Reactive Uptake Of Ozone Research Articles

Constraining the Reaction Rate of Criegee Intermediates with Carboxylic Acids during the Multiphase Ozonolysis of Aerosolized Alkenes

Criegee intermediates (CIs) are central to the ozonolysis of unsaturated organic compounds, controlling the formation of small fragmentation reaction products and higher molecular weight oligomeric compounds through competing unimolecular and bimolecular pathways. In particular, the reaction of thermalized CI with carboxylic acids (RCOOH) to produce oligomeric α-acyloxyalkyl hydroperoxides (AAHPs) is of interest to the chemical transformation of organic compounds in the atmosphere. In the gas phase, the CI + RCOOH reaction proceeds at supercollisional rates, consistent with a barrierless reaction mechanism. However, the rate of this reaction in condensed phases remains uncertain. Here, we report the results of aerosol flow tube studies of the ozonolysis of submicron organic aerosol containing mixtures of an internal n-alkene (Z-9-tricosene, tri) and a saturated acid (2-hexyldecanoic acid, HDA). The decay of the reactants and formation of reaction products are monitored using atmospheric pressure chemical ionization mass spectrometry (APCI–MS). A 6-fold decrease in the reactive uptake of ozone is observed with increasing acid concentration, consistent with a previous study using alcohol additives. The decay of HDA with ozone exposure shows that HDA scavenges CIs at rates comparable to competing unimolecular pathways involving CIs. The decay kinetics of HDA are analyzed using a simple kinetic model in order to constrain the ratio of the CI + RCOOH and unimolecular CI rate constants. Empirical fitting to this model, combined with theoretical estimates of the unimolecular loss rate, yields a CI + RCOOH rate constant of 1.85 ± 0.27 × 10–19 cm3 molec–1 s–1, which is six orders of magnitude slower than the expected diffusion limit in a liquid organic matrix. Stochastic kinetic simulations are conducted with different values of the CI + RCOOH rate constant to validate this result and show that the diffusion-limited rate is indeed much too rapid to reproduce the experimental results.

Reactive uptake of ozone to azo dyes in a coated-wall flow tube.

Azo dyes are the most common colorants in consumer products, including clothing and cosmetics. Some azo dyes and their products from reductive degradation are known to be mutagenic, so dermal exposure to these species has been studied extensively. In contrast, oxidative degradation of azo dyes in consumer products has not been studied so thoroughly. In the indoor environment, ozone is ubiquitous, so reactive uptake of ozone to azo dyes could lead to dermal exposure to other classes of degradation products. Here, we report the first measurements of the reactive uptake of ozone to thin films of three widely used commercial azo dyes: sunset yellow, amaranth, and tartrazine. Steady-state uptake was observed for all three dyes, under all conditions investigated, even at the lowest relative humidity (RH) of 0%. The uptake coefficients increased with RH. For sunset yellow at 100 ppb of ozone, the value at 80% RH, (2.0 ± 0.5) × 10-7, was 2.5 times greater than that at 0% RH, (8 ± 1) × 10-8, consistent with plasticization of the thin film due to absorption of water. The uptake coefficient of sunset yellow at 80% RH exhibited an inverse dependence on the ozone mixing ratio, approaching an asymptote of 1 × 10-7 above 250 ppb. At 80% RH and 100 ppb of ozone, the uptake coefficients for the three dyes were similar, (2.0 ± 0.5) × 10-7 for sunset yellow, (2.7 ± 0.6) × 10-7 for amaranth, and (3.2 ± 0.3) × 10-7 for tartrazine, despite differences in structural parameters related to the number of reactive sites at the surface. Together, these results are consistent with ozone diffusing into the thin film and the dye molecules mixing between the layers, such that reaction is not restricted to the surface of the film. Finally, the results are suggestive of a role for azo dyes, including the occurrence of their oxidation products, in indoor chemistry.

Ionic-Strength Effects on the Reactive Uptake of Ozone on Aqueous Pyruvic Acid: Implications for Air–Sea Ozone Deposition

A vertical wetted-wall flow-tube technique was used to explore the ionic strength effects at the air-water interface in mediating the sea-surface reaction between ozone (O3) and pyruvic acid (PA). The uptake coefficients of ozone on aqueous PA increase substantially with the concentrations of bromide (Br-) ions, clearly indicating that the dry deposition of ozone could be significantly enhanced due to the presence of carbonyl compounds such as PA at the bromide-rich sea surface. Based on the observed uptake coefficients, the estimated deposition velocity of ozone (100 ppb) for a nanomolar range of PA concentrations is ∼1 × 10-3 m s-1, which represents a significant contribution to the known deposition velocity of ozone at the sea surface. The analysis of reaction products by ultra-high-resolution Fourier transform-ion cyclotron resonance mass spectrometry suggests the formation of oligomers during both the dark and light-induced heterogeneous reactions between gaseous O3 and PA occurring at the surface of a dilute aqueous phase (representative of cloud droplets). The detected high-molecular-weight compounds are much more complex than the oligomeric species identified during the photolytic degradation of bulk aqueous PA alone.

Ozone reaction with interior building materials: Influence of diurnal ozone variation, temperature and humidity

Abstract Elevated tropospheric ozone concentrations are associated with increased morbidity and mortality. Indoor ozone chemistry affects human exposure to ozone and reaction products that also may adversely affect health and comfort. Reactive uptake of ozone has been characterized for many building materials; however, scant information is available on how diurnal variation of ambient ozone influences ozone reaction with indoor surfaces. The primary objective of this study is to investigate ozone-surface reactions in response to a diurnally varying ozone exposure for three common building materials: ceiling tile, painted drywall, and carpet tile. A secondary objective is to examine the effects of air temperature and humidity. A third goal is to explore how conditioning of materials in an occupied office building might influence subsequent ozone-surface reactions. Experiments were performed at bench-scale with inlet ozone concentrations varied to simulate daytime (ozone elevated) and nighttime (ozone-free in these experiments) periods. To simulate office conditions, experiments were conducted at two temperatures (22 °C and 28 °C) and three relative humidity values (25%, 50%, 75%). Effects of indoor surface exposures were examined by placing material samples in an occupied office and repeating bench-scale characterization after exposure periods of 1 and 2 months. Deposition velocities were observed to be highest during the initial hour of ozone exposure with slow decrease in the subsequent hours of simulated daytime conditions. Daily-average ozone reaction probabilities for fresh materials are in the respective ranges of (1.7–2.7) × 10−5, (2.8–4.7) × 10−5, and (3.0–4.5) × 10−5 for ceiling tile, painted drywall, and carpet tile. The reaction probability decreases by 7%–47% across the three test materials after two 8-h periods of ozone exposure. Measurements with the samples from an occupied office reveal that deposition velocity can decrease or increase with time. Influence of temperature and humidity on ozone-surface reactivity was not strong.

Reactive uptake of ozone at simulated leaf surfaces: Implications for ‘non-stomatal’ ozone flux

The reaction of ozone (O 3) with α-pinene has been studied as a function of temperature and relative humidity and in the presence of wax surfaces that simulate a leaf surface. The objective was to determine whether the presence of a wax surface, in which α-pinene could dissolve and form a high surface concentration, would lead to enhanced reaction with O 3. The reaction of O 3 itself with the empty stainless steel reactor and with aluminium and wax surfaces demonstrated an apparent activation energy of around 30 kJ mol −1 for all the surfaces, similar to that observed in long-term field measurements of O 3 fluxes to vegetation. However, the absolute reaction rate was 14 times greater for aluminium foil and saturated hydrocarbon wax surfaces than for stainless steel, and a further 5 times greater for beeswax than hydrocarbon wax. There was no systematic dependence on either relative or absolute humidity for these surface reactions over the range studied (20–100% RH). Reaction of O 3 with α-pinene occurred at rates close to those predicted for the homogeneous gas-phase reaction, and was similar for both the empty reactor and in the presence of wax surfaces. The hypothesis of enhanced reaction at leaf surfaces caused by enhanced surface concentrations of α-pinene was therefore rejected. Comparison of surface decomposition reactions on different surfaces as reported in the literature with the results obtained here demonstrates that the loss of ozone at the earth's surface by decomposition to molecular oxygen (i.e. without oxidative reaction with a substrate) can account for measured ‘non-stomatal’ deposition velocities of a few mm s −1. In order to quantify such removal, the effective molecular surface area of the vegetation/soil canopy must be known. Such knowledge, combined with the observed temperature-dependence, provides necessary input to global-scale models of O 3 removal from the troposphere at the earth's surface.

Reactive Uptake of Ozone by Chlorophyll at Aqueous Surfaces

We report the results of two complementary studies of the heterogeneous reaction between gas-phase ozone and aqueous chlorophyll. In the first experiment, the chlorophyll is present at the air-water interface and its concentration is measured as a function of time, using laser-induced fluorescence, to obtain the surface kinetics. Under most experimental conditions, these are well described using a Langmuir-Hinshelwood formalism. The second experiment was carried out in a wetted-wall flowtube apparatus and measured the uptake coefficient of ozone by the chlorophyll solution. The uptake coefficient decreases with increasing ozone concentration, consistent with the surface mechanism found in the fluorescence experiment. The two experiments agree that the uptake coefficient for ozone by such chlorophyll samples is approximately 2-5 x 10(-6) with unpolluted boundary layer ozone concentrations. At low wind speed, the reaction between ozone and chlorophyll at the sea surface may represent the driving force for ozone deposition at the ocean surface, significantly increasing its deposition velocity there.

Reactive uptake of ozone on mineral oxides and mineral dusts

Abstract A Knudsen cell apparatus was used to measure the heterogeneous reactive uptake of ozone on mineral oxide powders at 296 K. Commercially available powders including α-Al2O3, α-Fe2O3, SiO2 and kaolinite were investigated as well as two different authentic mineral dusts, China loess and Saharan sand. Initial reactive uptake coefficients, γo,BET, for the purchased powders were measured as 1.2±0.4×10−4 for α-Al2O3, 2.0±0.3×10−4 for α-Fe2O3, 6.3±0.9×10−5 for SiO2 and 3±1×10−5 for kaolinite. Authentic dust samples were found to have γο,BET values of 2.7±0.8×10−5 for China loess and 6±2×10−5 for ground Saharan sand. Pressure dependence studies of this reaction on α-Al2O3 and α-Fe2O3 suggest that the initial uptake of ozone on these mineral oxides is a first-order process. Furthermore, under conditions of this study, these powders exhibit catalytic behavior toward the decomposition of ozone, and have turnover rates greater than one. Additionally, the reactive uptake of ozone on α-Al2O3 showed a small temperature dependence over a range of temperatures from 250 to 330 K, consistent with reports of low energies of activation (∼5–10 kJ mol−1) for ozone destruction on oxide powders.

Reactive Uptake of Ozone by Oleic Acid Aerosol Particles: Application of Single-Particle Mass Spectrometry to Heterogeneous Reaction Kinetics

The technique of single-particle mass spectrometry has been coupled to a reaction flow tube to measure the uptake coefficient, γ, of ozone (O3) by oleic acid (9-octadecenoic acid) aerosol particles. The reaction was followed by monitoring the decrease of oleic acid in the size-selected particles as a function of O3 exposure. The reactive uptake coefficient is found to depend on the size of the particle, with γmeas ranging from (7.3 ± 1.5) × 10-3 to (0.99 ± 0.09) × 10-3 for particles ranging in radius from 680 nm to 2.45 μm. It is suggested that the decrease in γmeas with increasing particle size results from the reaction being limited by the diffusion of oleic acid within the particle, and based on our measurements we estimate the value of γ to be (5.8−9.8) × 10-3 for particles that are not limited by oleic acid diffusion. A reaction model that includes simultaneous diffusion and reaction of both O3 and oleic acid is developed and used to fit the observed rates of reaction. Solutions obtained from this model indicate that oleic acid must diffuse within the particle more slowly than is predicted by the measured oleic acid self-diffusion constant.1 It is proposed that this oleic acid-diffusion-limited uptake is attributable to the ozonolysis reaction products. Furthermore, these experiments demonstrate that it is not always possible to describe heterogeneous uptake by a model that decouples all relevant processes, including reaction and diffusion. Finally, the possible implications that these findings have for the role of particle morphology in the reaction of gas-phase species with atmospheric aerosols are discussed.

Reactive Uptake of Ozone by Aerosol-Associated Unsaturated Fatty Acids: Kinetics, Mechanism, and Products

The heterogeneous reaction between ozone and oleic and linoleic acids, prevalent components of both marine and urban organic aerosol, were studied in a flow reactor using electron impact and chemical ionization mass spectrometry. Liquids and frozen liquids were used as proxies for atmospheric aerosol. The reactive uptake coefficients, γ, were determined to be (8.3 ± 0.2) × 10-4 and (1.2 ± 0.2) × 10-3 for liquid oleic and linoleic acid respectively and (5.2 ± 0.1) × 10-5 and (1.4 ± 0.1) × 10-4 for frozen oleic and linoleic acid, respectively. Although, the reacto-diffusive length is estimated to be rather small in the liquid experiments, <10 nm, a clear indication of the participation of subsurface layers in the uptake is observed. This is in contrast to uptake by the frozen acids where the reaction is limited to the surface. Aldehydes were identified as the major volatile reaction products: 1-nonanal was detected following reaction with oleic acid, 2-nonenal, 4-nonenal, and 1-hexanal were detected follow...

Reactive uptake of ozone by proxies for organic aerosols: Surface‐bound and gas‐phase products

Gas‐phase and surface‐bound products were determined for the reaction of ozone with self assembled monolayers of alkanes and terminal alkenes serving as proxies for atmospheric organic aerosols. The organic surfaces were characterized using infrared (IR) spectroscopy (direct absorption and attenuated total reflection) as well as contact angle measurements with water before and after the reaction with ozone. The contact angle of the organic surfaces was reduced by ∼20° owing to the reaction. Following the reaction, IR absorption due to the presence of carbonyls and carboxylic acids was observed on the surface. Gas‐phase products were determined using infrared spectroscopy immediately above the reaction surface. Under dry conditions, gas‐phase formaldehyde yields of 0.5±0.1 for organic monolayers of allyltrichlorosilane (C3=) and octenyltrichlorosilane (C8=) terminal alkenes were observed, in good agreement with the yields observed for gas phase ozonolysis of terminal alkenes. Surfaces of n‐octane (C8) as well as processed alkene surfaces were nonreactive toward ozone. The reaction mechanism of ozone with the surface alkenes is discussed. Finally, the possible implications for the chemistry of organic aerosols are discussed and studied using a box model and realistic atmospheric scenarios.

Reactive uptake of ozone by proxies for organic aerosols: Surface versus bulk processes

Uptake measurements of ozone were conducted with two types of proxies for atmospheric organic aerosols: organic liquids and self‐assembled organic monolayers. Alkanes and terminal alkenes were used. The monolayer surface was characterized, prior to and after reaction, using IR spectroscopy. Uptake experiments were conducted using a flow tube reactor coupled to a chemical ionization mass spectrometer. The reactive uptake coefficient, γ, is shown to be due to reaction with the double bond. For the monolayers, γ is composed solely of a surface reactive component and is smaller by at least an order of magnitude than values obtained for a liquid of the same chain length. Uptake by the liquids is higher due to solubility and reaction in the bulk. The phase of the atmospheric organic aerosol will determine the appropriate use of a bulk or surface uptake probability in atmospheric models. Since the aerosol surface is processed and sites are consumed, γ is time variant. We define a parameter γ as the surface uptake probability per reactive site and determine its value as 9×10−19 cm2 molecule−1. This enables the modeling of surface reactions as surface site concentrations diminish following interaction with the gaseous species.

Reactive uptake of ozone by liquid organic compounds

The reaction probability of ozone on the surface of several different organic liquids is measured. Ozone reacts efficiently (γ≈10−2‐10−3) with organic liquids containing double bonds (1‐tridecene, α‐pinene, toluene, methacrolein and canola oil), and much less efficiently with an aldehyde, a ketone (tridecanal, 2‐tridecanone; γ≈10−4), an alkane, an alcohol and an acid (tridecane, 1‐tridecanol, tridecanoic acid; γ≤10−5). The results suggest that heterogeneous reactions with organic aerosol can be an important loss process for tropospheric ozone, if the aerosol contains unsaturated organic material.