A Mellouki

T J Wallington

J Chen

Hoch

HC(O)C(O)H, CH Cho

Ch

Atmospheric Chemistry of Oxygenated Volatile Organic Compounds (OVOCs): Impacts on Air Quality and Climate

Introduction

It is hard to overstate the importance of oxygenated organic compounds in atmospheric chemistry. Oxygenated organic compounds are emitted into the atmosphere from natural and man-made sources and they are formed in the atmosphere as oxidation products of all hydrocarbons present in the atmosphere. Oxygenated volatile organic compounds (OVOCs) are generally more reactive than the alkanes from which they are derived. OVOCs play an active role in the sequence of chemical reactions responsible for tropospheric ozone formation in both polluted and remote environments. The HO-radical initiated oxidation of CH 3 OH, the most abundant OVOC in the atmosphere, can be represented in simple terms by: HO + CH 3 transported from the stratosphere. [1][2] Ozone plays a pivotal role in atmospheric chemistry and is also an important greenhouse gas. IR absorption by ozone is responsible for approximately 10%

of the natural greenhouse effect by the radiatively active species H 2 O, CO 2 , O 3 , CH 4 , and N 2 O. 3 Historical measurements of ambient ozone levels and modeling studies suggest that as a result of human activities there has been a significant increase in the global tropospheric ozone concentration. The total radiative forcing estimated from increased tropospheric ozone since 1750 is approximately 0.40 W m -2 . [START_REF]Climate change 2013: The physical science basis[END_REF] In terms of radiative forcing of climate change as a result of human activities since 1750, changes in ozone account for approximately 17% of the total anthropogenic radiative forcing of 2.29 W m -2 . [START_REF]Climate change 2013: The physical science basis[END_REF] The ozonolysis of biogenic VOCs such as isoprene and monoterpenes gives multifunctional oxygenated organic compounds with low vapor pressures. These products partition into the aerosol phase leading to the formation of secondary organic aerosols.

Secondary organic aerosol formation during the atmospheric oxidation of biogenic organic compounds is estimated at 20-380 Tg yr -1 globally. [START_REF]Climate change 2013: The physical science basis[END_REF] It is well established that aerosols have a substantial influence on climate, however the magnitude of the effect of secondary organic aerosols on climate is unclear [START_REF]Climate change 2013: The physical science basis[END_REF] and is not addressed further in the present review.

The atmospheric degradation processes of different classes of OVOCs is summarized in the next sections. The focus is on experimental, gas phase laboratory based data, which have improved our understanding of the atmospheric chemistry of OVOCs. We start with an overview of the sources and representative atmospheric concentrations of OVOCs in Section 2. This is followed by an overview of their general atmospheric chemistry in Section 3. The rate constants for the reactions of the main atmospheric oxidants used to derive the atmospheric lifetimes of the OVOCs and the oxidation routes and products are given in Section 4. We discuss the contribution of OVOCs to ozone formation in the atmosphere based on the concept of photochemical ozone creation potential in Section 5. [START_REF] Derwent | [END_REF][START_REF] Jenkin | Photochemical ozone and PAN creation potentials: rationalisation and methods of estimation[END_REF] The radiative efficiencies and global warming potentials of OVOCs is discussed in Section 6. Our intent is to provide an overview of the atmospheric chemistry of OVOCs and their impacts on air quality and climate. For more detailed information concerning the gas-phase reactivity of OVOCs in the atmosphere, the reader is directed to recent comprehensive reviews [START_REF] Atkinson | [END_REF][START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF][START_REF] Mellouki | [END_REF] and references therein.

Oxygenated VOCs in the atmosphere

OVOCs enter the atmosphere by four routes: (i) atmospheric oxidation of hydrocarbons, (ii) emissions from biological sources such as growing plants, plant debris, and biomass burning, (iii) evaporation of oxygenated solvents or fuels used in industrial processes, commercial operations, or consumer products, and (iv) incomplete combustion in hydrocarbon-fueled mobile or stationary sources.

On a global basis, by far the most important source of OVOCs is the oxidation of hydrocarbons present in the atmosphere. , allowing for a small increase in the atmospheric burden of (14 Tg yr -1 ), the balance of 542 Tg yr -1 is oxidized and provides a large flux of HCHO, CH 3 OH, and CH 3 OOH into the atmosphere. [START_REF]Climate change 2013: The physical science basis[END_REF] Isoprene (2-methyl-1,3-butadiene) is emitted by plants in amounts comparable to the emissions of CH 4 . The global biogenic emission of isoprene in 2000 is estimated to be 535

Tg yr -1 . 12 Under high NO x conditions where peroxy radical reactivity is dominated by reaction with NO, the HO initiated oxidation of isoprene gives methyl vinyl ketone and methacrolein as the major stable products. [START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF] Under low-NO x conditions isomerization reactions can become important for the peroxy radicals produced from isoprene and a broad variety of oxygenated organic products become important. [13][14][15] CH 4 and isoprene are by far the highest volume HC emissions into the global atmosphere. In contrast to the approximately 535 Tg yr -1 biogenic emission of isoprene, the combined global anthropogenic emission of all non-methane VOCs (NMVOCs) is approximately 200 Tg yr -1 . [START_REF]Climate change 2013: The physical science basis[END_REF] Plants are major emitters of both VOCs and OVOCs. 12,16 Table 2 gives estimates for the top 15 biogenic emissions. 12 As seen from Table 2, methanol, acetone, ethanol, and acetaldehyde are emitted in large amounts. Methanol is the largest biogenic OVOC emission at approximately 100 Tg yr -1 . For perspective the global industrial production of methanol in 2012 was 65 Tg 17 and emissions from industrial sources are a small fraction of production. Methanol and acetone are by-products and acetaldehyde is an intermediate of plant metabolism and escape into the atmosphere 16 from plant leaves and stems. In conditions where there is insufficient oxygen (e.g., when roots are flooded), plants maintain energy production by switching from aerobic respiration to fermentation [18][19] . Fermentation produces ethanol, much of which is metabolized within the plant, but some escapes into the atmosphere. [20][21] 2.2 Anthropogenic OVOC emissions

Oxygenates are used extensively as fuels, fuel additives, solvents, and feedstocks for the chemical industry. The use of oxygenates in blends with gasoline serves three main purposes.

First, oxygenates such as ethanol, ethyl tert-butyl ether (ETBE), methyl tert-butyl ether (MTBE), and tert-amyl methyl ether (TAME), improve the antiknock quality (increase octane number) of fuel by resisting autoignition. Following the removal of tetraethyl lead from gasoline in the late 1970s, oxygenates such as MTBE found widespread use as blending components to boost the octane number of gasoline. Concerns regarding ground water contamination lead to the phase out of MTBE use in the U.S. in the 2000s. Second, by physically displacing or diluting some of the fuel components (e.g., aromatics), the presence of oxygenates helps to reduce certain harmful tailpipe emissions (e.g., benzene). Third, oxygenates derived from renewable sources such as ethanol from corn, sugar cane, and cellulose and fatty acid methyl esters from animal fats and vegetable oils displace petroleum and can improve energy security and reduce greenhouse gas emissions. As seen from Figures 1 and2 there has been a large increase in the use of ethanol in fuel in the U.S. and globally over the past 10-15 years. [START_REF]Annual Energy Review 2011[END_REF] Annual global ethanol fuel production is currently approximately 85 billion liters (67 Tg). Ethanol is also produced in large quantities for consumption in alcoholic beverages. Global beer production is approximately 1.9 x 10 11 liters 23 and wine production is approximately 2.7 × 10 10 liters. 24 Making the assumption that beer and wine have ethanol contents of 5% and 12%, respectively, gives an estimate of 13 billion liters (10 Tg) of ethanol production in the beverage industry. Approximately 9 Tg yr -1 of ethanol is used in commercial and industrial solvents. [START_REF] Kirstine | [END_REF] The anthropogenic emissions of ethanol are estimated to be approximately 6 Tg yr -1 and are dominated by emissions associated with use in commercial and industrial solvents. Global ethanol transportation fuel use [START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF][START_REF]Department-of-Energy; Alternative-Fuels-Data-Center[END_REF] Methanol is used as an additive to gasoline. Dimethyl ether is used as a diesel fuel. As illustrated in Figures 3 and4, methanol and dimethyl ether are finding increased use as transportation fuels, however the absolute use of these fuels is still small compared to the approximately 8 × 10 10 liters of ethanol and very small compared to the approximately 3 × 10 12 liters of petroleum derived fuel used annually in global transportation. The increasing ethanol content in gasoline has led to interest in the impact of ethanol on vehicle emissions. The single largest VOC emission from engines is unburned fuel. Modern internal combustion engines combust approximately 97-99% of the fuel to CO 2 and H 2 O leaving approximately 1-3% unburned or partial burned fuel in the engine-out exhaust. [START_REF] Wallington | [END_REF] Vehicles are equipped with emission control systems which remove approximately 95-99% of the organic compounds in the exhaust. Figure 5 shows a plot of emissions versus fuel ethanol content for by two different factors: fuel chemistry and engine calibration. 32 As the ethanol content increases fuel chemistry considerations dictate that the emissions of ethanol and its oxidation products (e.g., acetaldehyde) will increase and emissions of gasoline components (e.g., benzene, aromatics) will decrease. Fuel chemistry effects are fundamental in nature; the same trend of increased ethanol, acetaldehyde, formaldehyde, and CH 4 emissions (formed by decomposition of CH 3 CHO into CH 4 and CO by Rh catalysts 32 ) and decreased non-methane hydrocarbons (NMHC) and benzene emissions are expected for all FFVs. Engine calibration effects refer to how the operation of the engine is modified as the vehicle senses changes in ethanol content of the fuel. Engine calibration determines how emission trends for NO x and total hydrocarbons depend on the ethanol fuel content. Engine calibration are manufacturer and model specific and trends of NO x and total hydrocarbons emissions will not be the same for all FFVs. 32

Figure 5.

Federal test procedure cycle-weighted tailpipe emissions of total hydrocarbons (THC), methane, ethanol, NO x , acetaldehyde, and formaldehyde versus fuel ethanol concentration. 32

Background OVOC atmospheric concentrations

Figure 6 shows the observed distribution of OVOCs in the remote Pacific troposphere. 33 It is well established that OVOCs are important trace species in the global atmosphere. [33][34][35] Methanol is the most abundant OVOC in the atmosphere followed either by CH

S. Hemisphere

In the atmosphere, oxygenated volatile organic compounds from both anthropogenic and biogenic sources undergo various chemical and physical processes leading to their transformation or removal from the atmosphere. Removal of OVOCs occurs through photolysis and by wet and/or dry deposition. Most OVOCs have low Henry's law constants, below 10 3 M atm -1 , [START_REF] Sander | Compilation of Henry's law constants for inorganic and organic species of potential importance in environmental chemistry (Version 3)[END_REF] indicating that they will partition into the gas phase. [START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF] For example, ketones, aldehydes others than formaldehyde, esters and ethers are relatively insoluble in water while alcohols have some solubility especially those with short aliphatic chains. Incorporation into water for the nonsoluble OVOCs will not be of importance in the atmosphere. The highly oxidised OVOCs such as polyols are extremely water soluble, and wet and dry deposition are important for these species. Wet and dry deposition are important loss mechanisms for the smaller carboxylic acids in the troposphere.

The OVOCs have lower vapor pressures than the corresponding alkanes. For compounds with the same number of carbon atoms, the general trend in vapor pressures is alkanes > ethers > aldehydes  esters > alcohols > carboxylic acids. For molecules with a given number of carbons, the vapor pressure decreases dramatically with addition of oxygen atoms and increasing oxidation of the molecule as illustrated in Figure 7. [START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF] Low volatility multifunctional oxygenated organic compounds condense onto existing atmospheric particles and hence increase the organic fraction content of secondary organic aerosols. The contribution of OVOC oxidation to SOA formation is of interest with respect to its potential impacts on air quality, human health, and climate. The majority of OVOCs are oxidised in the atmosphere through chemical reactions in the gas phase [START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF][START_REF] Mellouki | [END_REF] . The degradation of saturated oxygenated volatile organic compounds is largely initiated by their reaction with hydroxyl radicals (OH). In addition, photolysis of carbonyls such as aldehydes and ketones can also play a significant role in their atmospheric degradation. The oxidation of unsaturated oxygenated compounds may be initiated by reaction with ozone, nitrate (NO 3 ) and hydroxyl radicals. The kinetics and mechanisms for these reactions have been comprehensively reviewed [START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF][START_REF] Mellouki | [END_REF] . OH radicals are formed following the photolysis of ozone and hence their concentration is significant during the day, but very low at night. In contrast, NO 3 radicals are photolyzed rapidly so their concentration during the day is very low, but can be significant at night. OH radical initiated oxidation of OVOCs is important during the day while NO 3 radical initiated oxidation can be important at night and depends on the reactivity of the OVOC towards NO 3 radicals and the local conditions. Chlorine atoms react rapidly with OVOCs 8,37 however the concentration of chlorine atoms in the troposphere is generally very low and hence reaction with chlorine atoms is not a major fate of OVOCs. The degradation of OVOCs in the troposphere leads to the production of a large range of secondary pollutants such as ozone, highly oxidised VOCs (HOVOCs), peroxyacyl nitrates, and secondary organic aerosols (SOA). Hence, the oxygenated compounds play an important role in determining the oxidizing capacity of the troposphere both on a regional and a global scale. Ozone is a greenhouse gas and at high concentrations it is known to have adverse effects on human health and ecosystems.

Understanding the contribution of various OVOCs to ozone formation is of particular interest.

Indeed, the control strategies of the OVOCs emissions into the atmosphere are mostly based on their individual contribution to photochemical ozone formation. 38 In addition to local air quality issues it is important to consider the potential direct and

Kinetics and Mechanisms of atmospheric degradation of OVOCs

Alcohols

Alcohols are an important class of oxygenated volatile organic compounds; their presence in ambient air is due to both natural and anthropogenic sources. They are emitted by grassland and agricultural vegetation and have long been used as industrial solvents and motor vehicle fuels and fuel additives.

Aliphatic alcohols, diols, cyclic and aromatic alcohols: In the atmosphere, aliphatic alcohols are mostly oxidised through their reaction with OH and NO 3 radicals, with the OH radical reaction being the dominant. Reactions with O 3 and photolysis are negligible loss processes. The smaller alcohols are highly water soluble but are also highly volatile and tend to partition into the gasphase. The Henry's law constants values for methanol and ethanol are 220 and 200 M atm -1 , respectively. [39][40] Dry and wet deposition contributes significantly the removal of these smaller alcohols from the atmosphere. For methanol it has been estimated that dry and wet deposition account for about 30% and 7% of its atmospheric removal. The rate constants at 298 K for reactions of OH with linear straight-chain alcohols increase with the alkyl chain length from 0.910 -12 for methanol to 1.310 -11 cm 3 molecule -1 s -1 for n-octanol. [START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF][START_REF] Calvert | The mechanisms of atmospheric oxidation of the alkenes[END_REF] The reactivities of the branched alcohols with OH also fall in this range. The tropospheric lifetimes of the aliphatic alcohols can be estimated by combining their reactivity towards OH radicals with a diurnal average [OH] = 10 6 molecule cm -3 to give a range of two weeks for methanol (the least reactive alcohol) to less than a day for more reactive alcohols such as n-octanol. The lifetimes of alcohols (see Table 4) are too short for them to make a significant contribution to radiative forcing of climate change.

 X = 1/k x [X],
where k is the rate constant for reaction of the OVOC with oxidants and [X] is the oxidant concentration; [OH] = 10 6 (24-hr average) for OVOCs with lifetimes > 1 day or 2. d Wet and dry deposition is an important atmospheric removal process for these compounds, see text for details.

The degradation of aliphatic alcohols under atmospheric conditions proceeds by H-atom abstraction from various C-H groups in the alkyl chain. H-atom abstraction from the O-H group in alcohols occurs with a rate constant of approximately 210 -13 cm 3 molecule -1 s -1 at 298 K and is of minor importance. In the reaction of OH with CH 3 OH, H-atom abstraction from CH 3 -group represents  85 % and that from -OH about 15 % of the overall reaction at 298 K. In the reaction of OH with CH 3 CH 2 OH, the abstraction occurs mainly from the -CH 2 -group (75 ± 15%), while abstraction from the CH 3 and OH groups represents approximately 5% for each channel. For linear-chain alcohols with three or more carbon atoms, H-atom abstraction from the α-carbon atom is likely to be the main reaction pathway, while abstraction from β-, and -carbon atoms will also make a significant contribution to the reaction products.

The oxidation products are carbonyl compounds such as aldehydes, ketones and hydroxycarbonyls. Scheme 1 shows a simplified OH-initiated degradation scheme for 2-butanol

CH 3 C(OH)CH 2 CH 3 CH 3 CH(OH)CHCH 3 O 2 CH 3 C(O)CH 2 CH 3 + HO 2 CH 3 CH(OH)CH(O)CH 3 + NO 2 O 2 /NO decomposition CH 3 CH(OH) + CH 3 CHO O 2 CH 3 CHO + HO 2 (~65%) (~35%)
Scheme 1. Simplified degradation scheme for the OH-initiated oxidation of 2-butanol Similarly to aliphatic alcohols, diols are also oxidized in the atmosphere via reaction with OH radicals. However, their reactivity is higher than that of the corresponding monoalcohols. [44][45][46] The tropospheric lifetime of the diols is less than a day. [45][46] Cyclic alcohols are removed from the atmosphere mainly via reaction with OH radicals and have lifetimes of the order of hours. The reaction is expected to occur predominately via H-atom from the -position leading to the corresponding cycloketones. H-atom abstraction from the other positions (βand -) may also contribute to the reaction. The overall reaction leads to products arising from ring retaining and cleavage degradation pathways. The OH-initiated oxidation of cyclohexanol has been reported to form cyclohexanone, 3-hydroxycyclohexanone and 4hydroxycyclohexanone as ring retaining products and hexanedial from the cleavage of the ring. 47 The main gas phase oxidation routes of aromatic alcohols in the atmosphere are their reactions with OH and NO 3 radicals. [START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF][48][49] Their lifetimes are of the order of a few hours. The reaction of OH may proceed through H-abstraction and OH-addition to the aromatic ring. The relative importance of these channels depends on the temperature. The available kinetic and mechanistic data indicate that for the atmospherically relevant temperature range, the reaction proceeds mainly via the addition channel. H-atom abstraction from the -OH group is of minor importance and accounts for <10 % of the overall reaction at 298 K. Mechanistic studies have shown that the OH-initiated oxidation of phenols and cresols produces the corresponding nitrophenols, benzoquinones, and dihydroxybenzenes. [START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF] The reaction of NO 3 with aromatic alcohols can produce nitrophenols and other nitro-containing aromatic compounds with high yields indicating that the H-atom abstraction channel is of importance.

Unsaturated Alcohols (R 1 R 2 C=CR 3 R 4 (OH)): Unsaturated alcohols are very reactive towards atmospheric oxidants, OH and NO 3 radicals and O 3 , their atmospheric degradation is controlled via chemical reactions with these oxidants. The atmospheric lifetimes of the unsaturated alcohols are shorter than their aliphatic analogues and are in the range of hours to minutes. They will be rapidly oxidized near their emission sources and may contribute to local ozone formation.

The OH-initiated oxidation of unsaturated alcohols is expected to proceed mainly by addition of OH to the C=C bond to form a series of hydroxyalkyl radicals which in general add O 2 and then react with NO to give the corresponding hydroxalkoxy radicals. The fate of the hydroxalkoxy radicals is decomposition, isomerisation and reaction with O 2 depending on their chemical structure. Hydroxyaldehydes and dihydroxycarbonyls have been reported among the main end products arising from the reaction of OH with unsaturated alcohols. [50][51][52][53] The reaction of ozone with unsaturated alcohols is expected to involve, as for other olefins, electrophilic addition at the carbon-carbon double bond leading to the formation of a trioxide followed by its unimolecular decomposition into two carbonyls and two biradicals (Criegee Intermediates, CIs). [54][55][56] CIs may form other carbonyls and free radicals such as HO x and contribute to the formation of SOA.

The reaction of NO 3 with unsaturated alcohols occurs predominantly via addition to the more substituted carbon atom in the C=C bond which leads under atmospheric conditions to the formation of nitrooxyalkyl peroxy radicals which react with NO to give the corresponding nitrooxyalkyl alkoxy radicals. These later radicals can decompose, isomerise or react with O 2 leading to carbonyls and nitrooxycarbonyls compounds as main end products. [57][58]

Ethers

Ethers are widely used in chemical industry, they are also used as fuels and fuel additives.

Aliphatic Ethers, Polyethers, Cyclic Ethers, Alkoxy Alcohols and Alkoxy Esters:

The atmospheric degradation of ethers, polyethers, cyclic ethers, alkoxy alcohols and alkoxy esters in the troposphere is predominantly initiated by reaction with OH radicals. Reaction with NO 3 radicals during the night-time contributes, to a small extent, to the atmospheric removal of some ethers.

Ethers do not absorb significantly at wavelengths > 200 nm and hence photolysis is not a significant atmospheric loss mechanism. [START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF] For unsaturated ethers reaction with O 3 can compete with reaction with OH and NO 3 radicals as an important loss mechanism.

The available rate constant data at room temperature for reactions of OH with linear chain ethers show a large increase in reactivity with increasing chain length. The reactivity of OH radicals towards ethers is greater than that of the corresponding alkanes, which has been attributed to the activating effect of the ether group (-O-). For example, compare: andk(OH+n-C 3 H 7 OC 3 H 7 )=2010 -12 with k(OH+n-C 6 H 14 )= 5.27 10 -12 cm 3 molecule -1 s - 1 . [START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF][START_REF] Calvert | The mechanisms of atmospheric oxidation of the alkenes[END_REF][START_REF] Ammann | Report on the 34th Session of the Joint Scientific Committee of the World Climate Research Programme 2[END_REF] The OH reaction rate constants at room temperature range from  310 -12 for CH 3 OCH 3 to  3010 -12 cm 3 molecule -1 s -1 for larger ethers such as di-n-butyl ether

k(OH+CH 3 OCH 3 ) = 2.8x10 -12 with k(OH+CH 3 CH 3 ) = 0.2410 -12 ; k(C 2 H 5 OC 2 H 5 )= 12.210 -12 with k(OH+n-C 4 H 10 ) = 2.3610 - 12 ,
(CH 3 (CH 2 ) 3 O(CH 2 ) 3 CH 3 ) and di-n-pentyl ether (CH 3 (CH 2 ) 4 O(CH 2 ) 4 CH 3 )
. Combining these values with an average daytime [OH] of 2.510 6 cm -3 for molecules with lifetimes <1 day and a diurnal average [OH] of 110 6 cm -3 for molecules with lifetimes >1 day, 8 provides a range of 4 hours to 4 days for the atmospheric lifetimes of typical ethers. The degradation of ethers in the atmosphere leads mainly to formates, acetates and other carbonyl-containing products. To illustrate the typical atmospheric degradation mechanism of ethers, scheme 2 shows the OHinitiated degradation of one of the simplest ethers, diethyl ether (CH 3 CH 2 OCH 2 CH 3 ). The main oxidation products of diethyl ether reported in the literature are ethyl formate, ethyl acetate, acetaldehyde and formaldehyde. [START_REF] Wallington | [END_REF][61][62][63] The reaction proceeds mainly by H-atom abstraction from the -CH 2 -groups followed by reaction with O 2 to give a peroxy radical which reacts with NO to form the alkoxy radical C 2 H 5 OC(O)HCH 3 . It has been shown in chamber studies that a substantial fraction of these alkoxy radicals are formed chemically activated. 63 The chemically activated alkoxy radicals either undergo "prompt" non-thermal decomposition or are thermalized by collisions. In the case of C are in the range (4-10)10 -11 cm 3 molecule -1 s -1 for OH, >10 -13 for NO 3 and >10 -16 for O 3 leading to very short atmospheric lifetimes for the unsaturated ethers, of the order of hours to minutes. 68- 71 The reactions proceed mainly through addition of the oxidants to the >C=C< bond leading to carbon-carbon bond scission and shorter chain length carbonyl products (nitrate products in the case of reaction with NO 3 ). 55,68,[72][73][74] A non-negligible yield formation of secondary organic aerosol has been reported for the ozonolysis reactions. 72,[75][76]

Aldehydes

Aldehydes are emitted directly to the atmosphere from anthropogenic and natural sources or produced in-situ as intermediates in the oxidation of other VOCs. The HCHO lifetime with respect to reaction with OH radicals is calculated to be around half a day. [START_REF] Calvert | The mechanisms of atmospheric oxidation of the alkenes[END_REF] The reaction of OH with formaldehyde leads to HCO radicals. The subsequent reactions following the photolysis and reaction with OH in the presence of NOx lead ultimately to the generation of ozone through the mechanism shown in scheme 3.

Photolysis frequency (10 It has been shown recently that photo-tautomerization to vinyl alcohol is a significant atmospheric fate of acetaldehyde 78 and that OH-initiated oxidation of enols may be an important source of carboxylic acids. 79 The atmospheric importance of photo-tautomerization of aldehydes is unclear and the subject of current research. In general, photolysis of the other aldehydes is less competitive with the OH reaction but still important mainly at higher altitudes of the troposphere. [START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF] The rate constants for reaction of OH with aldehydes are  10 -11 cm 3 molecule -1 s -1 which result in short atmospheric lifetimes (< 12 hours for a typical daytime [OH] of 2.510 6 cm -3 ) for these compounds. The reaction occurs mainly through H-atom abstraction from the aldehydic group (-CHO). Hydrogen atom abstraction from the C-H bonds of the alkyl chain is of minor importance for small aldehydes but can be significant for larger aldehydes. The products arising from the OH-initiated degradation of aldehydes are mainly shorter aldehydes and ketones. Abstraction of the aldehydic hydrogen gives acyl radicals which rapidly add O 2 to give acylperoxy radicals.

Acylperoxy radicals can add NO 2 to give acylperoxy nitrates

(RC(O)O 2 NO 2 ): RCHO + OH (+O 2 ) + M  RC(O)O 2 + H 2 O + M RC(O)O 2 + NO 2  RC(O)O 2 NO 2 + M
The most important member of this family is peroxyacetyl nitrate

(PAN), CH 3 C(O)O 2 NO 2 ,
which is stable at low temperatures, constitutes a reservoir for NO x , and provides through its transport a source of NOx in remote areas.

Hydroxyaldehydes and dialdehydes are decomposed within the atmosphere by reaction with OH and photolysis with this latter process being the dominant for short dialdehydes such as glyoxal cm 3 molecule -1 s -1 ). These rate constants values lead to lifetimes of the order of hours under atmospheric conditions. The reactions occur mainly through H-atom abstraction from the -CHO group with a non negligible H-atom abstraction from the ring, up to more than 10 % as reported for cyclobutanecarbaldehyde. 80 The abstraction of the aldehydic hydrogen atom may lead to the formation of peroxynitrates. Ring opening may occur following H-atom abstraction from the -CHO group or from the ring and would lead to shorter carbonyls.

The degradation of aromatic aldehydes in the atmosphere is controlled by photolysis and reaction Unsaturated Aldehydes: Unsaturated aldehydes are very reactive towards atmospheric oxidants, photolysis is likely a minor loss mechanism. 82 Removal by O 3 is less significant than by OH and NO 3 for the mono-unsaturated aldehydes but is important for the dienals. The rate constants for reactions of OH and NO 3 with mono-unsaturated aldehydes are in the ranges k OH (2-6)10 -11 and k NO3 (1-500)10 -15 cm 3 molecule -1 s -1 , respectively, depending on the structure and size of the molecule. The lifetimes of the mono-unsaturated aldehydes with respect to reaction with OH and NO 3 range from hours to 1 day. The dienals are even more reactive than the monounsaturated aldehydes, k OH 110 -10 and k NO3 210 -12 cm 3 molecule -1 s -1 , respectively. Their

CHO OH O O O NO 2 O O O O 2 N O O NO O 3 O OH NO 2 NO 2 O 2 NO -CO 2 +O 2
of the order of hours.

The reactions of OH and NO 3 with unsaturated aldehydes proceed by both H-atom abstraction from the -CHO group and addition to the >C=C< double bonds. H-atom abstraction from the -CHO group, in the presence of NOx, leads to the formation of peroxyacylnitrates, RC(O)O 2 NO 2 , such as peroxyacryloyl nitrate from acrolein, peroxycrotonoyl nitrate from crotonaldehyde, and peroxymethacryloyl nitrate from methacrolein. [83][84][85][86][87] As described above, peroxyacylnitrates serve as reservoirs for NO x and can transport NO x over long distances. The other products reported in the oxidation of unsaturated aldehydes are radicals and short-chain carbonyls which may play an important role in ozone formation as shown in scheme 3 for formaldehyde. in the oxidation of alkanes and alkane diols. [90][91] Hydroxyacetone is formed in the tropospheric oxidation of methacrolein which is itself a primary product of the degradation of isoprene. The atmospheric degradation of isoprene leads also to methyl vinyl ketone. The destruction of aromatic compounds in the atmosphere forms significant yields of a variety of dicarbonyls and unsaturated dicarbonyls. Butanedione is formed in the oxidation of o-xylene via a bridged bicyclic peroxy radical. Butanedione is also formed in the oxidation of methyl ethyl ketone under low NOx conditions via peroxy-peroxy radical reactions.

Aliphatic ketones, hydroxyketones, dicarbonyls cyclic and aromatic ketones:

The main loss processes of ketones from the atmosphere are photolysis and reaction with OH radicals.

Reactions of O 3 and NO 3 with saturated ketones are negligible under atmospheric conditions.

Ketones absorb quite strongly in the actinic region but their photolysis quantum yields are typically small for the pressures in the lower troposphere. [92][93][94] Photolysis is a more important removal process at higher altitudes. Acetone, one of the most important ketones in the atmosphere, is removed predominately by reaction with OH at the surface with photolysis making a more important contribution at higher altitude. [95][96][97] The lifetimes for photodissociation of ketones in the lower troposphere with an overhead sun are of the order of days to weeks (e.g., 14-22 days for acetone, 2.5 days for butanone, 4-7 days for 2-pentanone and 1-8 days for 2hexanone). [START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF] The photolysis of ketones is a substantial source of radicals in the atmosphere.

The rate constants for reactions of OH with ketones are larger than those with the corresponding alkanes. The presence of the carbonyl group deactivates the H-atom at the -position (attached to the carbon atom adjacent to the carbonyl group) but activates the hydrogen atoms at the βposition. [98][99] The difference increases to up to a factor 3 for the large ketones and the corresponding alkanes such as for 4-methyl-2-pentanone (CH 3 C(O)CH 2 CH(CH 3 ) 2 ) and 2methylpentane (CH 3 CH 2 CH 2 CH(CH 3 ) 2 ) for which the rate constants are 12.810 -12 and 5.2610 - 12 cm 3 molecule -1 s -1 at 298 K, respectively. [START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF][START_REF] Calvert | The mechanisms of atmospheric oxidation of the alkenes[END_REF] The rate constants for OH reactions with ketones are in the range 1.810 -13 for acetone to 2.510 -11 for 2,6-dimethyl-4-heptanone implying lifetimes with respect to OH of two months to a few hours depending on the structure of the molecule. [START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF] The reaction proceeds via an H-atom abstraction, preferentially from the β-position if available.

The OH-initiated oxidation of acetone in the presence of NO in air has been shown to form the 57 acetonoxy radical (CH 3 C(O)CH 2 O) which decomposes rapidly under atmospheric conditions to form HCHO and CH 3 CO. 100 This reaction has been suggested to be an important source of formaldehyde in the upper troposphere.

The reaction of OH with larger ketones occurs by H-atom abstraction from various sites and leads to a variety of products such as simple aldehydes, dicarbonyls and hydroxydicarbonyls produced following reaction with O 2 , decomposition, and isomerization of the initially formed alkoxy radicals. As an example, the series of the potential first generation products arising from the chemistry of the alkoxy radicals produced in the OH-initiated oxidation of 2-pentanone is given in Table 6. The reaction of OH with 2-pentanone can proceed by 4 pathways, all involving H-abstraction from the C-H bonds and leading to formation of the corresponding alkoxy radicals in the presence of O 2 and NO:

OH + CH 3 C(O)CH 2 CH 2 CH 3 H 2 O + CH 3 C(O)CHCH 2 CH 3 H 2 O + CH 2 C(O)CH 2 CH 2 CH 3 H 2 O + CH 3 C(O)CH 2 CHCH 3 H 2 O + CH 3 C(O)CH 2 CH 2 CH 2 O 2 NO NO 2 + CH 3 C(O)CH(O)CH 2 CH 3 NO 2 + OCH 2 C(O)CH 2 CH 2 CH 3 NO 2 + CH 3 C(O)CH 2 CH(O)CH 3 NO 2 + CH 3 C(O)CH 2 CH 2 CH 2 (O)
Organic nitrates may be also formed under high NOx conditions. The alkoxy radicals formed in the scheme shown above undergo reaction with O 2 , decomposition via C-C bond fission, and isomerization. Table 6 summarises the reaction products from different alkoxy radicals. Hydroxyketones are mainly removed from the atmosphere by reaction with OH radicals although photolysis can make an important contribution especially at high altitude. The lifetime of hydroxyacetone with respect to OH reaction is  3 days and in the range 5-11 days for photolysis in the lower troposphere under an overhead sun. The atmospheric lifetimes of larger hydroxyketones are shorter because of their greater reactivity towards OH radicals (k OH 10 -11 cm 3 molecule -1 s -1 ).

Photolysis and reaction with OH radicals compete for the removal of diketones from the atmosphere although photolysis is the dominant loss process for the simplest diketone, 2,3-with respect to photolysis with an overhead sun is less than 4 hours while that with respect to reaction with OH radicals is 50 days. For larger diketones, the reactions with OH radicals will be more significant. The general mechanism for the reaction of OH with diketones is expected to be mainly H-atom abstraction leading to a series of shorter carbonyls.

Both OH reaction and photolysis play an important role in the atmospheric removal of cyclic and aromatic ketones depending on their size and structure. For example, lifetimes with respect to photolysis in the lower troposphere for cyclobutanone and 1,4-naphthoquinone are quite short,  10 hours and  2 hours, respectively while those with respect to OH reaction are of the order of days. The contribution of OH reaction to the total atmospheric removal is more important for the larger cyclic and aromatic ketones but still of the order of a few days.

Unsaturated ketones:

The atmospheric destruction of unsaturated ketones are mostly controlled by reaction with OH radicals for the short unsaturated ketones (e.g. methyl vinyl ketone,

CH 3 C(O)CH=CH 2 )
. The contributions of the reactions of NO 3 and O 3 become more important and may dominate for some larger species (6-methyl-5-hepten-2-one,

CH 3 C(O)CH 2 CH 2 CH=C(CH 3 ) 2 )
). Lifetimes for photodissociation are relatively long, of the order of days while those with respect to reactions with OH, NO 3 and O 3 are of the order of hours to minutes depending on the size and the structure of the species. The atmospheric oxidation of the unsaturated ketones produces a variety of products following the addition of the oxidant to the >C=C< double bond. For example, formaldehyde, glycolaldehyde, methylglyoxal have been reported from the degradation of methyl vinyl ketone; propanal, and glycoladehyde in addition to minor yields of formaldehyde and 2-oxobutanal are expected from the degradation of ethyl vinyl ketone. [START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF] The NO 3 -initiated oxidation of the larger unsaturated ketones is a source of nitrates.

Both photolysis and reaction with OH radicals are very effective loss processes for unsaturated dicarbonyls leading to lifetimes of a few hours. Their degradation leads to short chain carbonyls through decomposition although isomerization may also occur leading to cyclisation or rearrangement. 102-105

Esters

Esters are emitted from natural and anthropogenic sources and are also formed in the atmosphere by the oxidation of ethers. Esters have low water solubility and following release partition into the gas-phase. Esters hydrolyze slowly and uptake into rain-cloud-sea water is generally of negligible importance. Esters do not absorb significantly at wavelengths greater than 240 nm and hence do not undergo photolysis in the lower atmosphere. The atmospheric chemistry of esters is dominated by their reaction with OH radicals. For unsaturated esters reactions with O 3 and NO 3 radicals also play a role. In the special case of highly fluorinated esters which are relatively unreactive towards OH radicals loss via hydrolysis can be an important atmospheric removal mechanism (see section IV.g). The available data concerning the atmospheric chemistry of esters has been the subject of a comprehensive recent review by Calvert et al. [START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF] An overview of the atmospheric chemistry of esters is provided below, for details readers are encouraged to consult the detailed review by Calvert et al. [START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF] As seen from Figure 9, the reactivity of esters towards OH radicals is substantially lower than for ethers of the same size. Small esters are less reactive than the corresponding alkanes, but for larger esters (>C 5 ) there is little, or no, discernable difference in reactivity with the corresponding alkanes. The ester functionality -C(O)Oin R 1 C(O)OR 2 deactivates the R 1 and R 2 alkyl groups to which it is attached with the deactivation being most pronounced for the R 1 group. [START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF] The deactivation effect does not appear to extend beyond the first carbon atom in the R 1 and R 2 groups and hence larger esters have reactivities which are similar to those of the corresponding alkanes (e.g., compare methyl hexanoate, CH 3 OC(O)OC 5 H 11 , and n-heptane, C 7 H 16 , in Figure 9). Combining the rate constants in Figure 9 with a diurnal average [OH] of 110 6 cm -3 gives lifetimes of esters ranging from 65 days for methyl formate to 1 day for nbutyl-n-butyrate.

As an example of the degradation mechanism of esters, scheme 4 shows a simplified mechanism for the oxidation of ethyl acetate. The majority (94%) of the reaction with OH radicals The solubility of carboxylic acids can be calculated using an effective Henry's Law coefficient (H*) which is defined as

H* = H  (1 + K a /[H + ])
, where K a is the acid dissociation constant (see, for example, Brasseur et al., 1999). 113 Temperature-dependent Henry's Law coefficients, pK a values [pK a = -log 10 (K a )], and effective Henry's Law coefficients evaluated for conditions representative of a typical cloud (pH  5, T  270 K) are given in Table 7 for selected organic acids. As seen in Table 7, the solubility of carboxylic acids decreases with increasing size of the hydrophobic alkyl chain R. Seinfeld and Pandis 114 have suggested that as a rough guide, species with Henry's Law constants below approximately 10 3 M atm -1 will partition strongly into the atmospheric gas phase, and wet/dry deposition will probably not be of major importance. In contrast, compounds with Henry's Law constants above approximately 10 6 M atm -1 will partition strongly into atmospheric aerosols and wet/dry deposition may be an important atmospheric loss process. For the most water soluble gases the global average time scale for removal by wet deposition is limited by rain events and is approximately 1 week. 113 For soluble carboxylic acids such as formic acid, effective scavenging into a typical cloud, occurs, and thus removal via rainout is anticipated on the timescale of about one week in the lower troposphere. 113 While scavenging of the larger monocarboxylic acids by rain water will be less effective than for the small members of the series, inspection of Table 7 shows that Carboxylic acids derived from reactions of ozone with terpenes: The ozonolysis of terpenes generates a large number of multi-functional organic acids. 108,111 These organic acids have extremely low vapor pressures (typically  10 -4 Pa at 298 K, 119 ) and partition into the condensed phase. With such low vapor pressures experimental studies of gas phase loss mechanisms are extremely difficult and have yet to be reported. km where UV radiation with wavelengths below 200 nm is available. 124 In contrast, fluorinated ketones have a strong absorption band at approximately 300 nm and undergo photolysis in the troposphere and have an atmospheric lifetime of approximately 1 week. [125][126] In contrast to nonfluorinated esters, uptake into the ocean and hydrolysis can be a significant atmospheric loss mechanism for fluorinated esters. [127][128] The lifetime of fluorinated esters with respect to loss to the ocean is of the order of a year. The wide range of lifetimes of halogenated OVOCs is illustrated by the data for representative compounds shown in Table 8.

Compounds containing C-F bonds have strong absorptions in the infra-red (IR)

"atmospheric window" region. Absorption in this region is effective in hindering the loss of terrestrial radiation into space and contributes to the greenhouse effect. Radiative efficiency is a measure, on a per molecule basis, of the ability of a compound to contribute to the greenhouse effect and has units of W m -2 ppb -1 . The radiative efficiencies for selected halogenated OVOCs evaluated by Hodnebrog et al. 122 are listed in Table 8. Radiative efficiency is evaluated on a per molecule basis and is dependent on the number and type of C-F bonds in the molecule. The global warming potential of a molecule is a measure of the ability of a given mass of gas to trap heat in the atmosphere relative to that of the same mass of CO 2 . The global warming potential is the time-integrated radiative forcing due to a pulse emission of a gas relative to that for the same mass of CO 2 . The global warming potentials of selected OVOCs are given in Table 8.

Organosulfates/organonitrates

Organosulfates (OSs, ROSO 3 H) and organonitrates (ONs, RONO 2 ) are significant components of aerosol organic matter. OSs and ONs contain sulfate or nitrate functional groups, which are hygroscopic or hydrophilic. Aerosols, containing OSs and ONs can act as cloud condensation nuclei (CCN) and hence can impact climate. OSs exist mainly in the aerosol phase.

ONs exist in both gas and aerosol phases. Aerosol OSs and ONs have been reported in laboratory-generated SOA, field measurement of particulates, rainwater, fog and cloud water. ). [131][132] OSs and ONs are found in fog 133 and cloud [134][135][136] in ambient particular aerosol from Asia [137][138] to North West Europe. 139 The first evidence of the formation of OSs in a laboratory study was provided in a study of the reactive uptake of glyoxal (HC(O)C(O)H) onto particulate matter in a Teflon chamber when inorganic seed particles including (NH 4 ) 2 SO 4 , (NH 4 ) 2 SO 4 / H 2 SO 4 were introduced. 140 A mechanism for the formation of glyoxal sulfates in particulate matter was proposed 140 in which glyoxal is first hydrated and protonated, followed by reaction with sulfate species, sulfuric acid, bisulfate or sulfate. Subsequent loss or gain of a proton results in the neutral compound , and cyclization of this compound can produce the organosulfate . OSs have been observed using aerosol mass spectrometry in studies of the reaction of gas phase pinonaldehyde with acidic sulfate aerosols. 141 In those experiments OSs were a significant fraction of the pinonaldehyde reaction products and OSs accounted for 6-51% of the initial SO 4 2mass. The existence of OSs was also confirmed in studies of the reaction system in bulk solution.

The formation of OSs suggests that conventional inorganic SO 4 2-chemical analysis may underestimate total sulfate mass in ambient aerosols. 141 Direct esterification reactions between alcohols and sulfuric acid to form sulfate esters in aerosol particles have been explored for a number of simple alcohols and shown to be of negligible atmospheric importance. 142 Sulfate esters are formed by photochemistry induced oligomerization processes involving CHOS molecules and are important constituents of the water-soluble organic fraction (WSOC) of SOA.

143 High resolution mass spectrometry analysis of aqueous extracts of SOA generated from the ozonolysis of d-limonene in the presence of (NH 4 ) 2 SO 4 aerosol has shown the formation of OSs. 144 The contribution of OSs to the total ambient aerosol organic mass varies greatly with location and time and is approximately 0.2-30%. OSs were found to comprise less than 1% of the average organic aerosol in Whistler, British Columbia. 145 A semi-quantitative analysis estimated that OSs account for less than 1% of PM 2.5 mass and 3.8% of total sulfate in four sites spanning urban and remote locations in Asia. 138 On average OSs have been reported to comprise about 10% of the organic mass in submicron Arctic aerosol. 146 In 12 sites across the U.S., OSs accounted for approximately 5-10% of the organic mass in the ambient aerosols. 147 OSs account for 6-14% of the sulfate concentration in ambient aerosol 148 , and may account for up to 30% of the total organic mass of ambient aerosol 149 collected in a background monitoring site in Hungary. In a study of isolated organic matter analytes from fog water it was found that neutral losses of SO 3 and SO 4 occurred in 85% and 27% of the CHOS compounds and in 42% and 0%

of the CHNOS compounds. 150 Single particle mass spectrometry indicated that OSs are present in 80% of particles in the tropical free troposphere and that IEPOX (epoxydiol,

O HO OH )
sulfate ester is one of the most abundant organic compounds measured in atmospheric aerosol. 151 Aerosol OSs are formed in the oxidation of biogenic precursors, such as isoprene, α-/βpinene, d-/l-limonene, α-/γ-terpinene, terpinolene, Δ Adapted from refs. 149,155,157 The uptake of reactive species on acidic sulfate aerosols leads to the formation of OSs. 141- 142,152,159-161 The reactive species include glyoxal, 140 pinonaldehyde, 141 methylglyoxal, 161 monoterpene oxides (α-pinene oxide and β-pinene oxide) and acid catalyzed isomerization compounds of α-pinene oxide (campholenic aldehyde and carveol), 152,159 and several carbonyl compounds (formaldehyde, octanal, trans,trans-2,4-hexadienal, 2,3-butanedione, 2,4-pentanedione, glutaraldehyde, and hydroxyacetone). 160 Nguyen et al. 162 investigated the reactive uptake of isoprene cis-and trans-IEPOX onto non-acidified inorganic seeds and demonstrated that the conversion of IEPOX to organic aerosol depends on the coupled relationship between the inorganic composition and liquid water content of the particle (P LWC ). The inorganic composition governs the catalyst and nucleophile characteristics, and P LWC provides a reaction medium for the partitioning of IEPOX and controls the activities of all the aqueous components. Surratt et al. 163 found that the NOx concentration has a significant effect on the formation of isoprene-derived OSs via two key reactive intermediates IEPOX and methacryloylperoxynitrate (MPAN) which are formed during isoprene oxidation under low-and high-NOx conditions, respectively. Isoprene low-NOx SOA is enhanced in the presence of acidified sulfate seed aerosol (mass yield 28.6%) over that in the presence of neutral aerosol (mass yield 1.3%). Hydroxy sulfate ester and its dimer are formed in the aerosol phase under low-NOx conditions due to increased aerosol acidity. Under high-NOx conditions, isoprene SOA formation occurs through oxidation of its reactive intermediate, MPAN. The similarity of the composition of SOA formed from the photooxidation of MPAN to that formed from isoprene and methacrolein suggests the role of MPAN in the formation of isoprene high-NOx SOA. 163 After loss of water in the decomposition of the C4-hydroxynitrate-PAN, the oligoester of 2methylglyceric (2-MG) is formed in the aerosol phase under high-NOx conditions. Worton et al. 164 concluded the strong temperature dependence of MPAN formation helps to explain observations of similar concentrations of IEPOX-derived OS and methacrylic acid epoxide (MAE)-derived OSs under cooler conditions (lower isoprene concentrations) and much higher IEPOX-OSs relative to MAE-OSs at higher temperatures (higher isoprene concentrations). The formation of the IEPOX- 163,165 and MAE-derived OSs 163,166-167 can be from the HO 2 and NO/NO 2 pathways, respectively. The organosulfates formed from IEPOX and MAE only form through ring-opening epoxide chemistry, due to kinetic limitations of the sulfate alcohol esterification reaction, 142 and have been speculated to be among the products responsible for the enhancement of SOA under acidic conditions. 156,163 Scheme 6 shows the formation of OSs and ONs from the addition of weak nucleophiles in the aqueous NH

Aerosol Phase

Gas Phase Scheme 6. Mechanism for OSs and ONs formation during isoprene oxidation. OSs and ONs are indicated by dotted boxes. Adapted from ref. 142,157,[162][163][164] Nitrooxy-organosulfates were observed as prominent products in the OH/NO 3 -initiated photooxidation of monoterpenes in the presence of acidified sulfate aerosol by Surratt et al. 149 ONs were shown to be an important component of organic aerosol by O'Brien et al. 168 in the 1970s and are still the subject of active research interest, [169][170][171][172] ONs typically comprise 10-20% of the carbonaceous aerosol mass in urban locations. [173][174] In wintertime measurements in coastal southern California in 2009, ON groups accounted for up to 10% of organic mass in submicron particles produced from urban combustion emissions. 175 Very recently, in PM 10 samples collected at a rural background site in Hamme, Belgium, -pinene-related nitrooxyorganosulfates were detected during the winter. 176 In marine rainwater samples collected in on the island of Bermuda, five compound classes 177 were identified that contained CHON + , CHONS + ,CHONP + , CHONSP + , CHN + . Bleier et al. 178 investigated the kinetics and thermodynamics of atmospherically relevant aqueous phase reactions of α-pinene oxides. Their results indicated that α-pinene oxide will react very quickly with aqueous atmospheric particles, even under low acidity conditions. Depending on the acid concentration of the aqueous solutions, a number of new products such as trans-sobrerol sulfate, trans-sobrerol nitrate, pinane-2-sulfato-1-ol and pinane-2-nitrato-ol are observed from the reaction of α-pinene oxide. No long-lived OSs or ONs species are observed.

Other important sulfur-/nitrogen-containing organics include alkyl-sulfonic acids such as methanesulfonic acid (CH 3 S(O) 2 OH, MSA), and peroxyacylnitrates (RC(O)O 2 NO 2 ), 179 such as peroxyacetyl nitrate (PAN) and its analogs (PANs). 180 MSA and many sulfur-containing organics such as dimethyl sulfoxide (CH 3 SOCH 3 , DMSO) and dimethyl sulfone (CH 3 SO 2 CH 3 , DMSO 2 ) are oxidation products dimethyl sulfide (DMS, CH 3 SCH 3 ). DMS is produced from the oceanic degradation of dimethylsulphoniopropionate (DMSP) released from some phytoplankton species. [181][182] On a global scale biogenic emissions of DMS are important with contributions to the sulfur budget of 15-20% and 50-60% in the Northern and Southern Hemispheres, respectively. [183][184][185][186] estimated an annual mean DMS emission of 28 Tg(S) yr -1 and a DMS burden in the atmosphere of 0.077 Tg(S) from marine sources. 188 MSA, DMSO and DMSO 2 are the main DMS gaseous oxidation products of sulfurcontaining organics. Barnes et al. et al. 184 Fischer et al. 194 found that many NMVOC emissions are responsible for PAN formation globally including isoprene (37%), alkanes (14%), and terpenes (9%). PAN formation in the OH-initiated atmospheric oxidation of isoprene and αpinene 192,[195][196][197][198] Scheme 7. Simplified reaction scheme illustrating the production of PAN during the OHinitiated oxidation of isoprene, propane and α-pinene adapted from ref. 195,198 In addition to PAN, other peroxyacyl nitrates detected in the atmosphere include peroxypropionyl nitrate (PPN, CH . PAN is the most abundant peroxyacyl nitrate and its concentration ranges from a few ppt in marine background air to more than 10 ppb in urban air masses. PPN is the second most abundant peroxyacyl nitrate, the PPN to PAN ratio is typically in the range of 0.1-0.3, the other peroxyacyl nitrates are typically present at lower concentrations. [START_REF] Atkinson | [END_REF][199][200][201][202][203][204][205][206][207] PAN reacts slowly with OH radicals and has a lifetime greater than a year with respect to reaction with OH. PAN is thermally unstable and decomposes to reform the peroxyacetyl radical, CH 3 C(O)O 2 , and NO 2 . [START_REF] Atkinson | [END_REF]202 PAN undergoes photolysis at a moderate rate. The lifetime of PAN with respect to photolysis is approximately 1.7 months 8 .

As shown in Figure 11, at low altitudes the lifetime of PAN is determined by thermal decomposition and is a few hours to a few days. Thermal decomposition is the most important loss mechanism of PAN at low altitudes but becomes rapidly less important with increasing altitude and decreasing temperature. At altitudes above 4-5 km the lifetime of PAN is determined by photolysis and is sufficiently long for long range transport of PAN to remote areas. Mixing back to lower altitudes followed by thermal decomposition provides an important mechanism for long-range transport of NOx thereby affecting the production of tropospheric O 3 in remote areas. [201][202][203]208 for the U.S. Standard Atmosphere using kinetic data from Atkinson et al. [START_REF] Atkinson | [END_REF] and photolysis data from Calvert et al. 8 Field study observations in Bakersfield, California by Rollins et al. 209 indicate that the nighttime formation of particulate organic nitrates increases with NO x , and is suppressed by high concentrations of organic molecules that react rapidly with nitrate radical (NO 3 ). The observations indicate that particulate organic nitrates are secondary products formed in reactions of NO 3 radicals with the primary products of the NO 3 radical-initiated of reactive biogenic Lifetime (days)

Ozone formation from the atmospheric oxidation of OVOCs

The atmospheric oxidation of VOCs is extremely complex and there is no simple relationship between VOC degradation and tropospheric ozone formation. Different VOCs make different contributions to ozone formation reflecting differences in VOC reactivity and chemical structure.

Some organic compounds react very slowly, give relatively unreactive products, and make little contribution to ozone formation. Other compounds react rapidly, give reactive products, and make large contributions to ozone formation. Recognition of the large range of abilities for scenarios representing conditions where ambient ozone is most sensitive to changes in VOC emissions. 217 These calculations require a model or models for airshed conditions, a method for quantifying ozone impacts, and a chemical mechanism to calculate the effects of VOC reactions on ozone formation in the atmosphere. MIR values are calculated using the SAPRC (Statewide Air Pollution Research Center) mechanism which has been updated over the years. The MIR method has been tested under various emission conditions 218 for a large number of compounds.

The POCP concept covers a longer time scale than MIR. POCP values are determined from the calculated formation of ozone in the boundary layer over a period of up to five days using a photochemical trajectory model. The POCP measures total additional ozone formed during a multi-day model by adding a given amount of volatile organic compound relative that of adding the same mass of ethane. [START_REF] Derwent | [END_REF][START_REF] Jenkin | Photochemical ozone and PAN creation potentials: rationalisation and methods of estimation[END_REF]215 The POCP for a given VOCx is given by: POCP x = (ozone increment with x th VOC/ozone increment with ethene)  100

The POCP for ethene is defined as 100. Ethene is used as a reference for the POCP scale because its chemical degradation scheme is well defined and because it is one of the most important ozone forming VOCs in northwest Europe. 215 The photochemical model used to derive POCP incorporates the near explicit chemical mechanism MCM (Master Chemical Mechanism) which describes the detailed atmospheric degradation of a large number of VOCs and their contribution to the formation of ozone under boundary layer conditions. [219][220][221] Initially, to develop regional ozone strategies in Europe, this concept has been employed to describe regional scale ozone in a single air parcel travelling across northwest Europe for idealised conditions.

 POCP =  1   S   R β (1- 2 n C )
where  POCP is the estimated POCP;  1 ,  1 and β are constants;  S is the structure based ozone formation index,  R is the reactivity based ozone formation index, and n C is the number of carbon atoms in the compound. The structure and reactivity based ozone formation indices are defined as:

 S = (n B /M)  (28/6) calculated with the SAPRC-07 chemical mechanism (used in MIR calculations). The study involved first-day ozone formation and then was largely representative of the chemistry of the emitted organic compounds and their first generation products. There is general agreement between POCPs using the two different mechanisms for the majority of the species. Table 10. Applying the lifetime correction proposed by (Hodnebrog et al. 2013) 122 to account for non-uniform mixing in the atmosphere gives the effective radiative efficiencies listed in Table 10. Finally, combining these values with the atmospheric lifetimes gives GWP values for 20 and 100 year time horizons (see Acknowledgement). As seen from the results in Table 10, the direct contribution of these compounds to radiative forcing of climate is negligible. Gas-, liquid-and heterogeneous-phase reactions of oxygenated organic compounds are of central importance to atmospheric chemistry and to understanding the impact of anthropogenic emissions on air quality and climate. Much has been learned over the past 50 years of the chemistry of oxygenated organic compounds, but much is yet to be discovered.

  Photochemistry is responsible for the formation of approximately 4500 Tg of ozone per

Figure 2 .

 2 Figure 2.Global ethanol transportation fuel use[START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF][START_REF]Department-of-Energy; Alternative-Fuels-Data-Center[END_REF]

Figure 3 .Figure 4 .

 34 Figure 3. Global methanol transportation fuel use (Methanol Institute, 2014). 29

Figure 6 . 33 Concentration

 633 Figure 6. Representative concentration profiles for the five most abundant OVOCs in the

Figure 7 .

 7 Figure 7. Semilog plot of vapor pressure vs reciprocal temperature for butane and its oxygenated

  indirect effects of OVOCs on climate change. In terms of potential direct effects the ability of OVOCs to contribute to radiative forcing of climate is dependent on their atmospheric lifetimes and the intensity and position of their IR absorption bands. With the exception of a few halogenated OVOCs discussed in a following section, the atmospheric lifetimes of OVOCs are relatively short (typically in the range of hours to weeks) and their IR absorption is relatively weak. As a consequence, with the exception of a few halogenated ethers, OVOCs have essentially no direct effect on climate. Changes in the oxidizing capacity of the troposphere both on a regional and a global scale due to the chemistry of the OVOCs may constitute an indirect contribution of these species to radiative forcing. The atmospheric degradation of OVOCs leads to the formation of radicals which may in turn affect the atmospheric lifetime of known GHGs such as methane and halogenated VOCs and hence their atmospheric concentrations. The tropospheric ozone concentration is ultimately linked to the chemistry of VOCs and NOx. The atmospheric chemistry of OVOCs impacts the ozone concentration and impacts the contribution of ozone to radiative forcing. The chemical processes leading to the atmospheric degradation of OVOCs and formation of intermediates or end products which contribute to radiative forcing of climate change are the subject of this article. Where atmospheric lifetimes and atmospheric degradation products of OVOCs are given we stress that these are typical lifetimes. Lifetimes and product distributions will vary with local conditions.

5 

 5 10 6 (typical day-time concentration) for OVOCs with lifetimes < 1 day, [O 3 ] = 10 12 (24-hr average), and [NO 3 ] = 3  10 9 molecule cm -3 (night-time value in polluted urban environments). Oxidant concentrations vary in time and space, the atmospheric lifetimes of OVOCs emitted at a particular place and time could be longer, or shorter, than the representative values listed above. c NO 3 radical concentrations during the day-time are very low, lifetimes exceeding 12 hours calculated using the night-time value for polluted urban areas have been multiplied by a factor of 2 to facilitate comparison with lifetimes calculated using 24-hour average [OH] values.

(CH 3

 3 CH(OH)CH 2 CH 3 ). The reaction proceeds predominately via H-atom abstraction from the tertiary C-H and secondary -CH 2bonds, H-atom abstraction from the primary CH 3 -and -OH groups is of minor importance. H-atom abstraction from the tertiary C-H bond leading to pentanone (CH 3 C(O)CH 2 CH 3 ) accounts for  65 % and H-atom abstraction from the secondary -CH 2 -bond leading to acetaldehyde accounts for approximately 30 % of the overall reaction.[START_REF] Chew | [END_REF][43]

  Aliphatic Aldehydes, hydroxyaldehydes, dialdehydes, cyclic and aromatic aldehydes: The atmospheric degradation of aldehydes is controlled by photolysis and by reaction with OH radicals depending on their molecular structure. Photolysis is more important for branched-chain aldehydes compared to the linear chain ones. For the branched chain aldehydes, photolysis competes with OH reaction while reaction with OH radical is generally the dominant loss process for linear-chain aldehydes. The available kinetic data indicate that reactions of NO 3 radicals and O 3 with aldehydes are of negligible atmospheric importance.[START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF] Formaldehyde (HCHO) is formed during the atmospheric degradation of all VOCs and is one of the most reactive and most important species in tropospheric photochemistry and ozone formation.[START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF] Its degradation in the atmosphere is controlled both by photolysis and reaction with OH radicals. The rate of photolysis depends on the solar flux which depends on latitude, altitude, time of day, and day of the year. At an altitude of 0.5 km with overhead sun HCHO has a lifetime with respect to photolysis of around 3 hours. The photolysis channels are:HCHO + h  HCO + H (I) HCHO + h  CO + H 2 (II) HCHO + h  CO + 2H (III)Channels (I) and (II) are important in the lower troposphere (Figure8). Channel (III) is significant in the upper troposphere and stratosphere as discussed byCalvert et al. 8

Figure 8 .

 8 Figure 8. HCHO photolysis frequencies (j-values) for processes I and II and the total versus

(

  HC(O)C(O)H) and methyl glyoxal (CH 3 C(O)C(O)H). The lifetimes for these compounds are of the order of a few hours. The available kinetic and mechanistic data on the atmospheric degradation of cyclic aldehydes indicate that they are very reactive towards OH and NO 3 radicals (k OH  10 -11 and k NO3  10 -15

81 Scheme 4 .

 814 Scheme 4. Atmospheric degradation of benzaldehyde (adapted fromCalvert et al. 8 )

8 b

 8 photolysis rates data taken fromCalvert et al. 8

8 NumberFigure 8 .Scheme 4 . 8 4. 6 .

 88486 Figure 8. Rate constants at 298 K for reaction of OH radicals with esters, ethers, and n-

  the presence of additional oxygenated function groups in the molecule greatly increases the solubility of carboxylic acids (e.g., compare CH 3 C(O)C(O)OH and CH 3 CH 2 C(O)OH). Acyclic acids: Rate constants for reactions of OH radicals with acyclic carboxylic acids are shown in Figure 10. As expected, there is an increase in the reactivity of RC(O)OH species with increasing length of the R alkyl group. The smallest members of the series, formic and acetic acid, are significantly more reactive than the corresponding alkanes and methyl esters (RC(O)OCH 3 ). Interestingly, despite the substantial strength of the RC(O)O-H bond (460 kJ mol -1 ) the majority of reaction of OH radicals with formic and acetic acid proceeds via Habstraction to give the RC(O)O radical. The increase in reactivity from CH 3 CH 2 C(O)OH to CH 3 (CH 2 ) 2 C(O)OH is similar to that expected from the additional reactivity of a -CH 2group in the alkanes. Combining the rate constants in Figure 10 with a diurnal average [OH] = 110 6 cm -3 gives lifetimes with respect to reaction with OH radicals for formic, acetic, n-propanoic, and nbutanoic acids of 26, 16, 10, and 6 days, respectively. For the smaller acids the atmospheric fate is dominated by incorporation into rain-cloud-fog water followed by wet deposition. For larger acids gas-phase reaction with OH radicals can be a competitive loss mechanism.Dicarboxylic acids: Dicarboxylic acids are produced in small yields in the gas phase and can be generated from the condensed-phase oxidation of multi-functional species; for example, species such as glycolaldehyde [HOCH 2 CHO], glyoxal [HC(O)CHO], glycolic acid [HOCH 2 C(O)OH] or glyoxylic acid [HC(O)C(O)OH] can be converted to oxalic acid [HOC(O)C(O)H] in aqueous media. 112 Dicarboxylic acids have very low vapor pressures, 115-116 are highly soluble, 117 and are ubiquitous components of organic aerosol and cloudwater. Dicarboxylic acids and their condensed phase by-products are removed from the atmosphere by heterogeneous processes (rainout, and aerosol wet and dry deposition) on a time scale of approximately 1 week. 8 Unsaturated carboxylic acids and ketoacids: Unsaturated organic acids are produced as minor products in the ozonolysis of dienes. Acrylic [CH 2 =CHC(O)OH] and methacrylic acids [CH 2 =CCH 3 C(O)OH] are formed following reaction of ozone with isoprene. 110 The dominant atmospheric fate of unsaturated carboxylic acids is reaction with OH radicals which occurs rapidly. Estimates of the atmospheric lifetimes for acrylic and methacrylic acid are 6 and 4 hours, respectively. The reaction occurs via OH addition to the >C=C< double bond, addition of O 2 to give a peroxy radical, reaction with NO to give the corresponding alkoxy radical which undergoes C-C bond scission. The oxidation of methacrylic acid [CH 2 =CCH 3 C(O)OH] gives pyruvic acid [CH 3 C(O)C(O)OH]. Pyruvic acid [CH 3 C(O)C(O)OH] reacts slowly with OH radicals 118 but undergoes rapid photolysis and has a lifetime of a few hours or less. 8

Figure 10 .

 10 Figure 10. Rate constants for reactions of OH radicals with HC(O)OH, CH 3 C(O)OH,

  Blando et al. 129 observed IR absorption features attributable to the presence of organosulfur compounds in particle samples collected in the Smoky Mountains at Look Rock, TN in 1995. It was concluded that secondary formation processes have a large influence on the concentrations, composition, and size distributions of the Smoky Mountain aerosol. OSs were identified in humic-like substances (HULIS) in atmospheric particulate matter (PM 10 ) in the region of Basel, Switzerland. 130 HULIS were separated from inorganic salts by size exclusion chromatography and detected by electrospray ionization. A representative molecular ion was identified at m/z 299 and many of its fragment spectra contained a fragment m/z 97 and a neutral loss of 80 u. Timeof-flight MS and deuterium exchange experiments identified m/z 97 as hydrogen sulfate (HSO 4 -).130 OSs, ONs, and organics containing both sulfates and nitrate groups were identified in the water-soluble organic fractions of aerosol samples collected in summer 2005 in Riverside,CA. 131 Evidence that some of the sulfur occurs as a sulfate moiety was provided by ESI-MS/MS with the loss of 80 u (-SO 3 from m/z 293) and the presence of m/z 97 (HSO 4 -). These fragmentations are consistent with published data of PM 10 material from Switzerland. ONs were identified from the fragments at 63 u (-HNO 3 ) and 62 u (NO 3 -

5 .

 5 Scheme 5. Proposed reaction pathways for the formation of sulfate esters in the photooxidation of

  outlined the OH and NO 3 -initiated DMS oxidation mechanism. The formation of sulfur-containing organics from DMS reaction with the OH radical can be summarized as follow:OH + CH 3 SCH 3 → CH 3 SCH 2 + H 2 O OH + CH 3 SCH 3 (+ M)  CH 3 S(OH)CH 3 (+ M) OH + CH 3 SCH 3 → CH 3 + CH 3 SOH OH + CH 3 SCH 3 → CH 3 S + CH 3 OH M is a third body, typically N 2 or O 2 . CH 3 S(OH)CH 3 + O 2 + M → HO 2 + CH 3 S(O)CH 3 (DMSO) + M CH 3 S(OH)CH 3 + O 2 → CH 3 OO + CH 3 SOH CH 3 S(OH)CH 3 + O 2 → OH + CH 3 S(O) 2 CH 3 (DMSO 2 ) CH 3 S(OH)CH 3 + O 2 → CH 3 + CH 3 S(O) 2 (OH) (MSA)The DMS oxidation products methane sulfonic acid and gas phase sulfuric acid lead to the formation aerosols and can impact climate. It has been postulated that emission of DMS from CH 3 C(O)O 2 +NO → CH 3 +CO 2 + NO 2 Peroxyacetyl radicals are formed in the oxidation of many VOCs. Using a global 3-D chemical transport model (GEOS-Chem)

Figure 11 .

 11 Figure 11. Altitude dependence of PAN (CH 3 C(O)O 2 NO 2 ) lifetime with respect to thermal

Figure 12 . 6 .

 126 Figure 12. POCPs for oxygenated VOCs calculated using SAPRC-07 and MCMv3.1 with a

Table 10 :Figure 13 :

 1013 Figure 13: IR spectra for the five most abundant OVOCs in the atmosphere measured in 700 Torr

  The atmospheric oxidation of all hydrocarbons gives OVOCs. The simplest hydrocarbon is CH 4 which undergoes atmospheric oxidation initiated by reaction with HO radicals to give CH 3 OH, HCHO, HC(O)OH, and CH 3 OOH which are then further oxidized to give CO and ultimately CO 2 . The oxidation of larger hydrocarbons gives rise to a spectacular variety and diversity of OVOCs.Calvert et al. 8 describe the atmospheric oxidation of n-butane leading to the approximately 60 aldehydes, alcohols, organic nitrates, peroxyacyl nitrates, carboxylic acids and percarboxylic acids listed in Table1.produced by hydrogen abstraction from C-H bonds by HO or NO 3 radicals, or via addition to >C=C< double bonds by O 3 , HO, or NO 3 . Peroxy radicals have the general formula RO 2 where R is an organic moiety (e.g., CH 3 , C 2 H 5 , CH 3 C(O)), the simplest example is CH 3 O 2 . Peroxy radicals react with NO, NO 2 other organic peroxy radicals, and with HO 2 radicals. The reaction with NO proceeds via two channels giving alkoxy radicals (RO) and NO 2 and organic nitrates (RONO 2 ). The reaction with other peroxy radicals proceeds via a disproportionation channel and a channel giving alkoxy radicals. The reaction with NO 2 is an association reaction and gives peroxynitrates which are typically unstable with respect to thermal decomposition back to reactants. The reaction with HO 2 radicals gives organic hydroperoxides (ROOH). These reactions are illustrated for the case of CH 3 O 2 below (M is a third body gas, typically N 2 )

	2.1 Biogenic OVOC emissions
	Global emissions of CH 4 are estimated to be 556 Tg in 2011 (354 Tg anthropogenic, 202 Tg
	natural)
	CH 3 O 2 + NO  CH 3 O + NO 2
	CH 3 O 2 + NO + M  CH 3 ONO 2 + M
	CH 3 O 2 + NO 2 + M  CH 3 O 2 NO 2 + M
	CH 3 O 2 + CH 3 O 2  CH 3 OH + HCHO + O 2
	CH 3 O 2 + CH 3 O 2  CH 3 O + CH 3 O + O 2
	CH 3 O 2 + HO 2  CH 3 OOH + O 2
	10

Table 2 :

 2 Global biogenic emissions estimated for the year 200012

	Compound	Emission (Tg yr -1 )	Compound	Emission (Tg yr -1 )
	Isoprene	535	β-Pinene	18.9
	Methanol	99.6	Propene	15.8
	α-Pinene	66.1	Limonene	11.4
	Acetone	43.7	Sabinene	9.0
	Ethene	26.9	Myrcene	8.7
	Ethanol	20.7	Butene	8.0
	Acetaldehyde	20.7	β-Caryophyllene	7.4
	t-β-Ocimene	19.4	Total VOC + OVOC	1007

  [START_REF] Kirstine | [END_REF]

Table 3

 3

	liters)	80			Brazil
	9 Ethanol Fuel Production (10	20 40 60			U.S. Europe World
		0
		1980	1990	Year	2000	2010

shows a listing of the top 20 by mass anthropogenic VOC and OVOC emissions in 2010 in the U.K.; 27 emissions of ethanol and methanol feature highly in both lists. The total emissions in the U.K. in 2010 of anthropogenic VOCs and OVOCs were approximately 540 and 260 ktonnes, respectively. These

Table 3 :

 3 Top

20 VOC and OVOC (by mass)

emissions from anthropogenic sources in the U.K. in 2010.

30 VOC OVOC Species Total emissions ktonnes yr -1 Fraction of the total emissions Species Total emissions ktonnes yr -1 Fraction of the total

	toluene	20.62		0.039	2-propanol	7.99	0.031
			4000
	acetone	19.15		0.036	butyl acetate	7.66	0.030
	ethylene 2-methylbutane pentane m-xylene trichloroethene hexane	3 15.01 tonnes) 13.91 13.71 13.25 12.72 Global DME Production (10 12.22	3000 1000 2000	0.028 0.026 0.026 0.025 0.024 0.023	ethyl acetate DME 4-methyl-2-pentanone 1-propanol 2-butoxyethanol 1-butanol acetaldehyde	7.13 5.62 3.52 3.22 3.21 2.93	0.028 0.022 0.014 0.013 0.013 0.012
	formaldehyde	11.37	0	0.021	1-methoxy-2-propanol	2.22	0.009
			2000 2002 2004 2006 2008 2010 2012 2014
	dichloromethane	11.32		0.021	Year methyl acetate	1.93	0.008
	2-butanone	10.80		0.020	furfural	1.88	0.007
	2-methylpropane	10.49		0.020	1-methoxy-2-propyl acetate 1.71	0.007
	benzene	9.34		0.017	dimethyl ether	1.70	0.007
	2-propanol	7.99		0.015	2-(2-butoxyethoxy)ethanol	1.43	0.006
	decane	7.98		0.015	2-(2-ethoxyethoxy)ethanol	1.34	0.005
							emissions
	ethanol	103.80		0.194	ethanol	103.80	0.407
	butane	54.09		0.101	methanol	30.42	0.119
	ethane	37.62		0.070	acetone	19.15	0.075
	methanol	30.42		0.057	formaldehyde	11.37	0.045
	propane	26.50		0.050	2-butanone	10.80	0.042

  order of hours) implies a much larger flux than for methanol the most abundant OVOC which has much longer atmospheric lifetime (order of weeks). HCHO is one of the most reactive and most important OVOCs in tropospheric photochemistry.

	atmospheric lifetime (
	Tailpipe emission (g/mi)	0.02 0.04 0.06 0.08 0.10		Total Hydrocarbons Methane Ethanol Acetaldehyde NOx Formaldehyde		THC CH 4 C 2 H 5 OH NO x CH 3 CHO
		0.00				HCHO
		0	20	40	60	80	100
				Ethanol (%v)
				20

3

OOH or acetone, depending on location. While HCHO is the fourth most abundant OVOC, its short

Table 4 :

 4 Kinetic data and estimated atmospheric lifetimes for alcohols with respect to gas-phase reactions with OH, O 3 , and NO 3 .

	Compound	k OH (10 -12 ) a  OH	b	k O3 (10 -17 ) a  O3	b	k NO3 (10 -13 ) a  NO3	b,c	 (total lifetime)
	Acyclic and Cyclic Alcohols
	CH 3 OH d	0.9	12.9 d	-	-		0.0013	60 d	10.6 d
	C 2 H 5 OH d	3.2	3.6 d	-	-		0.02	> 4 d	3.6 d
	n-C 3 H 7 OH	5.7	2 d		-	-		0.021	> 4 d	2.0 d
	CH 3 CH(OH)CH 3	5.1	2.3 d	-	-		0.014	6 d	1.7 d
	n-C 4 H 9 OH	8.2	1.4 d	-	-		0.028	> 3 d	1.4 d
	(CH 3 ) 2 CHCH 2 OH	9.6	1.2 d	-	-		-	-	1.2 d
	CH 3 CH 2 CH(OH)CH 3	8.3	1.4 d	-	-		0.02	4 d	1.0 d
	(CH 3 ) 3 COH	1.1	10.5 d	-	-		-	-	10.5 d
	(CH 3 ) 3 CCH 2 OH	5.5	2.1 d	-	-		-	-	2.1 d
	CH 3 (CH 2 ) 3 CH 2 OH	11	1.05 d	-	-		-	-	1.05 d
	CH 3 CH(OH)CH 2 CH 2 CH 3	11	1.05 d	-	-		-	-	1.05 d
	CH 3 CH 2 CH(OH)CH 2 CH 3	13	8.6 h	-	-		-	-	8.6 h
	CH 3 CH(CH 3 )CH 2 CH 2 OH	14	7.9 h	-	-		-	-	7.9 h
	(CH 3 ) 2 C(OH)CH 2 CH 3	3.2	3.6 d	-	-		-	-	3.6 d

a k OH, k NO3 and k O3 : rate constants of the reactions with OH, NO 3 radicals and O 3 in cm 3 molecule -1 s -1 at 298 K and 1 bar, data taken from

Calvert et al. 8 b

Lifetimes estimated by

  2 H 5 OC(O)HCH 3 radicals formed in reaction of the corresponding peroxy radical with NO, approximately 50% undergo prompt decomposition via elimination of CH 3 radicals or H-atoms. The remaining alkoxy radicals are thermalized and undergo decomposition (mainly via C-C bond scission with a minor channel via C-O bond scission) and reaction with O 2 as shown in Scheme 2. the range 2 hours to 12 days. Similarly to aliphatic ethers, the main OH-initiated oxidation products of polyethers and cycloethers are formates and acetates. The oxidation of polyethers and cycloethers oxidation leads to the formation of highly oxygenated compounds such as methoxymethyl formate (CH 3 OCH 2 OCHO) and dimethyl carbonate (CH 3 OC(O)OCH 3 )from dimethoxymethane (CH 3 OCH 2 OCH 3 ),[64][65][66] and methylene glycol diformate (HC(O)OCH 2 OCHO) from 1,3-dioxolane67 . The reaction rate constants of OH with ethylene oxide and propylene oxide are k OH  910 -14 and  510 -13 cm 3 molecule -1 s -1 and these species have lifetimes of approximately 4 months and 1 month, respectively. 3 molecule -1 s -1 for CH 3 C(O)OCH 2 CH 2 OC 2 H 5 and C 2 H 5 OCH 2 CH 2 C(O)OC 2 H , NO 3 and O 3 . Unsaturated ethers are very reactive towards these atmospheric oxidants. The reaction rate constant values are greater than those with the corresponding alkenes indicating an activating effect of the ether group (-O-) on the >C=C< double bond. The rate constant values

	radicals are in
	CH 3 CH 2 OCH 2 CH 3
	OH O 2
	CH 3 CH 2 OCH(OO)CH 3 + H 2 O
	NO
	[CH 3 CH 2 OCH(O)CH 3 ]* + NO 2	CH 3 CHO + HO 2
	Decomposition Stabilization		O 2
	CH 3 + CH 3 CH 2 OCHO	CH 3 CH 2 OCH(O)CH 3	CH 3 CH 2 O + CH 3 CHO
	CH 3 CH 2 OC(O)CH 3 + H	O 2	Decomposition
	2O 2 NO
	HCHO + NO 2 + HO 2	CH 3 CH 2 OC(O)CH 3 + HO 2 CH 3 CH 2 OCHO + CH 3
				2O 2 NO
				HCHO + NO 2 + HO 2
	Scheme 2. OH-initiated oxidation of diethyl ether under atmospheric conditions.
	Polyethers and cyclic ethers with the exception of ethylene oxide (cyclo-C 2 H 4 O-) and propylene
	oxide (CH 3 -cyclo-C 2 H 3 O-) are very reactive towards OH radicals (k OH (1-50)10 -12 cm 3

molecule -1 s -1 , respectively). Their atmospheric lifetimes with respect to reaction with OH The OH reaction rate constants with alkoxyethers are larger than 10 -11 cm 3 molecule -1 s -1 leading to atmospheric lifetimes for these species of 10 hours, or less, in the sunlit troposphere. The available mechanistic data show that the reactions produce mainly carbonyl products such as esters, hydroxyesters, hydroxyaldehydes, alkoxyaldehydes and alkoxyketones. The reactivity of OH radicals with alkoxy esters range from  110

-12

for HC(O)OCH 2 OCH 3 to  (10-20)10 -12 cm 5 . The calculated lifetimes for these compounds range from half a day to around a week. The main OH-initiated oxidation products reported are formates among which some are highly oxygenated, containing four oxygen atoms or more. These species might play a role in secondary organic aerosol (SOA) formation.

OH

Table 5 :

 5 Kinetic data and estimated atmospheric lifetimes for aldehydes with respect to photolysis and gas-phase reactions with OH, O 3 , and NO 3 .

	Compound			k OH (10 -12 ) a	 OH	b	k O3 (10 -18 ) a	 O3	b	k NO3 (10 -14 ) a  NO3	b,c	J d (s -1 )	 h	e	 (total lifetime)
	Acyclic	and	Cyclic
	aldehydes
	HCHO			8.5	1.4 d	-	-		0.058	13.3 d	9.02  10 -5	11 h	8 h
	CH 3 CHO			15.3	7.3 h	-	-		0.257	3 d		7.31  10 -6	6.9 d	6.4h
	CH 3 CH 2 CHO		18.7	5.9 h	-	-		0.63	1.2 d	1.18  10 -5	3.9 d	4.6 h
	n-C 3 H 7 CHO		23.7	4.7 h	-	-		1.14	8.1 d	1.98 × 10 -5	2.3 d	4.2 h
	(CH 3 ) 2 CHCHO		25.6	4.3 h	0.039	0.8 y	1.17	7.9 h	5.91  10 -5	15 h	2.3 h
	n-C 4 H 9 CHO		26.6	4.2 h	-	-		1.62	5.7 h	1.80 × 10 -5	2.5 d	2.3 h
	CH 3 CH 2 CH(CH 3 )CHO	33.3	3.3 h	-	-		2.67	3.5 h	-	-	1.7 h
	(CH 3 ) 2 CHCH 2 CHO		25.9	4.3 h	-	-		2.19	4.2 h	1.81 × 10 -5	2.4 d	2 h
	(CH 3 ) 3 CCHO		26.4	4.2 h	-	-		2.4	3.9 h	2.4 × 10 -5	1.9 d	1.9 h
	n-C 5 H 11 CHO		28.5	4.3 h	-	-		1.61	5.8 h	2.41 × 10 -5	1.9 d	2/3 h
	2-Methylpentanal		33	3.4 h	-	-		2.79	3.3 h	-	-	1.7 h

Table 6 :

 6 Potential reaction products of the OH-initiated oxidation of 2-pentanone (adapted from

	Atkinson et al.). 101
	Alkoxy radicals	Products			Reaction channels
	OCH 2 C(O)CH 2 CH 2 CH 3	HC(O)C(O)CH 2 CH 2 CH 3	reaction with O 2
		HCHO + CH 3 CH 2 CHO	decomposition
		HOCH 2 C(O)CH 2 C(O)CH 3	or	isomerization
		CH 3 CHO	+	2HCHO	or
		CH 3 CH(OH)CH 2 C(O)CHO
	CH 3 C(O)CH(O)CH 2 CH 3	CH 3 C(O)C(O)CH 2 CH 3	reaction with O 2
		CH 3 C(O)CHO + CH 3 CHO and	decomposition
		CH 3 CH 2 CHO + HCHO
	CH 3 C(O)CH 2 CH(O)CH 3	CH 3 C(O)CH 2 C(O)CH 3	reaction with O 2
		CH 3 CHO + 2HCHO	decomposition
		HOCH 2 C(O)CH 2 C(O)CH 3	or	isomerization
		CH 3 CHO + 2HCHO
	CH 3 C(O)CH 2 CH 2 CH 2 (O)	CH 3 C(O)CH 2 CH 2 CHO	reaction with O 2
		CH 3 C(O)CH 2 CHO + HCHO	decomposition

Table 7 .

 7 Henry

	's Law constants H(T) = H(298 K)  [exp(B  ((1/T)-(1/298))], pK a values, and
	effective Henry's Law constants, H*, at 270 K and pH = 5 for selected acids.

Table 8 .

 8 Atmospheric lifetimes, radiative efficiencies, and global warming potentials for selected halogenated OVOCs, unless otherwise indicated data were taken fromHodnebrog et al. 122 Compounds are ordered by GWP.

	Name	Formula	Lifetime	Radiative	Global
			(yr)	efficiency (W m -	Warming
				2 ppb -1 )	Potential
	HFE-125	CHF 2 OCF 3	119.0	0.41	12,400
	PFPMIE, perfluoropolymethylisopropylether	CF 3 OCF(CF 3 )CF 2 OCF 2 O CF 3	800	0.65	9,710
	HFE-227ea	CF 3 CHFOCF 3	51.6	0.44	6,450
	HFE-236ca12 (HG-10)	CHF 2 OCF 2 OCHF 2	25.0	0.65	5,350
	HFE-329mcc2	CHF 2 CF 2 OCF 2 CF 3	22.5	0.53	3,070
	HFE-338pcc13 (HG-01)	CHF 2 OCF 2 CF 2 OCHF 2	12.9	0.86	2,910
	HFE-43-10pccc124 (HG-11)	CHF 2 OCF 2 OC 2 F 4 OCHF 2	13.5	1.02	2,820
	HFE-236ea2 (desflurane)	CHF 2 OCHFCF 3	10.8	0.45	1,790
	HFE-236fa	CF 3 CH 2 OCF 3	7.5	0.36	979
	HFE-245fa1	CHF 2 CH 2 OCF 3	6.6	0.31	828
	HFE-245fa2	CHF 2 OCH 2 CF 3	5.5	0.36	812
	HFE-356pcf2	CHF 2 CH 2 OCF 2 CHF 2	5.7	0.37	719
	HFE-245cb2	CF 3 CF 2 OCH 3	4.9	0.33	654
	HFE-347mcc3 (HFE-7000)	CH 3 OCF 2 CF 2 CF 3	5.0	0.35	530
	HFE-143a	CH 3 OCF 3	4.8	0.18	523
	HCFE-235da2 (isoflurane)	CHF 2 OCHClCF 3	3.5	0.42	491
	HFE-449s1 (HFE-7100)	CH 3 OC 4 F 9 O	4.7	0.36	421
	HFE-347mmz1 (sevoflurane)	(CF 3 ) 2 CHOCH 2 F	2.2	0.32	216
	Trifluoromethyl formate	HC(O)OCF 3	1.0 a	0.31	167 a
	Perfluoroethyl formate	HC(O)OCF 2 CF 3	1.0 a	0.44	165 a
	HFE-569sf2 (HFE-7200)	C 4 F 9 OC 2 H 5	0.8	0.30	57
	2,2,2-Trifluoroethanol	CF 3 CH 2 OH	0.3	0.10	20

a: calculated assuming a lifetime of 1 year, see text.

  3 -carene, β-phellandrene, pinonaldehydes, and glyoxal in the presence of acid aerosols.149 Other precursor compounds for OSs include methylglyoxal, glycoaldehyde, methacrolein, methyl vinyl ketone, 152 and glycolic and lactic acids. It has been recognized recently that aromatic compounds can be important OS precursors,[153][154] the contribution of aromatic OS to total OSs has been measured at 63.5% in winter in Shanghai, China.154 Organic sulfate esters have been identified in laboratory investigations of the SOA formed from acidic seed particles 140 and the photochemical oxidation products of isoprene,[155][156] α-/βpinene, 155,157 limonene 158 and others 142 . Based on results from a series of controlled chamber experiments,Surratt et al. 155 proposed a formation mechanism of sulfate esters via alcohol and aldehyde intermediates generated in the photooxidation of isoprene and α-pinene. In the case of sulfate ester formation from alcohols, the proposed reactions likely involve nucleophilic substitution, where the sulfuric acid protonates the alcoholic group, making water the leaving group.155 Iinuma et al.

  4+ and H + -catalyzed ring opening of IEPOX to form low-volatility OSs, and the enhancement of SOA formation from isoprene under low and high-NOx conditions.

	Low-NOx		OH O 2	HO 2	ISOPOOH	HO OH	OH O	OH	HO	IEPOX O	OH	+ OH 2	NH 4 or H + +	HO	H + O	OH
	High-NOx OH O 2 /NO	O							HO	H + OH	OH			Nu= H 2 O NH 3 SO 4 2-
		O OH O 2		OH 2-methyltetrols OH OH HO	H 2 O	HO	OH	OH SO 4 2-	OSO 3 hydroxy sulfate ester -OH OH HO	HO	OH	OH OSO 3 H
		OO NO 2										hydroxy sulfate ester
		-NO 2 O OONO 2 OH	OH O 2 /NO	OH	O ONO 2 OONO 2			HO	O hydroxy sulfate ester dimer OH OSO 3 -OH OH OH
		O -NO 3		H +		O						H + IEPOX
	O	OH		SO 4 2-	MAE-derived organosulfate OH HO OSO 3 H			higher order hydroxy monosulfate IEPOX monomers ester oligomers from additional

  is shown in scheme 7.

	Isoprene	CH 3 CH 3		pinene
	OH			OH		OH
	MACR	MVK	CH 3 CHO		pinonal
	MGLY		CH 3 C(O)O 2	+	NO	CO 2 + NO 2
			-NO 2	NO 2
			CH 3 C(O)O 2 NO 2
			(PAN)

  3 CH 2 C(O)O 2 NO 2 ), peroxy-n-butyl nitrate (PnBN, CH 3 CH 2 CH 2 C(O)O 2 NO 2 ), peroxybenzoyl nitrate (PBzN, CH 3 CH 2 C(O)O 2 NO 2 ), and 85 peroxymethacryoyl nitrate (MPAN, CH 2 =C(CH 3 )(O)O 2 NO 2

  Organic nitrates represented about a third of the observed nighttime increase in organic aerosol, suggesting the importance of nighttime secondary organic aerosol from NO 3 radicals, produced as a result of anthropogenic NO x emissions, reacting with biogenic organic compounds.Rollins et al. 209 used a simple box model 210 to simulate SOA formation in the NO 3 radical initiated oxidation of limonene. The two reaction sites in limonene react at different rates with NO 3 , leading to one group of compounds with endocyclic double bonds, and another group with exocyclic double bonds. First generation products react with NO 3 at rates depending on the location of the remaining double bond. The simple model of limonene oxidation indicated secondary organic aerosol formation in nighttime NO 3 chemistry is a significant PM source in

	organics. Bakersfield. 209	Altitude (km)	10 -1 0 2 4 6 8 10	10 0	10 1	10 2	10 3 CH 3 C(O)O 2 NO 2 = CH 3 C(O)O 2 + NO 2 10 4 10 5 CH 3 C(O)O 2 NO 2 + hv = products Decomposition and photolysis	10 6

  [START_REF] Derwent | [END_REF]215 It has been adapted to other situations such as Scandinavia213,222 and South East Asia[223][224] .

Jenkin 6 developed a simplified estimation procedure which uses fundamental molecular properties of the VOCs (molecular weight, M; number of C-C and O-H bonds, n B ; and the number of carbon atoms in the molecule, n C ) and the rate constant for reaction with OH radicals, k OH , at 298 K in 760 Torr of air to estimate POCPs using the expression:

Table 9 ,

 9 taken fromDerwent et al., 226 contains the calculated POCPs for a series of oxygenated VOCs using the MCMv3.1 and SAPRC-07 mechanisms for selected test scenarios representing highly idealized ambient environmental conditions. The atmospheric oxidation of benzaldehyde leads to the formation of benzylperoxynitrate, C 6 H 5 C(O)OONO 2 , and nitrophenol which scavenge NOx resulting in a negative photochemical formation potential for benzaldehyde.Methylbenzaldehydes have similar oxidation mechanisms to benzaldehyde and also have negative POCPs. The scatterplot in Figure12shows that only a limited number of OVOCs exhibited inconsistent POCPs calculated using the MCMv3.1 and SAPRC-07 chemical mechanisms. Both sets of POCPs increase broadly with increasing k OH reactivity and the general pattern of reactivity within the oxygenate classes was similar using MCMv3.1 and SAPRC-07.The POCPs determined using both chemical mechanisms follow each other closely. This indicates that the representations of the mechanistic reactivities of the oxygenated are consistent.Derwent et al. 226 have concluded that MCMv3.1 and SAPRC-07 are able to characterize the reactivities of most of the oxygenated VOCs in a consistent, quantitative manner. The mechanisms used in MCMv3.1 and SAPRC-07 which are probably attributable to the lack of complete experimental data for the atmospheric degradation processes of these species. The list of these compounds includes glyoxal, methacrolein, i-propanol, 3-methyl-1-butanol, cyclohexanol and diacetone alcohol.Derwent et al. 226 attributed the observed discrepancies to the fact that the atmospheric degradation mechanisms for these species are not adequately described by the available experimental data.

Table 9 :

 9 OH reaction rate constants with oxygenated VOCs and POCPs estimated using different chemical mechanisms. k OH : rate constants of the reactions with OH radicals in cm 3 molecule -1 s -1 at 298 K and 1 bar, data taken from Calvert et al.[START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF] b fromDerwent et al. 226

	Compound	Formula	k OH (10 -12 ) a	SAPRC-07 b	MCMv3.1 b
				POCP s.d. c POCP	s.d. c
	Alcohols
	Methanol	CH 3 OH	0.9	7	0	8
	Ethanol	C 2 H 5 OH	3.2	14	2	17
	Propanol	C 3 H 7 OH	5.7	24	4	30
	i-Propanol	CH 3 CH(OH)CH 3	5.1	6	1	13
	n-Butanol	C 4 H 9 OH	8.2	28	4	35
	i-Butanol	(CH 3 ) 2 CHCH 2 OH	9.6	25	3	34
	sec-Butanol	CH 3 CH 2 CH(OH)CH 3	8.3	13	2	26
	3-Methyl-1-butanol	(CH 3 ) 2 CHCH 2 CH 2 OH	14	32	3	47
	Cyclohexanol	C 6 H 11 OH	17	19	4	45
	Glycols
	Ethylene glycol	HOCH 2 CH 2 OH	14	31	3	25
	Propylene glycol	CH 3 CH(OH)CH 2 OH	21	26	2	29
	Ethers
	Dimethylether	CH 3 OCH 3	0.27	8	1	18
	Diethylether	C 2 H 5 OC 2 H 5	12.2	40	2	53
	Di-i-propylether	(CH 3 ) 2 CHOCH(CH 3 ) 2	10.0	39	2	41
	Alkoxyethers
	2-Methoxyethanol	CH 3 OCH 2 CH 2 OH	13	31	1	34
	1-Methoxy-2-propanol	CH 3 OCH 2 CH(OH)CH 3	20	25	3	32
	2-Ethoxyethanol	CH 3 CH 2 OCH 2 CH 2 OH	19	39	2	42
	2-Butoxyethanol	C 4 H 9 OCH 2 CH 2 OH	30	30	2	38

a c s.d.: standard deviation POCP SAPRC-07

CH 3 CH(OH)CH(CH 3 ) 2

2,5-Dimethylphenol

Acknowledgments

Acknowledgments

The Labex Voltaire (ANR-10-LABX-100-01), the IRSES-EU Marie Curie Actions project "AMIS" (PIRSES-GA-2011-295132) the National Natural Science Foundation of China (No. 21190053) for support and Taishan Scholar Grant (ts20120552). We thank Øivind Hodnebrog for calculating the REs and GWPs for CH 3 OH, CH 3 C(O)CH 3 , CH 3 OOH, HCHO, and CH 3 CHO

the oceans acts as a negative feedback mechanism where biota can regulate the climate. 189 The idea, which has become known as the CLAW hypothesis (acronym of author names), is that increased ocean temperature causes increased phytoplankton activity leading to increased DMS emissions, increased cloud condensation nuclei, increased cloud albedo and reflection of solar radiation, and hence a negative feedback regulating global temperature. Interestingly, one of the authors of the CLAW hypothesis subsequently proposed there may be an anti-CLAW hypothesis positive feedback on climate. Increased temperatures could lead to increased stratification of the oceans, lower nutrient availability, lower phytoplankton activity, lower DMS emissions, lower cloud albedo and a positive feedback on global temperature. 190 While the sign and magnitude of the biological feedback mechanism regulating climate through DMS emissions is currently unclear it is clear that the gas-phase oxidation of DMS may have a significant influence on the Earth's radiation budget. PAN (CH 3 (O)O 2 NO 2 ) and peroxyacyl nitrates in general (R(O)O 2 NO 2 ) are well known components of photochemical smog and are formed by reactions involving VOCs and NO x . PAN was first observed in photochemical smog in California in the 1950s [191][192] and is now recognized to be a ubiquitous trace gas in the troposphere 33,193 . PAN is formed in the association reaction of peroxyacetyl radicals (CH 3 C(O)O 2 ) and NO 2 .

different VOCs to contribute to ozone formation has led to development of tools to quantify their ability to produce ground level ozone. Several different concepts for VOC ranking have been suggested and most of them include the use of atmospheric models. Atmospheric photochemical models describe the chemical and meteorological features of the atmosphere and are used to study atmospheric processes. Two scales are in common use to rank the ability of VOCs to contribute to ozone formation. Most focus to date has been placed on understanding local and regional ozone production. The scales in common use describe the ability of VOCs to contribute to local and regional ozone. It should be noted that longer lived VOCs can still contribute to ozone formation but on a larger spatial scale. To capture the effects on local and regional scales Maximum Incremental Reactivities (MIR) values are typically used in the US. [211][212] Photochemical Ozone Creation Potentials (POCP) values are typically used in Europe. [START_REF] Derwent | [END_REF][213][214][215][216] The MIR scale was developed to rank the ozone formation from different organic compounds when released in urban areas. 212,217 This reactivity scale is based on calculations of the absolute ozone impact, expressed as the number of grams of ozone formed per gram of VOC, when the VOC is added to the emissions in the model. MIRs have units of g O 3 / g VOC. MIRs can be computed for different chemical and atmospheric conditions. MIRs are based on model calculations of the effects of additions of VOCs on ozone formation in one-day box model

Where k OH ethene is the rate constant for the reaction of OH radicals with ethene at 298 K and 760

Torr of air (k OH ethene = 7.810 -12 cm 3 molecule -1 s -1 225 ). Jenkin showed that this approach can be used to estimate POCPs for a large variety of VOCs but that it overestimates ozone formation from VOCs whose atmospheric oxidation produces significant yields of unreactive products, in particular acetone, formates and alkyl nitrates. [START_REF] Derwent | [END_REF][START_REF] Jenkin | Photochemical ozone and PAN creation potentials: rationalisation and methods of estimation[END_REF] Acetone is relatively unreactive (k OH = 1.810 - 13 cm 3 molecule -1 s -1 at 298 K and 760 Torr 225 ) and its formation significantly inhibits the ability of the precursor VOC to generate ozone on the timescale of the trajectory calculation. The formation of organic nitrates inhibits ozone formation because they act as comparatively unreactive reservoirs for NO x and free radicals. 221 Good agreement was obtained between results from this simple estimation technique and those calculated using photochemical models for a large number of VOCs but discrepancies have been observed for some oxygenated VOCs as discussed by Jenkin. [START_REF] Jenkin | Photochemical ozone and PAN creation potentials: rationalisation and methods of estimation[END_REF] Derwent et al. 226 calculated POCP for 116 organic compounds representing different classes of organic compounds (alkanes, alkenes, aldehydes, ketones, aromatics, oxygenates, and halocarbons) using the Master Chemical Mechanism (MCMv3.1) and compared with those shown in Table 10. While this article is believed to contain correct information, Ford Motor Company (Ford) does not expressly or impliedly warrant, nor assume any responsibility, for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, nor represent that its use would not infringe the rights of third parties. Reference to any commercial product or process does not constitute its endorsement. This article does not provide financial, safety, medical, consumer product, or public policy advice or recommendation. Readers should independently replicate all experiments, calculations, and results. The views and opinions expressed are of the authors and do not necessarily reflect those of Ford. This disclaimer may not be removed, altered, superseded or modified without prior Ford permission.

Abdelwahid Mellouki was born in