Carbonaceous Particle Hydration III

Previous soot hydration studies have been extended to compare the water uptake properties of soots from selected fuels (JP-8 Jet fuel, kerosene, diesel, and metal containing and S-containing synthetics) prepared under varying conditions with corresponding n-hexane model soots. Adsorption and desorption isotherms have yielded such adsorption parameters as the surface coverages at the limit of chemisorption and at 83% relative humidity (RH). These values increase with soot surface oxidation over the range 35–85% RH, while hydration levels at lower RH down to 22% are a function of fuel composition and combustion conditions, thus determining the extent of water uptake at higher RH. Both S- and metal-containing soots exhibit higher levels of hydration than those of the base fuel soots, a result with its origin in availability of sulfate and metal centers at the surface.     

The Effect of Temperature and Humidity on the Reaction of Ozone with Combustion Soot: Implications for Reactivity near the Tropopause

The effect of temperature (296–238 K) on the reaction of combustion soot (n-hexane) with ozone at low concentration (6–8 ppm) has been measured. Long optical path FTIR spectroscopy has revealed the rate law for ozone loss beyond initial stages, second order in O₃, to be the same over this range of conditions. The reaction rate is 3.5 times lower at 238 K than at 296 K, and reveals an activation energy of 12.9 ± 0.5 kJ mol^–1. The effect of humidity on the reaction has been estimated using its recently determined rate law dependence (p^0.2). These data, differing from O₃ reaction kinetics obtained from other types of carbonaceous particles used as surrogates for atmospheric soot, have implications for the role of combustion soot in atmospheric chemistry. Any involvement of aircraft soot in ozone depletion near the tropopause, for example, should be estimated using these temperature and humidity dependences.     

Formulation and Evaluation of IMS, an Interactive Three-Dimensional Tropospheric Chemical Transport Model 2. Model Chemistry and Comparison of Modelled CH4, CO, and O3 with Surface Measurements

In part two of this series of papers on the IMS model, we present the chemistry reaction mechanism usedand compare modelled CH₄, CO, and O₃ witha dataset of annual surface measurements. The modelled monthly and 24-hour mean tropospheric OH concentrationsrange between 5–22 × 10⁵ moleculescm^–3, indicating an annualaveraged OH concentration of about 10 × 10⁵ moleculescm^–3. This valueis close to the estimated 9.7 ± 0.6 × 10⁵ moleculescm^–3 calculated fromthe reaction of CH₃CCl₃ with OH radicals.Comparison with CH₄ generally shows good agreementbetween model and measurements, except for the site at Barrow where modelledwetland emission in the summer could be a factor 3 too high.For CO, the pronounced seasonality shown in the measurements is generally reproduced by the model; however, the modelled concentrations are lower thanthe measurements. This discrepancy may due to lower the CO emission,especially from biomass burning,used in the model compared with other studies.For O₃, good agreement between the model and measurements is seenat locations which are away from industrial regions. The maximum discrepancies between modelled results and measurementsat tropical and remote marine sites is about 5–10 ppbv,while the discrepancies canexceed 30 ppbv in the industrial regions.Comparisons in rural areas at European and American continental sites arehighly influenced by the local photochemicalproduction, which is difficult to model with a coarse global CTM.The very large variations of O₃ at these locations vary from about15–25 ppbv in Januaryto 55–65 ppbv in July–August. The observed annual O₃amplitude isabout 40 ppbv compared with about 20 ppbv in the model. An overall comparison of modelled O₃ with measurements shows thatthe O₃seasonal surface cycle is generally governed bythe relative importance of two key mechanisms that drivea springtime ozone maximum and asummertime ozone maximum.     

Estimates of the Chemical Budget for Ozone at Waliguan Observatory

Waliguan Observatory (WO) is an in-land Global Atmosphere Watch (GAW) baseline station on the Tibetan plateau. In addition to the routine GAW measurement program at WO, measurements of trace gases, especially ozone precursors, were made for some periods from 1994 to 1996. The ozone chemical budget at WO was estimated using a box model constrained by these measured trace gas concentrations and meteorological variables. Air masses at WO are usually affected by the boundary layer (BL) in the daytime associated with an upslope flow, while it is affected by the free troposphere (FT) at night associated with a downslope flow. An anti-relationship between ozone and water vapor concentrations at WO is found by investigating the average diurnal cycle pattern of ozone and water vapor under clear sky conditions. This relationship implies that air masses at WO have both the FT and BL characteristics. Model simulations were carried out for clear sky conditions in January and July of 1996, respectively. The chemical characteristics of mixed air masses (MC) and of free tropospheric air masses (FT) at WO were investigated. The effects of the variation in NO_x and water vapor concentrations on the chemical budget of ozone at WO were evaluated for the considered periods of time. It was shown that ozone was net produced in January and net destroyed in July for both FT and MC conditions at WO. The estimated net ozone production rate at WO was –0.1 to 0.4 ppbv day^–1 in FT air of January, 0.0 to 1.0 ppbv day^–1 in MC air of January, –4.9 to –0.2 ppbv day^–1 in FT air of July, and –5.1 to 2.1 ppbv day^–1 in MC air of July.     

A Seasonal Comparison of the Ozone Photochemistry in Clean and Polluted Air Masses at Mace Head, Ireland

Measurements of the sum of peroxy radicals [HO₂ + RO₂],NO_x (NO + NO₂) and NO_y (the sum of oxidisednitrogen species) made at Mace Head, on the Atlantic coast of Ireland in summer 1996 and spring 1997 are presented. Together with a suite of ancillary measurements, including the photolysis frequencies of O₃ O(¹D)(j(O¹D)) and NO₂ (j(NO₂)), the measured peroxy radicals are used to calculate meandailyozone tendency (defined as the difference of the in-situphotochemical ozone production and loss rates); these values are compared with values derived from the photochemical stationary state (PSS) expression. Although the correlation between the two sets of values is good, the PSS values are found to be significantly larger than those derived from the peroxy radical measurements, on average, in line with previous published work. Possible sources of error in these calculations are discussed in detail. The data are further divided up into five wind sectors, according to the instantaneous wind direction measured at the research station. Calculation of mean ozone tendencies by wind sector shows that ozone productivity was higher during spring (April–May) 1997 than during summer (July–August) 1996across all airmasses, suggesting that tropospheric photochemistry plays an important role in the widely-reported spring ozone maximum in the Northern Hemisphere. Ozone tendencies were close to zero for the relatively unpolluted south-west, west and north-west wind sectors in the summer campaign, whereas ozone productivity was greatest in the polluted south-east sector for both campaigns. Daytime weighted average ozone tendencies were +(0.3± 0.1) ppbv h^–1 for summer 1996 and +(1.0± 0.5) ppbvh^–1 for spring 1997. These figures reflect the higher mixing ratios of ozone precursors in spring overall, as well as the higher proportion of polluted air masses from the south-east arriving at the site during the spring campaign. The ozone compensation point, where photochemical ozone destruction and production processes are in balance, is calculated to be ca. 14 pptv NO for both campaigns.     

Persistent high concentration of ozone during windstorm conditions in southern Korea

Summary Prior to and following the development of a windstorm in the mountainous coastal area of southern Korea, ground level ozone (O₃)-concentrations near Kangnung city, on the lee side of the mountains, show a maximum value at approximately 1300 LST, owing to a photolytic cycle of NO₂–NO–O₃ during the day and a minimum in concentrations at night as a result of the reverse cycle. During the development period of the windstorm, ozone concentrations are generally high all day, and slightly higher during the night. This distribution pattern of ozone is very different from the typical distribution of ozone in the absence of windstorms. High daytime concentrations of ozone during the windstorm are due to both the increase in the amount of ozone from photochemical reactions involving NO_x and the increase in O₃-concentration due to a decrease in the convective boundary layer thickness under the influence of downslope windstorm conditions on the lee-side of the mountains. At night, the windstorm increases in intensity as the westerly winds combine with a katabatic wind blowing downslope toward the surface at the coast. This causes momentum transport of air parcels in the upper levels toward the surface at the coast and the development of internal gravity waves, which generate a hydraulic jump directed upward over the coast and the East sea, thereby reducing to very thin the thickness of the nocturnal surface inversion layer (NSIL). The higher O₃-concentration at night depends mainly upon the shallow NSIL and on some O₃ being transported by the momentum transfer from the upper troposphere toward the ground in windstorm conditions.     

Photochemical Effects in the Heterogeneous Reaction of Soot with Ozone at Low Concentrations

The soot-ozone reaction at low concentrations (ppm O₃) hasbeen examined todetermine any influence of solar radiation on its products and kinetics. Theeffect of simulatedsolar radiation is to change the product distribution towardsCO₂(g), CO (g) and H₂O(g) at theexpense of soot surface functional groups formation. Little effect on theextent or rate ofdiminution of O₃ through this rapid reaction is observed. Theinitial rate laws for formation ofall products remain the same under simulated solar radiation, with changes inthe rate constants(and thus in the relative importance of mechanistic pathways) responsible forthe differingproduct distributions. Decarboxylation of soot surface functionalities hasbeen shown to be onepossible mechanism underlying these effects. Atmospheric soot, particularlythat emitted nearthe tropopause by increasing numbers of subsonic and supersonic aircraft, mayplay a role inozone depletion; the rapid diminution of ozone in soot's presence isunaffected by solarradiation.     

Ozone and PAN Formation Inside and Outside of the Berlin Plume – Process Analysis and Numerical Process Simulation

During the BERLIOZ field phase on 20 July 1998 a 40 km wide ozone-plume 30 to 70 km north of Berlin in the lee of the city was detected. The ozone mixing ratio inside the plume was app. 15 ppb higher than outside, mainly caused by high ozone precursor emissions in Berlin, resulting in a net chemical ozone production of 6.5 ppb h^–1, which overcompensates ozone advection of –3.6 ppb h^–1 andturbulent diffusion of –1.1 ppb h^–1. That means, although moreozone leaves the control volume far in the lee of Berlin than enters it at the leeside cityborder and although turbulent diffusion causes a loss of ozone in the leeside control volume the chemical production inside the volume leads to a net ozone increase. Using a semi-Lagrangian mass budget method to estimate the net ozone production, 5.0 ppb h^–1 are calculated for theplume. This means a fraction of about 20% of ozone in the plume is producedby local emissions, therefore called `home made' by the Berlin emissions. For the same area KAMM/DRAIS simulations using an observation based initialisation, results in a net production rate between 4.0 and 6.5 ppbh^–1, while the threefold nested EURAD model gives 6.0 ppbh^–1. The process analysis indicates in many cases goodagreement (10% or better) between measurements and simulations not only in the ozone concentrations but also with respect to the physical and chemical processes governing the total change. Remaining differences are caused by different resolution in time and space of the models and measurements as well as by errors in the emission calculation.The upwind-downwind differences in PAN concentrations are partly similar to those of ozone, because in the BERLIOZ case they are governed mainly by photochemical production. While in the stable boundary layer at night and windward of Berlin 0.1 to 0.3 ppb are detected, in the centre of the plume at noon concentrations between 0.75 ppb and 1.0 ppb are measured. The O₃/PAN ratio is about 80 to 120 and thus due to the relatively lowPAN concentrations significantly higher than found in previous studies. The low PAN formation on 20 July, was mainly restricted by the moderate nonmethane hydrocarbon levels, whereas high PAN concentrations of 3.0 ppb on 21 July, are caused by local production in the boundary layer and by large scale advection aloft.     

Effects of high CO2 levels on surface temperature and atmospheric oxidation state of the early Earth

One-dimensional radiative-convective and photochemical models are used to examine the effects of enhanced CO₂ concentrations on the surface temperature of the early Earth and the composition of the prebiotic atmosphere. Carbon dioxide concentrations of the order of 100–1000 times the present level are required to compensate for an expected solar luminosity decrease of 25–30%, if CO₂ and H₂O were the only greenhouse gases present. The primitive stratosphere was cold and dry, with a maximum H₂O volume mixing ratio of 10^–6. The atmospheric oxidation state was controlled by the balance between volcanic emission of reduced gases, photo-stimulated oxidation of dissolved Fe⁺² in the oceans, escape of hydrogen to space, and rainout of H₂O₂ and H₂CO. At high CO₂ levels, production of hydrogen owing to rainout of H₂O₂ would have kept the H₂ mixing ratio above 2×10^–4 and the ground-level O₂ mixing ratio below 10^–11, even if no other sources of hydrogen were present. Increased solar UV fluxes could have led to small changes in the ground-level mixing ratios of both O₂ and H₂.     

Segregation and Interpretation of Ozone and Carbon Monoxide Measurements by Air Mass Origin at the TOR Station Mace Head, Ireland from 1987 to 1995

Three independent methods have been used to sort the ozone, carbonmonoxide, and other radiatively important trace gases measured at Mace Head,Ireland, and thereby distinguish clean air masses transported over the NorthAtlantic from the more polluted air masses which have recently travelledfrom the European continent. Over the period April 1987–June 1995 theNorthern Hemisphere surface ozone baseline concentrations exhibited a meanconcentration of 34.8 ppb, with a small positive trend (+0.19 ppbyr^-1), while the corresponding trend in air originating fromthe polluted European areas was negative (–0.39 ppbyr^-1). Carbon monoxide measurements from March 1990 toDecember 1994 showed negative trends for both the unpolluted (–0.17ppb yr^-1) and polluted data (–13.6 ppbyr^-1). Overall the continent of Europe was shown to be a smallnet sink of 2.6 ppb for all occasions when European air was transported tothe North Atlantic.     

Characteristics of the ozone decline in the northern polar and middle latitudes during the winter-spring

Summary The total ozone decline during the past twenty years, especially strong during the winter-spring season poleward from 50° N, is well established with known average trends of 5–7% per decade. This study presents a number of additional characteristics such as ozone-mass deficiency (O₃MD) from the pre- 1976 base average, and areal extent with negative deviations greater than2 and3. Gridded satellite data combined with ground-based total ozone maps, permit calculations of daily and regional ozone deficiencies from the anthropogenically undisturbed average ozone levels of the 1960s and early 1970s. Then the quantity of the O₃MD and the changes in surface area, with deficiencies larger than-10 and-15% are integrated for the 1 January to 15 April period for each of the last 20 years, and compared. In addition, the polar vortex extent during the last 10 years is determined using the PV at 475°K. The quantity of the O₃MD within the sunlit part of the vortex is shown to contribute from15 to 35% of the overall ozone deficiency within the-10% contours over the area 35–90°N. The ozone deficiency, integrated for the first 105 days of each year, has increased dramatically from 2,800Mt in the early 1980s to7,800Mt in the 1990s, exceeded 12,000Mt in the winter-springs of 1993 and 1995. The latter quantity is comparable with the average O₃MD over the same Southern latitudes in the last ten austral springs. During the 1990s over the 35–90° latitudes the average ozone deficiency in the Southern hemisphere belt is less than over the Northern hemisphere belt by40%. It is known that the main ozone decline is observed in the lower stratosphere and the ozone loss over the Arctic is very sensitive to decreasing stratospheric temperatures; negative 50hPa monthly anomalies greater than 4°C have occurred during 7 of the springs in the last decade, thus possibly facilitating doubling the area with negative ozone deviations greater than-10% in the 1990s to5,000.10⁶km² and nearly tripling the O₃MD as stated above. The changes in total eddy heat fluxes as a proxy indicator of the long wave perturbations are positively correlated with the ozone deficiency in the 45–75°N. The strong anticorrelation between the ozone deficiency in the region>55° N. versus the 35–50° N belt is discussed in relation to possible transport of air masses with low ozone from the sub-tropics, which in some years are the dominant reason for the observed ozone deficiency.With 11 Figures     

Active Nitrogen in Surface Ozone Depletion Events at Alert during Spring 1998

Measurements of NO_x,y were made at Alert, Nunavut, Canada (82.5° N, 62.3° W) during surface layer ozone depletion events. In spring 1998, depletion events were rare and occurred under variable actinic flux, ice fog, and snowfall conditions. NO_y changed by less than 10% between normal, partially depleted, and nearly completely depleted ozone air masses. The observation of a diurnal variation in NO_x under continuous sunlight supports a source from the snowpack but with rapid conversion to nitrogen reservoirs that are primarily deposited to the surface or airborne ice crystals. It was unclear whether NO_x was reduced or enhanced in different stages of the ozone depletion chemistry because of variations in solar and ambient conditions. Because ozone was depleted from 15–20 ppbv to less than 1 ppbv in just over a day in one event it is apparent that the surface source of NO_x did not grossly inhibit the removal of ozone. In another case ozone was shown to be destroyed to less than the 0.5 ppbv detection limit of the instrument. However, simple model calculations show that the rate of depletion of ozone and its final steady-state abundance depend sensitively on the strength of the surface source of NO_x due to competition from ozone production involving NO_x and peroxy radicals. The behavior of the NO/NO₂ ratio was qualitatively consistent with enhanced BrO during the period of active ozone destruction. The model is also used to emphasize that the diurnal partitioning of BrO_x during ozone depletion events is sensitive to even sub ppbv variations in O₃.     

Concentrations of atmospheric constituents observed at Alert,Canada, in relation to air trajectories and synoptic systems

A meteorological analysis is presented for environmental data set obtained from the Canadian Arctic haze study, which is part of AGASP-II. Results of the study indicated that atmospheric carbon dioxide (CO₂), methane (CH₄), sulphate (SO₄ ⁼), ozone (O₃) and other air pollutants observed at Alert, N.W.T. underwent periodical fluctuations. It was found that high concentrations of these atmospheric constituents were associated with a deep (1430–2074 m) inversion and with a major anticyclone. In contrast, relatively low values of these constituents were associated with a cyclonic disturbance near Alert. High concentrations of these constituents occurred with air trajectories coming from the N-W direction, while low values occurred with S trajectories. In addition, examinations of satellite imagery with other meteorological data suggested that volcanic inputs of ash and gases from Augustine Island, Alaska were negligible for the observed high values of these constituents at the ground level at Alert.     

Surface ozone values in anomalous summer 2010 measured in Obninsk

Given and analyzed are the results of the measuring of concentration of ozone O₃, nitrogen oxides NO_x, and carbon monoxide CO at the surface as well as the sum of hydrocarbons and the aerosol optical depth in Obninsk (Kaluga oblast) during the warm period 2010 and 2011. The relationship between the air temperature and the maximum daily ozone values in May–September 2010 are characterized by the higher correlation coefficient than in May–September 2011: 0.82 ± 0.05 versus 0.64 ± 0.07. Increased concentration of surface ozone in Obninsk in July–August 2010 as compared to the similar period in 2011 were caused by the higher concentrations of the compounds-predecessors of ozone. The concentration of O₃ in August 2010 exceeded 200μg/m³ and was never registered in Obninsk during the observation period of 2004–2011. This is associated with the air masses that came to Obninsk from the areas with peat and forest fires that resulted in the dramatic increase in surface concentrations of NO_x, CO, and hydrocarbons.     

Correlations among combustion effluent species at Barrow,Alaska: Aerosol black carbon,carbon dioxide,and methane

As part of the second Arctic Gas and Aerosol Sampling Program (AGASP II) continuous measurements of atmospheric aerosol black carbon (BC) were made at the NOAA/GMCC observatory at Barrow, Alaska (71°19N, 156°36W) during the period March 21–April 22, 1986. Black carbon is produced only by incomplete combustion of carbonaceous materials and so is a particularly useful atmospheric indicator of anthropogenic activities. The BC data have been analyzed together with the concurrent measurements of carbon dioxide (CO₂), methane (CH₄), and condensation nuclei (CN) that are routinely made at the observatory. All four species showed elevated and highly variable concentrations due to local human activities, principally in the township of Barrow, 7 km to the southwest, and at the DEW Line radar installation 1 km to the northwest. We distinguish between those periods of the record that are affected by local activities and those that are not, on the basis of the short-term (periods of up to 1 hour) variability of the continuous CO₂ and CN records, with large short-term variabilities indicating local sources. We identified seven periods of time (events) with durations ranging from 13 to 37 hours when the BC, CO₂, and CH₄ concentrations changed smoothly over time, were highly correlated with each other, and were not influenced by local activities. These events had BC/CO₂ ratios in the range (50–103)×10^–6. These ratios are dimensionless since we convert the CO₂ concentrations to units of ng m^–3 of carbon. Such values of BC/CO₂ are characteristic of the combustion effluent from large installations burning heavy fuel oil or coal, automobiles, and domestic-scale natural gas usage. We conclude that these events are indicative of air masses that have been polluted with combustion emissions in a distant location and then transported to the Arctic. In the absence of species-selective loss mechanisms, these air masses will maintain their combustion effluent signatures during the transport. The BC/CO₂ ratios found for the local combustion activities are consistent with those expected from known combustion processes.     

华南地区春季平流层入侵对对流层低层臭氧影响的模拟研究

利用中尺度大气化学模式WRF/Chem对2013年3月6日华南地区一次平流层入侵事件及其对对流层低层臭氧的影响进行模拟研究。通过加入UBC（Upper Boundary Condition）上边界处理方案,弥补WRF/Chem模式未考虑平流层臭氧化学反应的不足。结合臭氧探空廓线资料、地面O₃、CO、NO_x、相对湿度、温度和风速等观测资料以及再分析资料对模拟结果进行定量评估,结果表明模式能较为真实地模拟本次平流层入侵过程。模拟分析进一步揭示:（1）副热带高空急流是本次平流层入侵的主要原因。当华南地区处在副热带急流入口区左侧下沉区域时,平流层入侵将富含臭氧的干燥空气输送到对流层中低层。（2）本次平流层入侵对对流层低层臭氧收支有重要影响,导致香港地区近地层臭氧体积混合比浓度明显上升,如塔门站夜间臭氧浓度升高21.3 ppb（1 ppb=1×10-9）。地面气象场和化学物种的分析进一步确认了平流层入侵的贡献。（3）采用动力学对流层顶高度时零维箱式模型和Wei公式计算得到的平流层入侵通量相当,分别为-1.42×10-3 kg m-2 s-1和-1.59×10-3 kg m-2 s-1,这一结果与前人研究相吻合,且与采用热力学对流层顶高度计算所得到的结果具有可比性。     

Arctic hazes in summer over Greenland and the North American Arctic. I: Incidence and origins

Airborne observations during August 1985 over Greenland and the North American Arctic revealed that dense, discrete haze layers were common above 850 mb. No such hazes were found near the surface in areas remote from local sources of particles. The haze layers aloft were characterized by large light-scattering coefficients due to dry particles (maximum value 1.24 × 10^–4m^–1) and relatively high total particle concentrations (maximum value 3100 cm^–3). Sulfate was the dominant ionic component of the aerosol (0.06 – 1.9 g m^–3); carbon soot was also present. Evidence for relatively fresh aerosols, accompanied by NO₂ and O₃ depletion, was found near, but not within, the haze layers. The hazes probably derived from anthropogenic sources and/or biomass burning at midlatitudes.It is hypothesized that the scavenging of particles by stratus clouds plays an important role in reducing the frequency and intensity of hazes at the surface in the Arctic in summer. Since the detection of haze layers aloft through measurements of column-integrated parameters from the surface (e.g., by lidar) cannot be carried out reliably when clouds are present, such measurements have likely underestimated the occurrence of haze layers in the Arctic, particularly in summer.     

Laboratory study of the rates and products of the phototransformations of naphthalene adsorbed on samples of titanium dioxide,ferric oxide,muscovite, and fly ash

The photodegradation of naphthalene (NPH), chosen as a model of polynuclear aromatic pollutants, has been studied in the presence of a layer of four water-insoluble inorganic solids which can be found in the troposphere (TiO₂, Fe₂O₃, muscovite, and a fly ash sample). Direct photolysis of NPH is negligible at >340 nm. Dark adsorption of NPH on TiO₂ (mainly anatase, nonporous, 50 m² g^–1) at 293 K corresponds to a surface coverage ofca. 50% at equilibrium. Under these conditions (saturated surface), the stationary-state photocatalytic degradation reaches 0.4 molecule nm^–2 h^–1 (>340 nm, radiant fluxca. 22 mW cm^–2). Dioxygen is required and its partial pressure in air is such that the degradation is zero order in O₂. Water vapor markedly increases the rate. The other particulates have also an effect, less important than that of TiO₂, however quite noticeable with respect to surface area unit for the fly ash sample which contains 3.2% Fe₂O₃. Apart from 1,4-naphthoquinone, which is the main intermediate product in all cases, 2-naphthol, phthalide, phthaldialdehyde, phthalic acid, acetophenone, benzaldehyde, benzoic acid are also formed on dry TiO₂. Depending on their volatility, these compounds are transferred to the gas phase or remain principally adsorbed on the solid particles where they are further transformed. For instance, phthalic acid (or anhydride) and benzoic acid are generated from 1,4-naphthoquinone. Degradation mechanisms are briefly discussed.     

The Gas Phase Reaction of Unsaturated Oxygenates with Ozone: Carbonyl Products and Comparison with the Alkene-Ozone Reaction

Carbonyl products have been identified and their formation yields measured in the gas phase reaction of ozone with unsaturated oxygenates in experiments carried out at ambient T, p = 1 atm. of purified humid air (RH = 50%) and with sufficient cyclohexane added to scavenge the hydroxyl radical. The compounds studied are the esters methyl acrylate, vinyl acetate and cis-3-hexenyl acetate, the carbonyl crotonaldehyde, the hydroxy-substituted diene linalool, the ether ethylvinyl ether and the keto-ether trans-4-methoxy-3-buten-2-one. The alkene 1-pentene was included for comparison. The nature and formation yields of the carbonyl products from this study and those measured in earlier work under the same conditions are compared to those of alkenes and are supportive of a reaction mechanism that is similar to that for the reaction of ozone with alkenes, i.e. O₃ + R₁R₂C=CR₃X (R₁COR₂ + R₃XCOO) + (1 – )(R₃COX + R₁R₂COO), where R_i are the alkyl substituents, X is the oxygen-containing substituent (–CHO for aldehydes; –C(O)R for ketones; –C(O)OR and –OC(O)R for esters; –OH and hydroxyalkyl for alcohols; and –OR for ethers), R₁COR₂ is the primary carbonyl, R₃COX is the other primary product and R₁R₂COO and R₃XCOO are the carbonyl oxide biradicals. The biradicals lead to carbonyls in reactions that are also analogous to those involved in carbonyl formation from biradicals in the ozone-alkene reaction. These features make it possible to predict the nature and formation yields of the major carbonyl products of the reaction of ozone with unsaturated oxygenates that may be components of biogenic emissions.