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Relative rate techniques are used elucidate the reactions of Cl atoms and OH radicals with ethylene glycol diacetate, C[H.sub.3]C(O)O(C[H.sub.2].sub.2)OC(O)C[H.sub.3], in 700 Torr of [N.sub.2]/[O.sub.2] diluent at 296 K. The reaction of C[H.sub.3]C(O)OC[H.sub.2][O.sub.2] with NO has produced chemically activated C[H.sub.3]C(O)OC[H.sub.2]O radicals, which might undergo decomposition through the [alpha]-ester rearrangement than C[H.sub.3]C(O)OC[H.sub.2]O radicals.

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 were 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. 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 FROM AUTHOR]

Hydroxyl (OH) and hydroperoxyl (HO2) radicals are key species driving the oxidation of volatile organic compounds that can lead to the production of ozone and secondary organic aerosols. Previous measurements of these radicals in forest environments with high isoprene, low NOx conditions have shown serious discrepancies with modeled concentrations, bringing into question the current understanding of isoprene oxidation chemistry in these environments. During the summers of 2008 and 2009, OH and peroxy radical concentrations were measured using a laser-induced fluorescence instrument as part of the PROPHET (Program for Research on Oxidants: PHotochemistry, Emissions, and Transport) and CABINEX (Community Atmosphere- Biosphere INteractions EXperiment) campaigns at a forested site in northern Michigan. Supporting measurements of photolysis rates, volatile organic compounds, NOx (NO + NO2) and other inorganic species were used to constrain a zerodimensional box model based on the Regional Atmospheric Chemistry Mechanism, modified to include the Mainz Isoprene Mechanism (RACM-MIM). The CABINEX model OH predictions were in good agreement with the measured OH concentrations, with an observed-to-modeled ratio near one (0.70±0.31) for isoprene mixing ratios between 1-2 ppb on average. The measured peroxy radical concentrations, reflecting the sum of HO2 and isoprene-based peroxy radicals, were generally lower than predicted by the box model in both years. [ABSTRACT FROM AUTHOR]

Hydroxyl (OH) and hydroperoxyl (HO2) radicals are key species driving the oxidation of volatile organic compounds that can lead to the production of ozone and secondary organic aerosols. Previous measurements of these radicals in forest environments with high isoprene, low NOx conditions have shown serious discrepancies with modeled concentrations, bringing into question the current understanding of isoprene oxidation chemistry in these environments. During the summers of 2008 and 2009, OH and peroxy radical concentrations were measured using a laser-induced fluorescence instrument as part of the PROPHET (Program for Research on Oxidants: PHotochemistry, Emissions, and Transport) and CABINEX (Community Atmosphere-Biosphere INteractions EXperiment) campaigns at a forested site in northern Michigan. Supporting measurements of photolysis rates, volatile organic compounds, NOx (NO + NO2) and other inorganic species were used to constrain a zero-dimensional box model based on the Regional Atmospheric Chemistry Mechanism, modified to include the Mainz Isoprene Mechanism (RACM-MIM). The CABINEX model OH predictions were in good agreement with the measured OH concentrations, with an observed-to-modeled ratio near one (0.70 ±0.31) for isoprene mixing ratios between 1-2 ppb on average. The measured peroxy radical concentrations, reflecting the sum of HO2 and isoprene-based peroxy radicals, were generally lower than predicted by the box model in both years. [ABSTRACT FROM AUTHOR]

The key role that biogenic volatile organic compounds (BVOC) play in atmospheric chemistry requires a detailed understanding of how BVOC concentrations will be affected by environmental change. Large-scale screening of BVOC emissions from whole forest ecosystems is difficult with enclosure methods. Leaf composition of BVOC, as a surrogate for direct emissions, can more easily reflect the distribution of BVOC compounds in a forest. In this study, BVOC composition in needles of 92 white pine trees (Pinus strobus), which are becoming a large part of Midwest forests, are tracked for three summers at the University of Michigan Biological Station (UMBS). α-Pinene, the dominant terpene in all samples, accounts for 30-50%of all terpenes on a mole basis. The most abundant sesquiterpenoid was a C15 alcohol identified as germacrene D-4-ol. The relationship between limonene and total other monoterpenes shows two distinct trends in the population of these forests. About 14%(n=13) of the trees showed high levels of limonene (up to 36% of the total BVOC) in the same trees every year. Assuming that needle concentrations scale with emission rate, we estimate that hydroxyl radical reactivity due to reaction with monoterpenes from white pine increases approximately 6% at UMBS when these elevated concentrations are included. We suggest that chemotypic variation within forests has the potential to affect atmospheric chemistry and that large-scale screening of BVOC can be used to study the importance of BVOC variation. [ABSTRACT FROM AUTHOR]

During the 1998, 2000, 2001, 2008, and 2009 summer intensives of the Program for Research on Oxidants: PHotochemistry, Emissions and Transport (PROPHET), ambient measurement of nitrogen oxides (NO + NO2 =NOx) were conducted. NO and NOx mole fractions displayed a diurnal pattern with NOx frequently highest in early morning. This pattern has often been observed in other rural areas. In this paper, we discuss the potential sources and contributing factors of the frequently observed morning pulse of NOx. Of the possible potential contributing factors to the observed morning pulse of NO and NOx, we find that surface-layer transport and slow upward mixing from soil emissions, related to the thermodynamic stability in the nocturnal boundary layer (NBL) before its morning breakup are the largest contributors. The morning NOx peak can significantly impact boundary layer chemistry, e.g. through production of HONO on surfaces, and by increasing the importance of NO3 chemistry in the morning boundary layer. [ABSTRACT FROM AUTHOR]

The key role biogenic volatile organic compounds (BVOC) play in atmospheric chemistry requires a detailed understanding of how BVOC concentrations will be affected by environmental change. Large-scale screening of ecosystems is difficult with enclosure methods. In this study, BVOC in needles of 71 white pine trees (Pinus strobus), which are becoming a large part of Midwest forests, are tracked for three summers at the University of Michigan Biological Station (UMBS). α-pinene, the dominant terpene in all samples, accounts for 30-50% of all terpenes on a mole basis. The most abundant sesquiterpenoid was a C15 alcohol identified as germacrene-D-4-ol. The abundance of this material and its atmospheric relevance has not been considered previously. The relationship between limonene and α-pinene clearly shows two distinct trends in the population of these forests. About 15% of the trees showed high levels of limonene (up to 36% of the total BVOC) in the same trees every year. With this mixture, limonene contributes 11% of the α-pinene contribution to total gas-phase OH loss at UMBS compared to less than 2% considering the composition of the majority trees. Hence we show that chemotypic variation within forests can affect atmospheric chemistry and that large-scale screening of BVOC can be used effectively to study the importance of BVOC variation for predicting atmospheric chemistry in future forests. [ABSTRACT FROM AUTHOR]