A comparison of isoprene nitrate concentrations at two forest‐impacted sites

Grossenbacher, John W.

doi:10.1029/2003jd003966

Cited by 35 publications

(52 citation statements)

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“…Ballschmitter and coworkers measured these compounds by chromatographic methods in remote areas (e.g., marine environments) where there were only very small concentrations (Fischer et al, 2000;Werner et al, 1999). Shepson and coworkers reported diurnal patterns for these compounds in forested regions in Michigan and Tennessee (Giacopelli et al, 2005;Grossenbacher et al, 2001Grossenbacher et al, , 2004 but focused mainly on the photochemical production from reactions of isoprene peroxy radicals with NO. For the P-3 flights during NEAQS 2004, there were no specific measurements of isoprene nitrates.…”

Section: Reactive Nitrogen Partitioningmentioning

confidence: 99%

Nocturnal isoprene oxidation over the Northeast United States in summer and its impact on reactive nitrogen partitioning and secondary organic aerosol

et al. 2009

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Abstract. Isoprene is the largest single VOC emission to the atmosphere. Although it is primarily oxidized photochemically during daylight hours, late-day emissions that remain in the atmosphere at sunset undergo oxidation by NO 3 in regionally polluted areas with large NO x levels. A recent aircraft study examined isoprene and its nocturnal oxidants in a series of night flights across the Northeast US, a region with large emissions of both isoprene and NO x . Substantial amounts of isoprene that were observed after dark were strongly anticorrelated with measured NO 3 and were the most important factor determining the lifetime of this radical. The products of photochemical oxidation of isoprene, methyl vinyl ketone and methacrolein, were more uniformly distributed, and served as tracers for the presence of isoprene at sunset, prior to its oxidation by NO 3 . A determination of the mass of isoprene oxidized in darkness showed it to be a large fraction (>20%) of emitted isoprene. Organic nitrates produced from the NO 3 +isoprene reaction, though not directly measured, were estimated to account for 2-9% of total reactive nitrogen. The mass of isoprene oxidized by NO 3 was comparable to and correlated with the organic aerosol Correspondence to: S. S. Brown (steven.s.brown@noaa.gov) loading for flights with relatively low organic aerosol background. The contribution of nocturnal isoprene oxidation to secondary organic aerosol was determined in the range 1-17%, and isoprene SOA mass derived from NO 3 was calculated to exceed that due to OH by approximately 50%.

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Section: Reactive Nitrogen Partitioningmentioning

confidence: 99%

Nocturnal isoprene oxidation over the Northeast United States in summer and its impact on reactive nitrogen partitioning and secondary organic aerosol

et al. 2009

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“…[14] The measured concentration of isoprene nitrates reached ,90 pptv in a forest site at Pellston, Michigan, [15] and as high as 150 pptv in rural Tennessee. [16] ANs were also detected in the lower stratosphere by the NASA ER-2 aircraft, covering a latitude range of 608N to 28S, 1158W to 1558W and altitudes to 20.5 km. [17] Methyl and ethyl nitrate account for ,20-40 % of the total light ANs.…”

Section: Introductionmentioning

confidence: 99%

“…This is in agreement with the recent report for a NO 2 quantum yield of unity from photodissociation of methyl and isopropyl nitrate. [58] In the presence of O 2 , the H and HCO radicals formed from reactions 11 and 13b, will rapidly react with O 2 , resulting in the formation of HO 2 , H 2 O 2 and OH (reactions [16][17][18], and the oxidisation of NO 2 into HNO 3 (reaction 20) and HO 2 NO 2 (reaction 21). HC(O)O 2 was reported to be the intermediate product in the HCO þ O 2 reaction, and it can decompose rapidly to CO and HO 2 because of its instability (reactions 19).…”

Section: Reaction Mechanisms Based On Observed Products Photolysis Mementioning

confidence: 99%

Photochemical reactions of methyl and ethyl nitrate: a dual role for alkyl nitrates in the nitrogen cycle

Chen

Zhang

2011

Environ. Chem.

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Environmental context. Alkyl nitrates are considered to be important intermediates in the atmospheric hydrocarbons-nitrogen oxides-ozone cycle, which significantly determines air quality and nitrogen exchange between the atmosphere and the Earth's surfaces. The present laboratory study investigates reaction products of alkyl nitrates to elucidate their photochemical reaction mechanisms in the atmosphere. The results provide a better understanding of the role played by alkyl nitrates in the atmospheric environment.Abstract. Alkyl nitrates (ANs) are important nitrogen-containing organic compounds and are usually considered to be temporary reservoirs of reactive nitrogen NO x (NO 2 and NO) in the atmosphere, although their atmospheric fates are incompletely understood. Here a laboratory study of the gas-phase photolysis and OH-initiated reactions of methyl nitrate (CH 3 ONO 2 ) and ethyl nitrate (C 2 H 5 ONO 2 ), as models of atmospheric ANs, is reported with a focus on elucidating the detailed photochemical reaction mechanisms of ANs in the atmosphere. A series of intermediate and end products were well characterised for the first time from the photochemical reactions of methyl and ethyl nitrate conducted under simulated atmospheric conditions. Notably, for both the photolysis and OH-initiated reactions of CH 3 ONO 2 and C 2 H 5 ONO 2 , unexpectedly high yields of HNO 3 (photochemically non-reactive nitrogen) were found and also unexpectedly high yields of peroxyacyl nitrates (RC(O)OONO 2 , where R ¼ H, CH 3 , CH 3 CH 2 ,y) (reactive nitrogen) have been found as CH 3 C(O)OONO 2 in the C 2 H 5 ONO 2 reaction or proposed as HC(O)OONO 2 in the CH 3 ONO 2 reaction. Although the yields of HNO 3 from the ANs under ambient conditions are likely variable and different from those obtained in the laboratory experiments reported here, the results imply that the ANs could potentially serve as a sink for reactive nitrogen in the atmosphere. The potential for this dual role of organic nitrates in the nitrogen cycle should be considered in the study of air quality and nitrogen exchange between the atmosphere and surface. Finally, an attempt was made to estimate the production of HNO 3 and peroxyacyl nitrates derived from NO x by ANs as intermediates in the atmosphere.

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“…Ambient measurements of specific individual RONO 2 have, with few exceptions (Fischer et al, 2000;Grossenbacher et al, 2001Grossenbacher et al, , 2004, been limited to simple alkyl nitrates. As a result of the development of thermal dissociation laser induced fluorescence (TD-LIF) by Day et al (2002), measurement of total alkyl-nitrates ( ANs) as a class has become routine.…”

Section: R Beaver Et Al: Organic Nitrates From Biogenic Vocsmentioning

confidence: 99%

“…Ambient measurements of isoprene nitrates are rare, but have been conducted over two forested locations in Michigan and Tennessee using gas chromatography followed by pyrolytic conversion to and subsequent detection of NO 2 (Grossenbacher et al, 2004(Grossenbacher et al, , 2001). This technique speciates the isomers of the isoprene nitrates, in contrast to the measurement made here which is the sum of the isomers.…”

Section: Suite Of Organic Nitrates Observedmentioning

confidence: 99%

Importance of biogenic precursors to the budget of organic nitrates: observations of multifunctional organic nitrates by CIMS and TD-LIF during BEARPEX 2009

et al. 2012

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Abstract. Alkyl and multifunctional organic nitrates, molecules of the chemical form RONO 2 , are products of chain terminating reactions in the tropospheric HO x and NO x catalytic cycles and thereby impact ozone formation locally. Many of the molecules in the class have lifetimes that are long enough that they can be transported over large distances. If the RONO 2 then decompose to deliver NO x to remote regions they affect ozone production rates in locations distant from the original NO x source. While measurements of total RONO 2 ( ANs) and small straight chain alkyl nitrates are routine, measurements of the specific multifunctional RONO 2 molecules that are believed to dominate the total have rarely been reported and never reported in coincidence with ambient ANs measurements. Here we describe observations obtained during the BEARPEX 2009 experiment including ANs and a suite of multifunctional nitrates including isoprene derived hydroxynitrates, oxidation products of those nitrates, 2-methyl-3-buten-2-ol (MBO) derived hydroxynitrates, and monoterpene nitrates. At the BEARPEX field site, the sum of the individual biogenically derived nitrates account for two-thirds of the ANs, confirming predictions of the importance of biogenic nitrates to the NO y budget. Isoprene derived nitrates, transported to the site, are a much larger fraction of the ANs at the site than the nitrates derived from the locally emitted MBO. Evidence for additional nitrates, possibly from nocturnal chemistry of isoprene and α-pinene, is presented.

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A comparison of isoprene nitrate concentrations at two forest‐impacted sites

Cited by 35 publications

References 35 publications

Nocturnal isoprene oxidation over the Northeast United States in summer and its impact on reactive nitrogen partitioning and secondary organic aerosol

Nocturnal isoprene oxidation over the Northeast United States in summer and its impact on reactive nitrogen partitioning and secondary organic aerosol

Photochemical reactions of methyl and ethyl nitrate: a dual role for alkyl nitrates in the nitrogen cycle

Importance of biogenic precursors to the budget of organic nitrates: observations of multifunctional organic nitrates by CIMS and TD-LIF during BEARPEX 2009

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