced in urban plumes advected to this forested site, isoprene was found to contribute = 28% of the total ozone production. We observe that many of the peaks in isoprene oxidation products at this surface site arise from downward mixing of more photochemically processed air aloft, as the nocturnal inversion breaks up in the morning. We estimate that, in the daytime, t3pically 1-2% of the NOy at this NOx-rich site is composed of isoprene nitrates.