The Effect of Air/Fuel Ratio on Properties and Reactivity of Combustion Soots

The dependence of specific properties of black carbon (BC) soots on fuel type and combustion conditions has been studied, and the effects of these properties on soot particle hydration and reaction with ozone determined. Series of soots were prepared from n-hexane, diesel and JP8 aircraft fuels, utilizing a flow combustion system designed for accurate control of the air/fuel ratio in premixed flames. It has been shown that, for each of these, linear relationships exist between the state of soot surface oxidation, surface area, unpaired electron spin density, and air/fuel ratio. The interrelationship of these properties potentially enables the preparation of soots with pre-selected characteristics by establishing combustion conditions for each fuel type. Predictable variations in these soot characteristics have been demonstrated through preparations near sea level and at higher elevation. Soot hydration and its reactivity with ozone are quantitatively related to surface oxidation and, thus, the air/fuel combustion ratio for soot's formation in premixed flames. The effect of relative humidity (RH) on the soot-ozone reaction over the O₃ concentration and RH ranges 2–4.8 ppm and17–78%, respectively, is expressed by–d[O₃]/dt =k[O₃]²[H₂O]^0.2and is directly related to particle surface oxidation.     

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.     

Surface ozone concentrations in Agra: links with the prevailing meteorological parameters

Measurements of surface ozone (O₃), nitric oxide (NO), nitrogen dioxide (NO₂), oxides of nitrogen (NO_x=NO+NO₂) and meteorological parameters have been made at Agra (North Central India, 27°10??N, 78°05??E) in post monsoon and winter season. The diurnal variation in O₃ concentration shows daytime in situ photochemical production with diurnal maximum in noon hours ranging from 51 to 54 ppb in post monsoon and from 76 to 82 ppb in winter, while minimum (16?C24 ppb) during nighttime and early morning hours. Average 8-h O₃ concentration varied from 12.4 to 83.9 ppb. The relationship between meteorological parameters (solar radiation intensity, temperature, relative humidity, wind speed and wind direction) and surface O₃ variability was studied using principal component analysis (PCA), multiple linear regression (MLR) and correlation analysis (CA). PCA and MLR of daily mean O₃ concentrations on meteorological parameters explain up to 80 % of day to day ozone variability. Correlation with meteorology is strongly emphasized on days having strong solar radiation intensity and longer sunshine time.     

Seasonal and Diurnal Variation of Surface Ozone and a Preliminary Analysis of Exceedance of its Critical Levels at a Semi-arid Site in India

The mixing ratios of surface O₃ were measured at St. John's College, Agra, an urban and traffic influenced area for the period of 2000–2002. The monthly averaged O₃ mixing ratios ranged between 8 to 40 ppb with an annual average of 21 ppb. Strong diurnal and seasonal variations in O₃ mixing ratios were observed throughout the year except for monsoon season. The mixing ratios of O₃ follow the surface temperature cycle and solar radiation (r = 0.72 and r = 0.65 with temperature and solar radiation, respectively). Concentrations were higher with winds associated with NE and NW direction indicating the impact of pollution sources on surface O₃ concentration. Exceedance of ozone critical level was calculated using the AOT 40 index and found to be 840 ppb.h and 2430 ppb.h for summer and winter seasons, respectively. The present O₃ exposures are lower than the critical level of O₃ and suggest that the present level of O₃ does not have any impact on reduction in crop yields.     

A New Index Developed for Fast Diagnosis of Meteorological Roles in Ground-Level Ozone Variations

China experienced worsening ground-level ozone(O₂) pollution from 2013 to 2019. In this study, meteorological parameters, including surface temperature(T₂), solar radiation(SW), and wind speed(WS), were classified into two aspects,(1) Photochemical Reaction Condition(PRC = T₂× SW) and(2) Physical Dispersion Capacity(PDC = WS). In this way, a Meteorology Synthetic Index(MSI = PRC/PDC) was developed for the quantification of meteorology-induced ground-level O₂pollution. The positive linear relationship between the 90 th percentile of MDA8(maximum daily 8-h average) O₂concentration and MSI determined that the contribution of meteorological changes to ground-level O-3 varied on a latitudinal gradient, decreasing from ~40% in southern China to 10%–20% in northern China. Favorable photochemical reaction conditions were more important for ground-level O₂pollution. This study proposes a universally applicable index for fast diagnosis of meteorological roles in ground-level O₂variability, which enables the assessment of the observed effects of precursor emissions reductions that can be used for designing future control policies.     

Diurnal Variations of Atmospheric Hydrogen Peroxide Concentrations in Saxony (Germany)

During a 3-year study, gaseous hydrogenperoxide (H₂O₂) concentrations were measuredas part of the SANA project at the Melpitz FieldResearch Station and in the city of Leipzig. Typicaldaily mean H₂O₂ mixing ratios on sunny dayswere 0.15 to 0.25 ppbv with maximum values of 0.3 to0.5 ppbv at Melpitz, and 0.3 to 0.6 ppbv with maximumvalues of 0.4 to 1.0 ppbv in Leipzig. Over the entireperiod of the project the maximum hourly mean valueswere 2.1 ppbv and 5.3 ppbv in Melpitz and Leipzig,respectively. The data were not complete enough to show a trend.Linear regression analysis shows, that ozone(O₃), temperature and solar radiation arepositively correlated with H₂O₂, whereasnitrogen oxides (NO_x), carbon monoxide (CO) andrelative humidity are negatively correlated. Negativecorrelation between H₂O₂ and CO is caused byjoint occurrence of CO with NO_x in exhaust gases.Negative correlation between H₂O₂ andrelative humidity is not necessarily in contradictionto the accelerating effect of water vapour onH₂O₂ formation. The strong positivecorrelation of H₂O₂ with the dew pointdifference however seems to better reflect theinfluence of water vapour. Multiple linear regression analysis (MLRA) of thecomponents measured, indicates the great influence of CO on the formation of H₂O₂ in the gasphase.     

Tropospheric degradation products of CH2FCF3 (HFC-134a)

Chlorine atom-initiated photooxidations of CH₂FCF₃ (HFC-134a) in O₂-N₂ diluent were carried out to identify the products formed from the \(CF_3 CHF\dot O\) radical reactions and to determine the product yields as a function of temperature, pressure and O₂ concentration. CF₃C(O)F and HC(O)F were the major ‘first-generation’ products observed, along with smaller yields of C(O)F₂ and, as yet, undetermined yields of CF₃OOOCF₃ and CF₃OOC(O)F. The relative importance of the two major \(CF_3 CHF\dot O\) reaction pathways, is expressed by the rate constant ratio $$k_{O_2 } /k_d = 3.2 \times 10^{ - 25} e^{(3510 \pm 470)/T} cm^3 molecule^{ - 1}$$ The decomposition reaction leading to HC(O)F and ?F₃ radical products is predicted to be the dominant pathway at the Earth's surface while mainly CF₃C(O)F formation will occur at the tropopause.     

NUMERICAL SIMULATION OF THE SEASONAL VARIATION OF TROPOSPHERIC OZONE OVER CHINA

An updated version of the Regional Acid Deposition Model(RADM)driven by meteorologicalfields derived from Chinese Regional Climate Model(CRegCM)is used to simulate seasonal variationof tropospheric ozone over the eastern China.The results show that:(1)Peak O_3 concentration moves from south China to north China responding to the changing ofsolar perpendicular incidence point from south to north.When solar perpendicular incidence pointmoves from north to south,so does the peak O_3 concentration.(2)In the eastern China.the highest O_3 month-average concentration appears in July.thelowest in January and the medium in April and October.The pattern mainly depends on the solarradiation,the concentration of O_3 precursors NO_x and NMHC and the ratio of NMHC/NO_x.(3)Daily variations of O_3 over the eastern China are clear.Namely,O_3 concentrations rise withthe sun rising and the maximums appear at noon.then O_3 concentrations decrease.The highest dailyvariation range of O_3 appears in summer(40×10~(-9) in volume fraction)and the lowest in winter(20×10~(-9) in volume fraction).(4)Daily variations of O_3 over the western China are not clear.The daily variation range of O_3 isless than 10×10~(-9) in volume fraction.     

The heterogeneous formation of N2O over bulk condensed phases in the presence of SO2 at high humidities

In view of the uncertainty of the origin of the secular increase of N₂O, we studied heterogeneous processes that contribute to formation of N₂O in an environment that comes as close as possible to exhaust conditions containing NO and SO₂, among other constituents. The N₂O formation was followed using electron capture gas chromatography (ECD-GC). The other reactants and intermediates (SO₂, NO, NO₂ and HONO) were monitored using gas phase UV-VIS absorption spectroscopy. Experiments were conducted at 298 and 368 K as well as at dry and high humidity (approaching 100% rh) conditions. There is a significant heterogeneous rate of N ₂ O formation at conditions that mimic an exhaust plume from combustion processes.The simultaneous presence of NO, SO₂, O₂ in the gas phase and condensed phase water, either in the bulk liquid or adsorbed state has been confirmed to be necessary for the production of significant levels of N₂O. The stoichiometry of the overall reaction is: 2 NO+SO₂+H₂O N₂O+H₂SO₄. The maximum rate of N₂O formation occurred at the beginning of the reaction and scales with the surface area of the condensed phase and is independent of its volume. A significant rate of N₂O formation at 368 K at 100% rh was also observed in the absence of a bulk substrate. The diffusion of both gas and liquid phase reactants is not rate limiting as the reaction kenetics is dominated by the rate ofN₂O formation under the experimental conditions used in this work. The simultaneous presence of high humidity (90–100% rh at 368 K) and bulk condensed phase results in the maximum rate and final yield of N₂O approaching 60% and 100% conversion after one hour in the presence of amorphous carbon and fly-ash, respectively.Work performed in partial fulfillment of the requirements of Dr ès Sciences at EPFL.     

The heterogeneous formation of N2O in air containing NO2, O3 and NH3

In a nighttime system and under relatively dry conditions (about 15 ppm H₂O), the reaction mixture of NO₂, O₃, and NH₃ in purified air turns out to result in the formation of nitrous oxide (N₂O). The experiments were performed in a continuous stirred flow reactor, in the concentration region of 0.02–2 ppm.N₂O is thought to arise through the heterogeneous reaction of gaseous N₂O₅ and absorbed NH₃ at the wall of the reaction vessel % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l% b9peea0lb9sq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9pue9Fve9% Ffc8meGabaqaciGacaGaaeqabaWaaeaaeaaakeaatCvAUfKttLeary% qr1ngBPrgaiuaacqWFOaakcqWFobGtcqWFibasdaWgaaWcbaGae83m% amdabeaakiab-LcaPmaaBaaaleaacqWFHbqyaeqaaOGaey4kaSIaai% ikaiab-5eaonaaBaaaleaacqWFYaGmaeqaaOGae83ta80aaSbaaSqa% aiab-vda1aqabaGccaGGPaWaaSbaaSqaaiaadEgaaeqaaOGaeyOKH4% Qae8Nta40aaSbaaSqaaiab-jdaYaqabaGccqWFpbWtcqGHRaWkcqWF% ibascqWFobGtcqWFpbWtdaWgaaWcbaGae83mamdabeaakiabgUcaRi% ab-HeainaaBaaaleaacqWFYaGmaeqaaOGae83ta8eaaa!59AC!\[(NH_3 )_a + (N_2 O_5 )_g \to N_2 O + HNO_3 + H_2 O\]In principle, there is competition between this reaction and that of adsorbed H₂O with N₂O₅, resulting in the formation of HNO₃. At high water concentrations (RH>75%), no formation of N₂O was found. Although the rate constant of adsorbed NH₃ with gaseous N₂O₅ is much larger than that of the reaction of adsorbed H₂O with gaseous N₂O₅, the significance of the observed N₂O formation for the outside atmosphere is thought to be dependent on the adsorption properties of H₂O and NH₃ on a surface. A number of NH₃ and H₂O adsorption measurements on several materials are discussed.     

Atmospheric chemistry of carbon disulphide

The oxidation of carbon disulphide has been studied under conditions which are likely to pertain in the atmosphere. The quantum yield for direct photo-oxidation of CS₂ in air at 1 atm pressure, using near UV radiation was 0.012, with OCS as a major product. The rate coefficient (k ₁) for the reaction of OH with CS₂, was determined from measurements of OCS formation in the near UV photolysis of HONO?CS₂?O₂?N₂ mixtures. k ₁ was dependent on oxygen concentration rising from ≤4×10^-14 cm³ molecule^-1 s^-1 at O₂≤15 Torr to (2.0±1.0)×10^-12 cm³ molecule^-1 s^-1 at 1 atm air and 300 K. Equimolar amounts of carbonyl sulphide and sulphur dioxide were the major reaction products. The concentration of carbon disulphide in the ambient atmosphere was measured and the concentration to be expected in the background atmosphere was estimated. Rate and concentration data were used to show that carbon disulphide oxidation represents a major source for atmospheric carbonyl sulphide. It can also serve as an alternate source for atmospheric sulphur dioxide in addition to that produced from hydrogen sulphide and dimethyl sulphide. A consideration of atmospheric concentrations and rate data for these trace sulphur gases suggests that the natural sulphur budget is much smaller than the yearly amounts of sulphur dioxide emitted from anthropogenic sources.     

NUMERICAL SIMULATION OF THE INFLUENCE OFO3,CO2 AND SPECTRUM VARIATION ON THE PHOTOSYNTHESIS OF CROP CANOPY*

Coupled the photosynthesis with transpiration and adjustment of stoma,a dynamic ecological model for simulating the canopy photosynthesis of winter wheat was established by scaling up from the biochemical scale to canopy scale,in which the effects of O₃,CO₂ and solar spectrum on crop photosynthesis were fully considered.Validation of the model against the data measured with CI-301PS portable photosynthesis analyzer showed that the leaf photosynthesis model passed the correlation significance test and had a fairly high accuracy.Numerical analysis showed that the canopy photosynthesis rate would be reduced by 29% if the O₃ concentration increases from 0 ppbv to 200 ppbv,whereas the canopy photosynthesis rate would increase by about 37% while the CO₂ concentration increases from 330 ppmv to 660 ppmv,and the canopy photosynthesis rate would be reduced by 27%0 or so under the condition that the spectrum coefficient changed from 0.5 to 0.4.If the O₃ concentration reached 200 ppbv at noon on the typical sunny day with higher radiation,the canopy photosynthesis will be reduced slightly in the suburb area where the pollution is serious and the photochemical fog is easy to be formed,contrast with that in the clear region and regardless of the climate change,due to the fact that the positive effect of CO₂ on crop photosynthesis can not compensate the negative effect of O₃ on crop photosynthesis.The canopy photosynthesis will be reduced by 35% or so than the BASE value at present,when the spectrum of photosynthetic active radiation(PAR) reduces to 0.4 or so.     

Solar eclipse-induced variations in solar flux, j(NO2) and surface ozone at Kannur, India

Surface ozone is mainly produced by the photodissociation of nitrogen dioxide (NO₂) by solar UV radiation. Subsequently, solar eclipses provide one of the unique occasions to explore the variations in the photolysis rate of NO₂ and their significant impact on the production of ozone at a location. This study aims to examine the diurnal variations in the photodissociation rate coefficient of NO₂, (j(NO₂*)), and mixing ratios of surface ozone and NO _X * (NO?+?NO₂*) during the solar eclipse that occurred on 15 January 2010 at Kannur (11.9°N, 75.4°E, 5?m amsl), a tropical coastal site on the Arabian Sea in South India. This investigation was carried out on the basis of the ground level observations of surface ozone and its prominent precursor NO₂*. The j(NO₂*) values were estimated from the observed solar UV-A flux data. A sharp decline in j(NO₂*) and surface ozone was observed during the eclipse phase because of the decreased efficiency of the ozone formation from NO₂. The NO₂* levels were found to increase during this episode, whereas the NO levels remained unchanged. The surface ozone concentration was reduced by 57.5%, whereas, on the other hand, that of NO _X * increased by 62.5% during the solar eclipse. Subsequently a reduction of *% in the magnitude of j(NO₂*) was found here during the maximum obscuration. Reductions in solar insolation, air temperature and wind speed were also observed during the solar eclipse event. The relative humidity showed a 6.4% decrease during the eclipse phase, which was a unique observation at this site.     

RESEARCH ON SURFACE O3 WITH METEOROLOGICAL CONDITIONS UNDER ATMOSPHERIC BACKGROUND CONDITIONS IN NORTHEAST CHINA*

Surface O₃ concentration and its precursors have been observed at Longfengshan station,Heilongjiang Province for a period of one year from August 13,1994 to July 30,1995. Relationship between surface O₃ and the meteorological conditions during this period is analyzed in this study.Observation results show that diurnal variation of surface O₃ follows a pattern of double-peaks with amplitude of 27-28 ppb under fine days in summer and autumn.Although the diurnal variation is small(14 ppb),it is still detectable when it is overcast.Diurnal variation of O₃ is irregular under rainy days.Surface O₃ concentration rises when wind speed starts to increase at 0800 BT(Beijing Time)from 0 to 6 m s^-1in autumn,winter and summer.Relative high surface O₃ concentration is noticed frequently when S,SSW,SW and WSW wind are encountered at the station during all seasons.At 0800 BT and 1400 BT the surface O₃ concentration increases with the increase of global radiation accordingly during fine days in winter,spring and autumn.During fine days average peak of O₃ concentration in summer is 20 ppb higher than that in winter while the average peak of global radiation in summer is almost twice as high as that in winter.The average surface O₃ concentration under fine days in autumn at Longfengshan station is 14 ppb lower in comparison to the observation results from Lin'an station where Lin'an is at about the same longitude and lower latitude,with same environment,which is mainly caused by the difference of global radiation due to different latitudes in these two areas(difference of average peak global radiation about 100 W m^-2).     

Laboratory Study of O(1S) Formation Process in the Photolysis of O3 and its Atmospheric Implications

A high-sensitive technique to detect O(¹S) atoms using vacuum ultraviolet laser-induced fluorescence (VUV-LIF) spectroscopy has been applied to study the O(¹S) production process from the UV photodissociation of O₃, N₂O, and H₂O₂. The quantum yields for O(¹S) formation from O₃ photolysis at 215 and 220 nm are determined to be (1.4 ± 0.4) × 10⁻⁴ and (5 ± 3) × 10⁻⁵, respectively. Based on thermochemical considerations, the O(¹S) formation from O₃ photolysis at 215 and 220 nm is attributed to a spin-forbidden process of O(¹S)+O₂(X³Σ_g ⁻). Analysis of the Doppler profile of O(¹S) produced from O₃ photolysis at 193 nm also indicates that the O(¹S) atoms are produced from the spin-forbidden process. In the photolysis of N₂O and H₂O₂ at 193 nm, no discernible signal of O(¹S) atoms has been detected. The upper limit values of the quantum yields for O(¹S) production from N₂O and H₂O₂ photolysis at 193 nm are estimated to be 8 × 10⁻⁵ and 3 × 10⁻⁵, respectively. Using the experimental results, the impact of the O(¹S) formation from O₃ photolysis on the atmospheric OH radical formation through the reaction of O(¹S)+H₂O has been estimated. The calculated results show that the contribution of the O(¹S)+H₂O reaction to the OH production rate is ∼2% of that of the O(¹D)+H₂O reaction at 30 km altitude in mid-latitude. Implications of the present laboratory experimental results for the terrestrial airglow of O(¹S) at 557.7 nm have also been discussed.     

Observation of hydrogen peroxide concentrations in a Japanese red pine forest

In order to study the concentrations of hydrogen peroxide (H₂O₂) and the factors controlling its concentrations, we monitored concentrations of H₂O₂ and other gases such as sulfur dioxide, ozone, and NO _x as well as meteorological factors such as air temperature, relative humidity, and wind direction/speed during eight measurement periods from 2000 to 2002 in a Japanese red pine forest in Japan. The H₂O₂ concentrations ranged from below 0.01 to 1.64 ppb, and analysis of the diurnal variation in H₂O₂ concentration showed high concentrations around noon, and low concentrations in the morning and late afternoon. The H₂O₂ concentrations were high in early summer, when O₃ concentration, temperature, and solar radiation were high, and were low in fall, when O₃ concentration, temperature, and solar radiation were low. We propose that O₃ concentration affects the production of H₂O₂ in the monitored region during the period under study, but that high H₂O₂ concentrations were sometimes caused by the transport of polluted air from urban regions. H₂O₂ concentrations decreased remarkably when SO₂ concentrations increased by transported volcanic emission on Miyake Island. In the absence of the effects of SO₂, H₂O₂ concentrations increased with increasing O₃ concentration and temperature.     

A reliable and efficient two-stream algorithm for spherical radiative transfer: Documentation of accuracy in realistic layered media

We present a fast and well documented two-stream algorithm for radiative transfer and particle transport in vertically inhomogeneous, layered media. The physical processes considered are internal production (emission), scattering, absorption, and Lambertian reflection at the lower boundary. The medium may be forced by internal sources as well as by parallel or uniform incidence at the top boundary. This two-stream algorithm is based on a general purpose multi-stream discrete ordinate algorithm released previously. It incorporates all the advanced features of this well-tested and unconditionally stable algorithm, and includes two new features: (i) corrections for spherical geometry, and (ii) an efficient treatment of internal sources that vary rapidly with depth. It may be used to compute fluxes, flux divergences and mean intensities (actinic fluxes) at any depth in the medium. We have used the numerical code to investigate the accuracy of the two-stream approximation in vertically inhomogeneous media. In particular, computations of photodissociation and warming/cooling rates and surface fluxes of ultraviolet and visible radiation for clear, cloudy and aerosol-loaded atmospheres are presented and compared with results from multi-stream computations. The O₃ +hv O(¹D) + O₂ and O₃ +hv O(³P) + O₂ photodissociation rates were considered for solar zenith angles between 0.0–70.0° and surface albedos in the range 0.0–1.0. For small and moderate values of the solar zenith angle and the surface albedo the error made by the two-stream approximation is generally smaller, <10%, than the combined uncertainty in cross sections and quantum yields. Surface ultraviolet and visible fluxes were calculated for the same range of solar zenith angles and surface albedos as the photodissociation rates. It was found that surface ultraviolet and visible fluxes may be calculated by the two-stream approximation with 10% error or less for solar zenith angles less than 60.0° and surface albedos less than 0.5. For large solar zenith angles and/or large surface albedos, conditions typical at high latitudes, the error made by the two-stream approximation may become appreciable, i.e. 20% or more for the photodissociation rates in the lower stratosphere and for ultraviolet and visible surface fluxes for large surface albedos. The two-stream approximation agrees well with multi-stream results for computation of warming/cooling rates except for layers containing cloud and aerosol particles where errors up to 10% may occur. The numerical code provides a fast, well-tested and robust two-stream radiative transfer program that can be used as a software tool by aeronomers, atmospheric physicists and chemists, climate modellers, meteorologists, photobiologists and others concerned with radiation or particle transport problems. Copies of the FORTRAN77 program are available to interested users.     

Primary Product Distribution from the Reaction of Hydroxyl Radicals with Toluene at ppb NOX Mixing Ratios

A study has been conducted to examine the OH-initiated degradation products of toluene in the presence of sub part-per-million levels of NO_X. The experiments were conducted in a dynamic reactor to minimize the conversion of the aromatic compounds while allowing a sufficient mass of products to be collected for analysis. The major primary products detected in the toluene system (with molar yields) include glyoxal (0.238), methylglyoxal (0.167), o-cresol (0.120), benzaldehyde (0.06), 4-oxo-2-pentenal (0.03), and p-cresol (0.03). Six other reaction products, most being ring cleavage products, were measured at yields below 3%. Corrections for secondary OH reactions with the products were made where necessary. The formation of the cresol isomers was found to be invariant to the NO₂ concentrations which indicates that under atmospheric conditions the initial hydroxycyclohexadienyl radical reaction with NO₂ is a minor process and that most of the reaction occurs with O₂. The product yields found in this study are expected to be representative of those that occur in the urban atmosphere at ambient NO₂ concentrations.     

On the potential importance of sulfur-induced activation of soot particles in nascent jet aircraft exhaust plumes

The chemical conversion of emitted SO₂ and SO₃ to gaseous H₂SO₄ in nascent aircraft exhaust plumes and subsequent adsorption of the fully oxidized sulfur species on the surfaces of emitted combustion aerosols (soot) is investigated. Results are presented for the mass fractions of SO₃ and H₂SO₄ acquired per soot particle early in the plume, suggesting that sulfur-induced activation is an efficient pathway to increase the ability of exhaust soot emitted at altitude to host heterogeneous chemical reactions and to trigger the formation of cirrus clouds.