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- Tsiligiannis, Epameinondas, et al.
(författare)
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A Four Carbon Organonitrate as a Significant Product of Secondary Isoprene Chemistry
- 2022
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Ingår i: Geophysical Research Letters. - : American Geophysical Union (AGU). - 0094-8276 .- 1944-8007. ; 49:11
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Tidskriftsartikel (refereegranskat)abstract
- Oxidation of isoprene by nitrate radicals (NO3) or by hydroxyl radicals (OH) under high NOx conditions forms a substantial amount of organonitrates (ONs). ONs impact NOx concentrations and consequently ozone formation while also contributing to secondary organic aerosol. Here we show that the ONs with the chemical formula C4H7NO5 are a significant fraction of isoprene-derived ONs, based on chamber experiments and ambient measurements from different sites around the globe. From chamber experiments we found that C4H7NO5 isomers contribute 5%-17% of all measured ONs formed during nighttime and constitute more than 40% of the measured ONs after further daytime oxidation. In ambient measurements C4H7NO5 isomers usually dominate both nighttime and daytime, implying a long residence time compared to C-5 ONs which are removed more rapidly. We propose potential nighttime sources and secondary formation pathways, and test them using a box model with an updated isoprene oxidation scheme.
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| 5. |
- Wu, R. R., et al.
(författare)
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Molecular composition and volatility of multi-generation products formed from isoprene oxidation by nitrate radical
- 2021
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 21:13, s. 10799-10824
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Tidskriftsartikel (refereegranskat)abstract
- Isoprene oxidation by nitrate radical (NO3) is a potentially important source of secondary organic aerosol (SOA). It is suggested that the second or later-generation products are the more substantial contributors to SOA. However, there are few studies investigating the multi-generation chemistry of isoprene-NO3 reaction, and information about the volatility of different isoprene nitrates, which is essential to evaluate their potential to form SOA and determine their atmospheric fate, is rare. In this work, we studied the reaction between isoprene and NO3 in the SAPHIR chamber (Julich) under near-atmospheric conditions. Various oxidation products were measured by a high-resolution time-offlight chemical ionization mass spectrometer using Br as the reagent ion. Most of the products detected are organic nitrates, and they are grouped into monomers (C-4 and C-5 products) and dimers (C-10 products) with 1-3 nitrate groups according to their chemical composition. Most of the observed products match expected termination products observed in previous studies, but some compounds such as monomers and dimers with three nitrogen atoms were rarely reported in the literature as gas-phase products from isoprene oxidation by NO3. Possible formation mechanisms for these compounds are proposed. The multi-generation chemistry of isoprene and NO3 is characterized by taking advantage of the time behavior of different products. In addition, the vapor pressures of diverse isoprene nitrates are calculated by different parametrization methods. An estimation of the vapor pressure is also derived from their condensation behavior. According to our results, isoprene monomers belong to intermediate-volatility or semi-volatile organic compounds and thus have little effect on SOA formation. In contrast, the dimers are expected to have low or extremely low volatility, indicating that they are potentially substantial contributors to SOA. However, the monomers constitute 80% of the total explained signals on average, while the dimers contribute less than 2 %, suggesting that the contribution of isoprene NO3 oxidation to SOA by condensation should be low under atmospheric conditions. We expect a SOA mass yield of about 5% from the wall-loss- and dilution-corrected mass concentrations, assuming that all of the isoprene dimers in the low- or extremely low-volatility organic compound (LVOC or ELVOC) range will condense completely.
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- Brownwood, B., et al.
(författare)
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Gas-Particle Partitioning and SOA Yields of Organonitrate Products from NO3-Initiated Oxidation of Isoprene under Varied Chemical Regimes
- 2021
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Ingår i: Acs Earth and Space Chemistry. - : American Chemical Society (ACS). - 2472-3452. ; 5:4, s. 785-800
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Tidskriftsartikel (refereegranskat)abstract
- Alkyl nitrate (AN) and secondary organic aerosol (SOA) from the reaction of nitrate radicals (NO3) with isoprene were observed in the Simulation of Atmospheric PHotochemistry In a large Reaction (SAPHIR) chamber during the NO(3)Isop campaign in August 2018. Based on 15 day-long experiments under various reaction conditions, we conclude that the reaction has a nominally unity molar AN yield (observed range 90 +/- 40%) and an SOA mass yield of OA + organic nitrate aerosol of 13-15% (with similar to 50 mu g m(-3) inorganic seed aerosol and 2-5 mu g m-3 total organic aerosol). Isoprene (5-25 ppb) and oxidant (typically similar to 100 ppb O-3 and 5-25 ppb NO2) concentrations and aerosol composition (inorganic and organic coating) were varied while remaining close to ambient conditions, producing similar AN and SOA yields under all regimes. We observe the formation of dinitrates upon oxidation of the second double bond only once the isoprene precursor is fully consumed. We determine the bulk partitioning coefficient for ANs (K-p similar to 10(-3) m(3) mu g(-1)), indicating an average volatility corresponding to a C-5 hydroxy hydroperoxy nitrate.
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- Carlsson, P. T. M., et al.
(författare)
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Comparison of isoprene chemical mechanisms under atmospheric night-time conditions in chamber experiments: evidence of hydroperoxy aldehydes and epoxy products from NO3 oxidation
- 2023
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 23:5, s. 3147-3180
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Tidskriftsartikel (refereegranskat)abstract
- The gas-phase reaction of isoprene with the nitrate radical (NO3) was investigated in experiments in the outdoor SAPHIR chamber under atmospherically relevant conditions specifically with respect to the chemical lifetime and fate of nitrato-organic peroxy radicals (RO2). Observations of organic products were compared to concentrations expected from different chemical mechanisms: (1) the Master Chemical Mechanism, which simplifies the NO3 isoprene chemistry by only considering one RO2 isomer; (2) the chemical mechanism derived from experiments in the Caltech chamber, which considers different RO2 isomers; and (3) the FZJ-NO3 isoprene mechanism derived from quantum chemical calculations, which in addition to the Caltech mechanism includes equilibrium reactions of RO(2 )isomers, unimolecular reactions of nitrate RO(2 )radicals and epoxidation reactions of nitrate alkoxy radicals. Measurements using mass spectrometer instruments give evidence that the new reactions pathways predicted by quantum chemical calculations play a role in the NO3 oxidation of isoprene. Hydroperoxy aldehyde (HPALD) species, which are specific to unimolecular reactions of nitrate RO2, were detected even in the presence of an OH scavenger, excluding the possibility that concurrent oxidation by hydroxyl radicals (OH) is responsible for their formation. In addition, ion signals at masses that can be attributed to epoxy compounds, which are specific to the epoxidation reaction of nitrate alkoxy radicals, were detected. Measurements of methyl vinyl ketone (MVK) and methacrolein (MACR) concentrations confirm that the decomposition of nitrate alkoxy radicals implemented in the Caltech mechanism cannot compete with the ring-closure reactions predicted by quantum chemical calculations. The validity of the FZJ-NO3 isoprene mechanism is further supported by a good agreement between measured and simulated hydroxyl radical (OH) reactivity. Nevertheless, the FZJ-NO3 isoprene mechanism needs further investigations with respect to the absolute importance of unimolecular reactions of nitrate RO2 and epoxidation reactions of nitrate alkoxy radicals. Absolute concentrations of specific organic nitrates such as nitrate hydroperoxides would be required to experimentally determine product yields and branching ratios of reactions but could not be measured in the chamber experiments due to the lack of calibration standards for these compounds. The temporal evolution of mass traces attributed to product species such as nitrate hydroperoxides, nitrate carbonyl and nitrate alcohols as well as hydroperoxy aldehydes observed by the mass spectrometer instruments demonstrates that further oxidation by the nitrate radical and ozone at atmospheric concentrations is small on the timescale of one night (12 h) for typical oxidant concentrations. However, oxidation by hydroxyl radicals present at night and potentially also produced from the decomposition of nitrate alkoxy radicals can contribute to their nocturnal chemical loss.
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- Salvador, Christian Mark, 1989, et al.
(författare)
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Ambient nitro-aromatic compounds - biomass burning versus secondary formation in rural China
- 2021
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 21:3, s. 1389-1406
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Tidskriftsartikel (refereegranskat)abstract
- Nitro-aromatic compounds (NACs) were measured hourly at a rural site in China during wintertime to monitor the changes due to local and regional impacts of biomass burning (BB). Concurrent and continuous measurements of the concentrations of 16 NACs in the gas and particle phases were performed with a time-of-flight chemical ionization mass spectrometer (CIMS) equipped with a Filter Inlet for Gases and AEROsols (FIGAERO) unit using iodide as the reagent ion. NACs accounted for <2 % of the mass concentration of organic matter (OM) and total particulate matter (PM), but the total particle mass concentrations of these compounds can reach as high as 1000 ng m(-3) (299 ng m(-3) avg), suggesting that they may contribute significantly to the radiative forcing effects of atmospheric particles. Levels of gas-phase NACs were highest during the daytime (15:00-16:00 local time, LT), with a smaller night-time peak around 20:00LT. Box-model simulations showed that this occurred because the rate of NAC production from gas-phase sources exceeded the rate of loss, which occurred mainly via the OH reaction and to a lesser degree via photolysis. Data gathered during extended periods with high contributions from primary BB sources (resulting in 40 %-60 % increases in NAC concentrations) were used to characterize individual NACs with respect to gas-particle partitioning and the contributions of regional secondary processes (i.e. photochemical smog). On days without extensive BB, secondary formation was the dominant source of NACs, and NAC levels correlated strongly with the ambient ozone concentration. Analyses of individual NACs in the regionally aged plumes sampled on these days allowed precursors such as phenol and catechol to be linked to their NAC derivatives (i.e. nitrophenol and nitrocatechol). Correlation analysis using the high time resolution data and box-model simulation results constrained the relationships between these compounds and demonstrated the contribution of secondary formation processes. Furthermore, 13 of 16 NACS were classified according to primary or secondary formation process. Primary emission was the dominant source (accounting for 60 %-70 % of the measured concentrations) of 5 of the 16 studied NACs, but secondary formation was also a significant source. Photochemical smog thus has important effects on brown carbon levels even during wintertime periods dominated by primary air pollution in rural China.
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