Measuring Biogenic Volatile Organic Compounds (BVOCs) from Vegetation in Terms of Ozone Reactivity

Matsumoto, Jun

doi:10.4209/aaqr.2012.10.0275

Cited by 17 publications

(29 citation statements)

References 27 publications

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“…While the reactivity of NO 3 has never been directly measured (e.g. Brown et al, 2011, and references therein), some recent studies have addressed O 3 reactivity (Park et al, 2013;Matsumoto, 2014). So far no one has modelled the reactivity of either O 3 or NO 3 .…”

Section: Introductionmentioning

confidence: 99%

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Simulations of atmospheric OH, O3 and NO3 reactivities within and above the boreal forest

et al. 2015

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Abstract. Using the 1-D atmospheric chemistry transport model SOSAA, we have investigated the atmospheric reactivity of a boreal forest ecosystem during the HUMPPA-COPEC-10 campaign (summer 2010, at SMEAR II in southern Finland). For the very first time, we present vertically resolved model simulations of the NO 3 and O 3 reactivity (R) together with the modelled and measured reactivity of OH. We find that OH is the most reactive oxidant (R ∼ 3 s −1 ) followed by NO 3 (R ∼ 0.07 s −1 ) and O 3 (R ∼ 2 × 10 −5 s −1 ). The missing OH reactivity was found to be large in accordance with measurements (∼ 65 %) as would be expected from the chemical subset described in the model. The accounted OH radical sinks were inorganic compounds (∼ 41 %, mainly due to reaction with CO), emitted monoterpenes (∼ 14 %) and oxidised biogenic volatile organic compounds (∼ 44 %). The missing reactivity is expected to be due to unknown biogenic volatile organic compounds and their photoproducts, indicating that the true main sink of OH is not expected to be inorganic compounds. The NO 3 radical was found to react mainly with primary emitted monoterpenes (∼ 60 %) and inorganic compounds (∼ 37 %, including NO 2 ). NO 2 is, however, only a temporary sink of NO 3 under the conditions of the campaign (with typical temperatures of 20-25 • C) and does not affect the NO 3 concentration. We discuss the difference between instantaneous and steadystate reactivity and present the first boreal forest steady-state lifetime of NO 3 (113 s). O 3 almost exclusively reacts with inorganic compounds (∼ 91 %, mainly NO, but also NO 2 during night) and less with primary emitted sesquiterpenes (∼ 6 %) and monoterpenes (∼ 3 %). When considering the concentration of the oxidants investigated, we find that OH is the oxidant that is capable of removing organic compounds at a faster rate during daytime, whereas NO 3 can remove organic molecules at a faster rate during night-time. O 3 competes with OH and NO 3 during a short period of time in the early morning (around 5 a.m. local time) and in the evening (around 7-8 p.m.). As part of this study, we developed a simple empirical parameterisation for conversion of measured spectral irradiance into actinic flux. Further, the meteorological conditions were evaluated using radiosonde observations and ground-based measurements. The overall vertical structure of the boundary layer is discussed, together with validation of the surface energy balance and turbulent fluxes. The sensible heat and momentum fluxes above the canopy were on average overestimated, while the latent heat flux was underestimated.

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Section: Introductionmentioning

confidence: 99%

“…Rannik et al, 2012;Wolfe et al, 2011). Until now there has been only one publication about direct measurements of O 3 reactivity, in which the author measured the reactivity in the lab (Matsumoto, 2014). Unfortunately, the detection limit of that instrument is so high that ambient measurements are impossible.…”

Section: Relative Oxidative Strengthmentioning

confidence: 99%

Simulations of atmospheric OH, O3 and NO3 reactivities within and above the boreal forest

et al. 2015

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“…Volatile Organic Compounds (VOCs) released into the air through various sources have been widely studied in the recent years (Chang et al, 2013;Matsumoto, 2014;Pervez et al, 2014). VOCs in the environment might cause adverse effects on human health (Hwang et al, 2011).…”

Section: Introductionmentioning

confidence: 99%

Sorption of Volatile Organic Compounds on Organic Substance-Modified Titanate Nanotubes

Wang

Peng

Chao

2015

Aerosol Air Qual. Res.

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This study investigates the removal of volatile organic compounds (VOCs) from the air through the use of organic substance-modified titanate nanotubes (TNTs). The TNTs were derived from TiO 2 through a hydrothermal method, and were modified using hexadecyltrimethylammonium bromide and octadecyltrichlorosilane (OTS) to change the surface hydrophilicity to hydrophobicity. The properties of the TNT and modified TNT were characterized through scanning electron microscopy , transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, contact angle measurements, and nitrogen adsorption-desorption isotherms. The fabricated adsorbents were used to remove the VOCs of toluene, ethylbenzene 1,1,2-trichloroethane, and tetrachloroethene in the air. The adsorption amounts of the VOCs were estimated using the Thomas equation. The results revealed that adsorbent modification raised the adsorption capacities of these VOCs, which also grew with increasing surface hydrophobicity. The aromatic compounds accumulated easily in the pores to generate relatively high adsorption amounts. VOCs adsorbed on the TNT surface or partitioned into the organic substance on TNTs. The adsorption amounts of VOCs on the OTSmodified TNTs were higher than those on commercial activated carbon. The results imply that organic substance-modified TNTs can effectively remove VOCs in the air and become excellent adsorbents.

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“…where¸R is the reaction time in the reactor, k is the reaction rate coefficient of VOC 14,15 From the natural logarithm of eq 1, the relationship as follows can be acquired:…”

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confidence: 99%

“…11 Cyclohexane was added to the sample as a scavenger of OH radical, which can be formed secondarily in the reactor. 11,13,15,16 The O 3 flow was mixed with the sample in the reactor. In this study, following settings of flow rates were adopted: total flow rate at reactor F = 1.2 © 10 3 sccm (standard cubic centimeter per minute at 293 K), which composed of 10 sccm from ozone supply, 50 sccm of scavenger, and 1.1 © 10 3 sccm of the VOC sample.…”

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confidence: 99%

Temperature Dependence of Rate Constant for the Gas-phase Reaction of Ozone with Linalool

Matsumoto¹

2016

Chem. Lett.

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To determine the reaction rate coefficient of volatile organic compounds (VOCs) with ozone, the reduction of ozone through a flow-tube reactor was measured by a sensitive chemiluminescent detector. In this study, temperature dependence of the rate constant of ozone with linalool, k(T) = A exp(¹B/T), was explored (T = 299322 K). Consequently, temperature-dependent parameters A and B were experimentally determined as (1.6 « 0.4) © 10 ¹15 cm 3 molecule ¹1 s ¹1 and 396 « 26 K, respectively, for the first time. The rate constant of linalool + O 3 reaction varied by 10% with changes in temperatures from 299 to 322 K. Keywords: Volatile organic compound | Linalool | OzonolysisVolatile organic compounds (VOCs) have been a focus as critical precursors of photochemical oxidants and secondary organic aerosols (SOAs).1,2 VOCs are emitted into the atmosphere from biogenic sources such as vegetation and plants, as well as from anthropogenic sources. It has been estimated that the annual global VOC flux is 1150 TgC, consisting of 44% isoprene and 11% monoterpenes, both of which are representative biogenic VOCs (BVOCs).3 To investigate the impact of BVOCs on air quality and pollution, atmospheric BVOCs have been one of the most discussed topics in atmospheric chemistry in recent decades. Initial reactions of VOCs with atmospheric radicals are important to capture both the atmospheric degradation of VOCs and production of oxidants and SOAs. For some VOCs like alkenes, reactions with ozone (O 3 ) are significant. It is known that the first step of ozonolysis of alkenes is the addition of O 3 to the C=C double bonds.1 Many BVOCs have C=C double bonds and their reactions with O 3 are important.To discuss the fate of BVOCs and the secondary products in the atmosphere, reactions with O 3 should be explored. However, there are various BVOCs whose reaction coefficients are still not reported at present. In particular, temperature dependence of reaction coefficients should be explored further in order to capture the variation and distribution of BVOCs with season, latitude, and altitude in the atmosphere.Linalool, (CH 3 ) 2 C=CHCH 2 CH 2 C(OH)(CH 3 )CH=CH 2 , is a monoterpene alcohol, which is one of the compositions of various plants. Previous studies reported on the emission of linalool from vegetation to the atmosphere. 47 It is also known that linalool is utilized in indoor environment as an aromatherapy essential oil.8 It is important to study the fate of linalool in the atmosphere and/or indoor air. Linalool has two C=C double bonds in the molecule and its reaction with ozone can be important. In this decade, SOA formation by linalool + O 3 has been studied experimentally utilizing reaction chambers.9,10 As for the kinetics of the reaction of linalool with ozone, some studies reported the reaction rate coefficient, k, around 298 K. 1113Temperature dependence of the reaction coefficient, k(T), of O 3 with linalool has not been understood sufficiently yet to the best of our knowledge. Grosjean and Grosjean 12 tried to measure k at ...

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Measuring Biogenic Volatile Organic Compounds (BVOCs) from Vegetation in Terms of Ozone Reactivity

Cited by 17 publications

References 27 publications

Simulations of atmospheric OH, O<sub>3</sub> and NO<sub>3</sub> reactivities within and above the boreal forest

Simulations of atmospheric OH, O<sub>3</sub> and NO<sub>3</sub> reactivities within and above the boreal forest

Sorption of Volatile Organic Compounds on Organic Substance-Modified Titanate Nanotubes

Temperature Dependence of Rate Constant for the Gas-phase Reaction of Ozone with Linalool

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Measuring Biogenic Volatile Organic Compounds (BVOCs) from Vegetation in Terms of Ozone Reactivity

Cited by 17 publications

References 27 publications

Simulations of atmospheric OH, O&lt;sub&gt;3&lt;/sub&gt; and NO&lt;sub&gt;3&lt;/sub&gt; reactivities within and above the boreal forest

Simulations of atmospheric OH, O&lt;sub&gt;3&lt;/sub&gt; and NO&lt;sub&gt;3&lt;/sub&gt; reactivities within and above the boreal forest

Sorption of Volatile Organic Compounds on Organic Substance-Modified Titanate Nanotubes

Temperature Dependence of Rate Constant for the Gas-phase Reaction of Ozone with Linalool

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Product

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Simulations of atmospheric OH, O<sub>3</sub> and NO<sub>3</sub> reactivities within and above the boreal forest

Simulations of atmospheric OH, O<sub>3</sub> and NO<sub>3</sub> reactivities within and above the boreal forest