Thirdhand smoke: heterogeneous oxidation of nicotine and secondary aerosol formation in the indoor environment

Tobacco smoking is well-known as a significant source of primary indoor air pollutants. However, only recently has thirdhand smoke (THS) been recognized as a contributor to indoor pollution due to the role of indoor surfaces. Here, the effects of relative humidity (<10% RH and ～ 45% RH) and substrate (cellulose, cotton, and paper) on secondary organic aerosol (SOA) formation from nicotine-ozone-NO(x) reactions are discussed. SOA formation from the sorbed nicotine-ozone reaction ([O(3)] = 55 ppb) varied in size distribution and number, depending on RH and substrate type, indicating the role of substrate and water interactions in SOA formation. This led to SOA yields from cellulose sorbed nicotine-ozone reaction of ～ 1 and 2% for wet and dry conditions, respectively. SOA formation from nicotine-NO(x) reactions was not distinguishable from background levels. Simultaneously, cellulose sorbed nicotine-ozone reaction kinetics ([O(3)] = 55 ppb) were obtained and revealed pseudofirst-order surface rate constants of k(1) = (1 ± 0. 5) × 10(-3) and k(1) < 10(-4) min(-1) under <10% and ～ 45% RH, respectively. Given the toxicity of some of the identified products and that small particles may contribute to adverse health effects, the present study indicates that exposure to THS ozonation products may pose additional health risks.     

Indoor hydrogen peroxide derived from ozone/d-limonene reactions

In this pilot study, performed in an office manipulated to resemble an environment with a strong indoor ozone source or a significant influx of outdoor air during a smog event, reactions between ozone and d-limonene produced hydroperoxides. Hydrogen peroxide (H202) presumably constituted the majority of the measured hydroperoxides, although a small amount of organic hydroperoxides (ROOH) may have contributed to the signal. Total hydroperoxides were 1.0-1.5 ppb at low air exchange rates (0.5-4 h(-1)) and 0.6-0.8 ppb at high air exchange rates (12-18 h-1). The net estimated yield ranged from 1.5 to 3.2%, consistent with values reported in the literature. Based on these yields and typical indoor scenarios, peak indoor concentrations of H202 are projected to be comparable with, but not significantly larger than, peak outdoor concentrations. Hygroscopic secondary organic aerosols (SOA; 10-100 microg m(-3)) were simultaneously generated by the ozone/d-limonene reactions; their co-occurrence with H202 provides a mechanism whereby H2O2 can be transported into the lower respiratory tract. The results demonstrate that reduced air exchange rates lead to increased concentrations of H2O2 and SOA as well as a shift in the size-distribution toward larger particles (0.3-0.7 microm diameter), potentially increasing the amount of H2O2 delivered to the lower respiratory region. This study increases our understanding of H2O2 exposures, including exposures to H2O2 associated with co-occurring hygroscopic aerosols. It also re-emphasizes the potential of ozone-driven chemistry to alter indoor environments, often producing products more irritating than their precursors.     

Surface reaction rate and probability of ozone and alpha-terpineol on glass, polyvinyl chloride, and latex paint surfaces

Ozone can react homogeneously with unsaturated organic compounds in buildings to generate undesirable products. However, these reactions can also occur on indoor surfaces, especially for low-volatility organics. Conversion rates of ozone with α-terpineol, a representative low-volatility compound, were quantified on surfaces that mimic indoor substrates. Rates were measured for α-terpineol adsorbed to beads of glass, polyvinylchloride (PVC), and dry latex paint, in a plug flow reactor. A newly defined second-order surface reaction rate coefficient, k(2), was derived from the flow reactor model. The value of k(2) ranged from 0.68 × 10(-14) cm(4)s(-1)molecule(-1) for α-terpineol adsorbed to PVC to 3.17 × 10(-14) cm(4)s(-1)molecule(-1) for glass, but was insensitive to relative humidity. Further, k(2) is only weakly influenced by the adsorbed mass but instead appears to be more strongly related to the interfacial activity α-terpineol. The minimum reaction probability ranged from 3.79 × 10(-6) for glass at 20% RH to 6.75 × 10(-5) for PVC at 50% RH. The combination of high equilibrium surface coverage and high reactivity for α-terpineol suggests that surface conversion rates are fast enough to compete with or even overwhelm other removal mechanisms in buildings such as gas-phase conversion and air exchange.     

Ozone-initiated chemistry in an occupied simulated aircraft cabin

We have used multiple analytical methods to characterize the gas-phase products formed when ozone was added to cabin air during simulated 4-hour flights that were conducted in a reconstructed section of a B-767 aircraft containing human occupants. Two separate groups of 16 females were each exposed to four conditions: low air exchange (4.4 (h-1)), <2 ppb ozone; low air exchange, 61-64 ppb ozone; high air exchange (8.8 h(-1)), <2 ppb ozone; and high air exchange, 73-77 ppb ozone. The addition of ozone to the cabin air increased the levels of identified byproducts from approximately 70 to 130 ppb at the lower air exchange rate and from approximately 30 to 70 ppb at the higher air exchange rate. Most of the increase was attributable to acetone, nonanal, decanal, 4-oxopentanal (4-OPA), 6-methyl-5-hepten-2-one (6-MHO), formic acid, and acetic acid, with 0.25-0.30 mol of quantified product volatilized per mol of ozone consumed. Several of these compounds reached levels above their reported odor thresholds. Most byproducts were derived from surface reactions with occupants and their clothing, consistent with the inference that occupants were responsible for the removal of >55% of the ozone in the cabin. The observations made in this study have implications for other indoor settings. Whenever human beings and ozone are simultaneously present, one anticipates production of acetone, nonanal, decanal, 6-MHO, geranyl acetone, and 4-OPA.     

Surprising formation of p-cymene in the oxidation of α-pinene in air by the atmospheric oxidants OH, O3, and NO3

Anthropogenic sources release into the troposphere a wide range of volatile organic compounds (VOCs) including aromatic hydrocarbons, whose major sources are believed to be combustion and the evaporation of fossil fuels. An important question is whether there are other sources of aromatics in air. We report here the formation of p-cymene [1-methyl-4-(1-methylethyl) benzene, C6H4(CH3)(C3H7)] from the oxidation of α-pinene by OH, O3, and NO3 at 1 atm in air and 298 K at low (<5%) and high (70%) relative humidities (RH). Loss of α-pinene and the generation of p-cymene were measured using GC-MS. The fractional yields of p-cymene relative to the loss of α-pinene, Δ [p-cymeme]/Δ [α-pinene], were measured to range from (1.6±0.2)×10(-5) for the O3 reaction to (3.0±0.3)×10(-4) for the NO3 reaction in the absence of added water vapor. The yields for the OH and O3 reactions increased by a factor of 4-8 at 70% RH (uncertainties are ±2s). The highest yields at 70% RH for the OH and O3 reactions, ～15 times higher than for dry conditions, were observed if the walls of the Teflon reaction chamber had been previously exposed to H2SO4 formed from the OH oxidation of SO2. Possible mechanisms of the conversion of α-pinene to p-cymene and the potential importance in the atmosphere are discussed.     

Products of ozone-initiated chemistry in a simulated aircraft environment

We used proton-transfer-reaction mass spectrometry (PTR-MS) to examine the products formed when ozone reacted with the materials in a simulated aircraft cabin, including a loaded high-efficiency particulate air (HEPA) filter in the return air system. Four conditions were examined: cabin (baseline), cabin plus ozone, cabin plus soiled T-shirts (surrogates for human occupants), and cabin plus soiled T-shirts plus ozone. The addition of ozone to the cabin without T-shirts, at concentrations typically encountered during commercial air travel, increased the mixing ratio (v:v concentration) of detected pollutants from 35 ppb to 80 ppb. Most of this increase was due to the production of saturated and unsaturated aldehydes and tentatively identified low-molecular-weight carboxylic acids. The addition of soiled T-shirts, with no ozone present, increased the mixing ratio of pollutants in the cabin air only slightly, whereas the combination of soiled T-shirts and ozone increased the mixing ratio of detected pollutants to 110 ppb, with more than 20 ppb originating from squalene oxidation products (acetone, 4-oxopentanal, and 6-methyl-5-hepten-2-one). For the two conditions with ozone present, the more-abundant oxidation products included acetone/propanal (8-20 ppb), formaldehyde (8-10 ppb), nonanal (approximately 6 ppb), 4-oxopentanal (3-7 ppb), acetic acid (approximately 7 ppb), formic acid (approximately 3 ppb), and 6-methyl-5-hepten-2-one (0.5-2.5 ppb), as well as compounds tentatively identified as acrolein (0.6-1 ppb) and crotonaldehyde (0.6-0.8 ppb). The odor thresholds of certain products were exceeded. With an outdoor air exchange of 3 h(-1) and a recirculation rate of 20 h(-1), the measured ozone surface removal rate constant was 6.3 h(-1) when T-shirts were not present, compared to 11.4 h(-1) when T-shirts were present.     

The global atmospheric environment for the next generation

Air quality, ecosystem exposure to nitrogen deposition, and climate change are intimately coupled problems: we assess changes in the global atmospheric environment between 2000 and 2030 using 26 state-of-the-art global atmospheric chemistry models and three different emissions scenarios. The first (CLE) scenario reflects implementation of current air quality legislation around the world, while the second (MFR) represents a more optimistic case in which all currently feasible technologies are applied to achieve maximum emission reductions. We contrast these scenarios with the more pessimistic IPCC SRES A2 scenario. Ensemble simulations for the year 2000 are consistent among models and show a reasonable agreement with surface ozone, wet deposition, and NO2 satellite observations. Large parts of the world are currently exposed to high ozone concentrations and high deposition of nitrogen to ecosystems. By 2030, global surface ozone is calculated to increase globally by 1.5 +/- 1.2 ppb (CLE) and 4.3 +/- 2.2 ppb (A2), using the ensemble mean model results and associated +/-1 sigma standard deviations. Only the progressive MFR scenario will reduce ozone, by -2.3 +/- 1.1 ppb. Climate change is expected to modify surface ozone by -0.8 +/- 0.6 ppb, with larger decreases over sea than over land. Radiative forcing by ozone increases by 63 +/- 15 and 155 +/- 37 mW m(-2) for CLE and A2, respectively, and decreases by -45 +/- 15 mW m(-2) for MFR. We compute that at present 10.1% of the global natural terrestrial ecosystems are exposed to nitrogen deposition above a critical load of 1 g N m(-2) yr(-1). These percentages increase by 2030 to 15.8% (CLE), 10.5% (MFR), and 25% (A2). This study shows the importance of enforcing current worldwide air quality legislation and the major benefits of going further. Nonattainment of these air quality policy objectives, such as expressed by the SRES-A2 scenario, would further degrade the global atmospheric environment.     

Facilitation of cleaning of alumina surfaces fouled with heat-treated bovine serum albumin by ozone treatment

Facilitation of cleaning of alumina (A12O3) particles fouled with heat-treated bovine serum albumin (BSA), which contains sulfhydryl groups on the molecule, by gaseous ozone was studied. With increasing temperature of heat treatment, the amount of adsorbed BSA onto A12O3 surfaces increased, whereas the rate of BSA desorption during alkali cleaning decreased markedly, resulting in the larger amounts of BSA remaining on 12O3 surfaces. No significant amounts of BSA were removed from A12O3 surfaces by alkali cleaning alone when treated at temperatures above 120 degrees C. Before alkali cleaning, the heat-treated, BSA-fouled AI2O3 at 150 degrees C were treated with 0.05 to 0.30% (vol/vol) gaseous ozone at room temperature. Ozone pretreatment markedly accelerated the rate of BSA desorption during subsequent alkali cleaning. The effect of ozone pretreatment on BSA removal depended on the concentration of ozone and treatment time and hence on the total amount of ozone supplied. The molecular weight (MW) of desorbed BSA during alkali cleaning without ozone pretreatment coincided with the MW of the native BSA, whereas the MW of desorbed BSA during the combined ozone-alkali cleaning was lower than the MW of the native BSA. This indicated that the heat-treated BSA molecules adsorbed on A12O3 were partially decomposed into some fragments by ozone pretreatment, resulting in the facilitation of the removal of BSA during alkali cleaning.     

Indoor secondary pollutants from household product emissions in the presence of ozone: A bench-scale chamber study

Ozone-driven chemistry is a source of indoor secondary pollutants of potential health concern. This study investigates secondary air pollutants formed from reactions between constituents of household products and ozone. Gas-phase product emissions were introduced along with ozone at constant rates into a 198-L Teflon-lined reaction chamber. Gas-phase concentrations of reactive terpenoids and oxidation products were measured. Formaldehyde was a predominant oxidation byproduct for the three studied products, with yields for most conditions of 20-30% with respect to ozone consumed. Acetaldehyde, acetone, glycolaldehyde, formic acid, and acetic acid were each also detected for two or three of the products. Immediately upon mixing of reactants, a scanning mobility particle sizer detected particle nucleation events that were followed by a significant degree of secondary particle growth. The production of secondary gaseous pollutants and particles depended primarily on the ozone level and was influenced by other parameters such as the air-exchange rate. Hydroxyl radical concentrations in the range 0.04-200 x 10(5) molecules cm(-3) were determined by an indirect method. OH concentrations were observed to vary strongly with residual ozone level in the chamber, which was in the range 1-25 ppb, as is consistent with expectations from a simplified kinetic model. In a separate chamber study, we exposed the dry residue of two products to ozone and observed the formation of gas-phase and particle-phase secondary oxidation products.     

Response Surface Modeling for the Inactivation of Escherichia coli O157:H7 on Green Peppers (Capsicum annuum) by Ozone Gas Treatment

ABSTRACT: :
The effects of ozone gas concentration (2 to 8 mg/l), relative humidity (RH) (60 to 90%), and treatment time (10 to 40 min) on inactivation of E. coli O157:H7 on green peppers were studied using response surface methodology. A 3-factor Box-Behnken experimental plan was designed and microbial log reduction was measured as a response. The statistical analysis of developed predictive model suggested that ozone gas concentration, RH, and treatment time all significantly (P < 0.01) increased the rate of log reduction of E. coli O157:H7. Among the 3 factors, the effect of ozone gas concentration on bacterial inactivation was the greatest, while the effect of RH was the least. The interaction between ozone gas concentration and RH exhibited a significant and synergistic effect (P < 0.05).     

Photochemical modeling of emissions trading of highly reactive volatile organic compounds in Houston, Texas. 2. Incorporation of chlorine emissions

As part of the State Implementation Plan for attaining the National Ambient Air Quality Standard for ozone, the Texas Commission of Environmental Quality has created a Highly Reactive Volatile Organic Compounds (HRVOC) Emissions Cap and Trade Program for industrial point sources in the Houston/Galveston/Brazoria area. This series of papers examines the potential air quality impacts of this new emission trading program through photochemical modeling of potential trading scenarios; this paper examines the air quality impact of allowing facilities to trade chlorine emission reductions for HRVOC allocations on a reactivity weighted basis. The simulations indicate that trading of anthropogenic chlorine emission reductions for HRVOC allowances at a single facility or between facilities, in general, resulted in improvements in air quality. Decreases in peak 1-h averaged and 8-h averaged ozone concentrations associated with trading chlorine emissions for HRVOC allocations on a Maximum Incremental Reactivity (MIR) basis were up to 0.74 ppb (0.63%) and 0.56 ppb (0.61%), respectively. Air quality metrics based on population exposure decreased by up to 3.3% and 4.1% for 1-h and 8-h averaged concentrations. These changes are small compared to the maximum changes in ozone concentrations due to the VOC emissions from these sources (5-10 ppb for 8-h averages; up to 30 ppb for 1-h averages) and the chlorine emissions from the sources (5-10 ppb for maximum concentrations over wide areas and up to 70 ppb in localized areas). The simulations indicate that the inclusion of chlorine emissions in the trading program is likely to be beneficial to air quality and is unlikely to cause localized increases in ozone concentrations ("hot spots").     

Considering the Air Quality Impacts of Bioenergy Crop Production: A Case Study Involving Arundo donax

The expanding production of bioenergy crops may impact regional air quality through the production of volatile organic compounds such as isoprene. To investigate the effects of isoprene-emitting crops on air quality, specifically ozone (O(3)) and secondary organic aerosol (SOA) formation, we performed a series of model runs using the Weather Research and Forecasting model with Chemistry (WRF/Chem) coupled with the Model of Emissions of Gases and Aerosols from Nature (MEGAN) simulating a proposed cropland conversion to the giant cane Arundo donax for biomass production. Cultivation of A. donax in the relatively clean air of northeastern Oregon resulted in an average increase in 8 h O(3) levels of 0.52 ppb, while SOA was largely unaffected (<+0.01 μg m(-3)). Conversions in U.S. regions with reduced air quality (eastern Texas and northern Illinois) resulted in average 8 h O(3) increases of 2.46 and 3.97 ppb, respectively, with daily increases up to 15 ppb in the Illinois case, and daytime SOA increases up to 0.57 μg m(-3). While cultivation of isoprene-emitting bioenergy crops may be appropriate at some scales and in some regions, other areas may experience increased O(3) and SOA, highlighting the need to consider isoprene emissions when evaluating potential regional impacts of bioenergy crop production.     

Management of tropospheric ozone by reducing methane emissions

Background concentrations of tropospheric ozone are increasing and are sensitive to methane emissions, yet methane mitigation is currently considered only for climate change. Methane control is shown here to be viable for ozone management. Identified global abatement measures can reduce approximately 10% of anthropogenic methane emissions at a cost-savings, decreasing surface ozone by 0.4-0.7 ppb. Methane controls produce ozone reductions that are widespread globally and are realized gradually (approximately 12 yr). In contrast, controls on nitrogen oxides (NOx) and nonmethane volatile organic compounds (NMVOCs) target high-ozone episodes in polluted regions and affect ozone rapidly but have a smaller climate benefit. A coarse estimate of the monetized global benefits of ozone reductions for agriculture, forestry, and human health (neglecting ozone mortality) justifies reducing approximately 17% of global anthropogenic methane emissions. If implemented, these controls would decrease ozone by -1 ppb and radiative forcing by approximately 0.12 W m(-2). We also find that climate-motivated methane reductions have air quality-related ancillary benefits comparable to those for CO2. Air quality planning should consider reducing methane emissions alongside NOx and NMVOCs, and because the benefits of methane controls are shared internationally, industrialized nations should consider emphasizing methane in the further development of climate change or ozone policies.     

Influence of tropospheric ozone control on exposure to ultraviolet radiation at the surface

Improving air quality by reducing ambient ozone (O(3)) will likely lower O(3) concentrations throughout the troposphere and increase the transmission of solar ultraviolet (UV) radiation to the surface. The changes in surface UV radiation between two control scenarios (nominally 84 and 70 ppb O(3) for summer 2020) in the Eastern two-thirds of the contiguous U.S. are estimated, using tropospheric O(3) profiles calculated with a chemistry-transport model (Community Multi-Scale Air Quality, CMAQ) as inputs to a detailed model of the transfer of solar radiation through the atmosphere (tropospheric ultraviolet-visible, TUV) for clear skies, weighed for the wavelengths known to induce sunburn and skin cancer. Because the incremental emission controls differ according to region, strong spatial variability in O(3) reductions and in corresponding UV radiation increments is seen. The geographically averaged UV increase is 0.11 ± 0.03%, whereas the population-weighted increase is larger, 0.19 ± 0.06%, because O(3) reductions are greater in more densely populated regions. These relative increments in exposure are non-negligible given the already high incidence of UV-related health effects, but are lower by an order of magnitude or more than previous estimates.     

Ozone removal in the sampling of parts per billion levels of terpenoid compounds: an evaluation of different scrubber materials

Some reactive volatile organic compounds (VOCs) are prone to degradation during sampling in an ozone-rich environment. A wide variety of different chemicals have been used to remove the ozone prior to sampling, but the possibility of interference by such chemicals with the sampled VOCs has not been thoroughly examined. In the present investigation, the retention/degradation of four terpenes (alpha-pinene, beta-pinene, 3-carene, and limonene) and isoprene together with some of their oxidation products (alpha-pinene oxide, nopinone, 4-acetyl-1-methylcyclohexene (AMCH), methylglyoxal, and methacrolein) has been studied, using various ozone-removing chemicals in an attempt to evaluate their potential as ozone scrubbers in the sampling of ambient air. The chemicals included in this first screening and their ozone-removing capacity are as follows: KI, MnO2, and Na2SO3 removed ozone for more than 24 h when exposed to 73-78 ppb (150-160 microg/m3) at a sampling flow rate of 500 mL/min. Silanized poly(1,4-phenylene sulfide) (PFS) removed ozone for 5 h, unsilanized PFS removed ozone for 1 h and 50 min, and Na2S2O3 removed ozone for 20 min. The recovery of the selected compounds with the different scrubbers was >95% for all compounds for KI; >95% for the terpenes oxidation products; >90% for the terpenes and isoprene for PFS; >90% for the terpenes and isoprene for MnO2 on copper nets, Na2SO3, and Na2S2O3; and <90% for the terpenes and isoprene for carulite (a commercial mixture between MnO2, CuO, and Al2O3), CuO, and indigo carmine.     

Field sampling method for quantifying odorants in humid environments

Most air quality studies in agricultural environments use thermal desorption analysis for quantifying semivolatile organic compounds (SVOCs) associated with odor. The objective of this study was to develop a robust sampling technique for measuring SVOCs in humid environments. Test atmospheres were generated at ambient temperatures (23 +/- 1.5 degrees C) and 25, 50, and 80% relative humidity (RH). Sorbent material used included Tenax, graphitized carbon, and carbon molecular sieve (CMS). Sorbent tubes were challenged with 2, 4, 8, 12, and 24 L of air at various RHs. Sorbent tubes with CMS material performed poorly at both 50 and 80% RH dueto excessive sorption of water. Heating of CMS tubes during sampling or dry-purging of CMS tubes post sampling effectively reduced water sorption with heating of tubes being preferred due to the higher recovery and reproducibility. Tenaxtubes had breakthrough of the more volatile compounds and tended to form artifacts with increasing volumes of air sampled. Graphitized carbon sorbent tubes containing Carbopack X and Carbopack C performed best with quantitative recovery of all compounds at all RHs and sampling volumes tested. The graphitized carbon tubes were taken to the field for further testing. Field samples taken from inside swine feeding operations showed that butanoic acid, 4-methylphenol, 4-ethylphenol, indole, and 3-methylindole were the compounds detected most often above their odor threshold values. Field samples taken from a poultry facility demonstrated that butanoic acid, 3-methylbutanoic acid, and 4-methylphenol were the compounds above their odor threshold values detected most often, relative humidity, CAFO, VOC, SVOC, thermal desorption, swine, poultry, air quality, odor.     

Photodegradation of antibiotics on soil surfaces: laboratory studies on sulfadiazine in an ozone-controlled environment

Among the processes affecting transport and degradation of antibiotics released to the environment during application of manure and slurry to agricultural land, photochemical transformations are of particular interest. Drying-out of the top soil layer under field conditions enables sorption of surface-applied antibiotics to soil dust, thus facilitating direct, indirect, and sensitized photodegradation at the soil/atmosphere interface. For studying various photochemical transformation processes of sulfadiazine, a photovolatility chamber designed in accordance with the requirements of the USEPA Guideline and 161-3 was used. Application of 14C-labeled sulfadiazine enabled complete mass balances and allowed for investigating the impact of various surfaces (glass and soil dust) and environmental factors, i.e., irradiation and atmospheric ozone, on photodegradation and volatilization. Volatilization was shown to be a negligible process. Even after increasing the air temperature up to 35 degrees C only minor amounts of sulfadiazine and transformation products (0.01-0.28% of applied radioactivity) volatilized. Due to direct and indirect photodegradation, the highest extent of mineralization to 14CO2 (3.9%), the formation of degradation products and of nonextractable soil residues was measured in irradiated soil dust experiments using ozone concentrations of 200 ppb. However, even in the dark significant mineralization was observed when ozone was present, indicating ozone-controlled transformation of sulfadiazine to occur at the soil surface.     

Relative effects of surfactants and humidity on soil/air desorption of chloroacetanilide and dinitroaniline herbicides

Herbicides are typically applied as formulation mixtures in order to ensure uniform application and improve biocide performance, but little is known about the effects of formulated surfactants on herbicide exchange between soil and the atmosphere. Desorption experiments were performed for seven herbicides from the chloroacetanilide and dinitroaniline families with model anionic-nonionic surfactant mixtures under a range of relative humidity (RH) conditions (3-66%) on two soils. Enhanced desorption of herbicides from soil to the gas phase was observed asthe concentration of surfactant mixture or the RH increased. Multiple linear regression models developed to summarize the soil/air desorption behavior of these herbicides revealed that surfactant concentration, relative humidity, and herbicide properties (i.e., K(H), K(OA)) all have significant contributions to herbicide desorption. However, the ANOVA results indicated that surfactant concentration only accounted for 1.4% of the variance in desorption, RH accounted for 40-60%, and herbicide properties, logK(H) or logK(OA), accounted for 20-40%. The study results predict that less than a 20% increase (study range 1.5-21.0%) in surfactant concentration could double the atmospheric losses of herbicide from their soil application sites, and about a 60% increase in ambient RH (3-66%) elevated the losses by 10-40 times.     

Full-scale chamber investigation and simulation of air freshener emissions in the presence of ozone

Volatile organic compound (VOC) emissions from one electrical plug-in type of pine-scented air freshener and their reactions with O3 were investigated in the U.S. Environmental Protection Agency indoor air research large chamber facility. Ozone was generated from a device marketed as an ozone generator air cleaner. Ozone and oxides of nitrogen concentrations and chamber conditions such as temperature, relative humidity, pressure, and air exchange rate were controlled and/or monitored. VOC emissions and some of the reaction products were identified and quantified. Source emission models were developed to predict the time/concentration profiles of the major VOCs (limonene, alpha-pinene, beta-pinene, 3-carene, camphene, benzyl propionate, benzyl alcohol, bornyl acetate, isobornyl acetate, and benzaldehyde) emitted bythe air freshener. Gas-phase reactions of VOCs from the air freshener with O3 were simulated by a photochemical kinetics simulation system using VOC reaction mechanisms and rate constants adopted from the literature. The concentration-time predictions were in good agreement with the data for O3 and VOCs emitted from the air freshener and with some of the primary reaction products. Systematic differences between the predictions and the experimental results were found for some species. Poor understanding of secondary reactions and heterogeneous chemistry in the chamber is the likely cause of these differences. The method has the potential to provide data to predict the impact of O3/VOC interactions on indoor air quality.     

Multiphase chemical kinetics of the nitration of aerosolized protein by ozone and nitrogen dioxide

Proteins contained in pollen and other biological particles are nitrated by ozone and nitrogen dioxide in polluted air. The nitration can enhance the allergenic potential of proteins, which may contribute to the increasing prevalence of allergic diseases. The reactive uptake of NO(2) by aerosolized protein (bovine serum albumin) was investigated in an aerosol flow tube using the short-lived radioactive tracer (13)N. In the absence of O(3), the NO(2) uptake coefficient was below detection limit (γ(NO2) < 10(-6)), but with 20-160 ppb O(3) γ(NO2) increased from ~10(-6) to ~10(-4). Using the kinetic multilayer model of surface and bulk chemistry (KM-SUB), the observed time and concentration dependence can be well reproduced by a multiphase chemical mechanism involving ozone-generated reactive oxygen intermediates (ROIs), but not by NO(3) radicals formed in the gas phase. Product studies show the formation of protein dimers, suggesting that the ROIs are phenoxy radical derivatives of the amino acid tyrosine (tyrosyl radicals) which are also involved in physiological protein nitration processes. Our results imply that proteins on the surface of aerosol particles undergo rapid nitration in polluted air, while the rate of nitration in bulk material may be low depending on phase state and surface-to-volume ratio.