Top-down versus bottom-up oxidation of a neonicotinoid pesticide by OH radicals.

Emerging contaminants (EC) distributed on surfaces in the environment can be oxidized by gas phase species (top-down) or by oxidants generated by the underlying substrate (bottom-up). One class of EC is the neonicotinoid (NN) pesticides that are widely distributed in air, water, and on plant and soil surfaces as well as on airborne dust and building materials. This study investigates the OH oxidation of the systemic NN pesticide acetamiprid (ACM) at room temperature. ACM on particles and as thin films on solid substrates were oxidized by OH radicals either from the gas phase or from an underlying TiO2 or NaNO2 substrate, and for comparison, in the aqueous phase. The site of OH attack is both the secondary >CH2 group as well as the primary -CH3 group attached to the tertiary amine nitrogen, with the latter dominating. In the case of top-down oxidation of ACM by gas phase OH radicals, addition to the -CN group also occurs. Major products are carbonyls and alcohols, but in the presence of sufficient water, their hydrolyzed products dominate. Kinetics measurements show ACM is more reactive toward gas phase OH radicals than other NN nitroguanidines, with an atmospheric lifetime of a few days. Bottom-up oxidation of ACM on TiO2 exposed to sunlight outdoors (temperatures were above 30 °C) was also shown to occur and is likely to be competitive with top-down oxidation. These findings highlight the different potential oxidation processes for EC and provide key data for assessing their environmental fates and toxicologies.

Automotive braking is a source of highly charged aerosol particles.

Although the last several decades have seen a dramatic reduction in emissions from vehicular exhaust, nonexhaust emissions (e.g., brake and tire wear) represent an increasingly significant class of traffic-related particulate pollution. Aerosol particles emitted from the wear of automotive brake pads contribute roughly half of the particle mass attributed to nonexhaust sources, while their relative contribution to urban air pollution overall will almost certainly grow coinciding with vehicle fleet electrification and the transition to alternative fuels. To better understand the implications of this growing prominence, a more thorough understanding of the physicochemical properties of brake wear particles (BWPs) is needed. Here, we investigate the electrical properties of BWPs as emitted from ceramic and semi-metallic brake pads. We show that up to 80% of BWPs emitted are electrically charged and that this fraction is strongly dependent on the specific brake pad material used. A dependence of the number of charges per particle on charge polarity and particle size is also demonstrated. We find that brake wear produces both positive and negative charged particles that can hold in excess of 30 elementary charges and show evidence that more negative charges are produced than positive. Our results will provide insights into the currently limited understanding of BWPs and their charging mechanisms, which potentially have significant implications on their atmospheric lifetimes and thus their relevance to climate and air quality. In addition, our study will inform future efforts to remove BWP emissions before entering the atmosphere by taking advantage of their electric charge.

Peroxides on the Surface of Organic Aerosol Particles Using Matrix-Assisted Ionization in Vacuum (MAIV) Mass Spectrometry.

Organic peroxides are key intermediates in the atmosphere but are challenging to detect, especially in the particle phase, due to their instability, which has led to substantial gaps in the understanding of their environmental effects. We demonstrate that matrix-assisted ionization in vacuum (MAIV) mass spectrometry (MS), which does not require an ionization source, enables in situ characterization of peroxides and other products in the surface layers of organic particles. Hydroxyl radical oxidation of glutaric acid particles yields hydroperoxides and organic peroxides, which were detected with signals of the same order of magnitude as the major, more stable products. Product identification is supported by MS/MS analysis, peroxide standards, and offline high-resolution MS. The peroxide signals relative to the stable carbonyl and alcohol products are significantly larger using MAIV compared to those in the offline bulk analysis. This is also the case for analysis using fast, online easy ambient sonic-spray ionization mass spectrometry. These studies demonstrate the advantage of MAIV for the real-time characterization of labile peroxides in the surface layers of solid particles. The presence of peroxides on the surface may be important for surface oxidation processes as well as for the toxicity of inhaled particles.

Exposure to environmentally relevant concentrations of ambient fine particulate matter (PM2.5) depletes the ovarian follicle reserve and causes sex-dependent cardiovascular changes in apolipoprotein E null mice.

BACKGROUND: Fine particulate matter (PM2.5) exposure accelerates atherosclerosis and contains known ovotoxic chemicals. However, effects of exposure to PM2.5 on the finite ovarian follicle pool have hardly been investigated, nor have interactions between ovarian and cardiovascular effects. We hypothesized that subchronic inhalation exposure to human-relevant concentrations of PM2.5 results in destruction of ovarian follicles via apoptosis induction, as well as accelerated recruitment of primordial follicles into the growing pool. Further, we hypothesized that destruction of ovarian follicles enhances the adverse cardiovascular effects of PM2.5 in females. RESULTS: Hyperlipidemic apolipoprotein E (Apoe) null ovary-intact or ovariectomized female mice and testis-intact male mice were exposed to concentrated ambient PM2.5 or filtered air for 12 weeks, 5 days/week for 4 h/day using a versatile aerosol concentration enrichment system. Primordial, primary, and secondary ovarian follicle numbers were decreased by 45%, 40%, and 17%, respectively, in PM2.5-exposed ovary-intact mice compared to controls (P < 0.05). The percentage of primary follicles with granulosa cells positive for the mitosis marker Ki67 was increased in the ovaries from PM2.5-exposed females versus controls (P < 0.05), consistent with increased recruitment of primordial follicles into the growing pool. Exposure to PM2.5 increased the percentages of primary and secondary follicles with DNA damage, assessed by γH2AX immunostaining (P < 0.05). Exposure to PM2.5 increased the percentages of apoptotic antral follicles, determined by TUNEL and activated caspase 3 immunostaining (P < 0.05). Removal of the ovaries and PM2.5-exposure exacerbated the atherosclerotic effects of hyperlipidemia in females (P < 0.05). While there were statistically significant changes in blood pressure and heart rate variability in PM2.5-compared to Air-exposed gonad-intact males and females and ovariectomized females, the changes were not consistent between exposure years and assessment methods. CONCLUSIONS: These results demonstrate that subchronic PM2.5 exposure depletes the ovarian reserve by increasing recruitment of primordial follicles into the growing pool and increasing apoptosis of growing follicles. Further, PM2.5 exposure and removal of the ovaries each increase atherosclerosis progression in Apoe-/- females. Premature loss of ovarian function is associated with increased risk of osteoporosis, cardiovascular disease and Alzheimer's disease in women. Our results thus support possible links between PM2.5 exposure and other adverse health outcomes in women.

The future of airborne sulfur-containing particles in the absence of fossil fuel sulfur dioxide emissions.

Sulfuric acid (H2SO4), formed from oxidation of sulfur dioxide (SO2) emitted during fossil fuel combustion, is a major precursor of new airborne particles, which have well-documented detrimental effects on health, air quality, and climate. Another precursor is methanesulfonic acid (MSA), produced simultaneously with SO2 during the atmospheric oxidation of organosulfur compounds (OSCs), such as dimethyl sulfide. In the present work, a multidisciplinary approach is used to examine how contributions of H2SO4 and MSA to particle formation will change in a large coastal urban area as anthropogenic fossil fuel emissions of SO2 decline. The 3-dimensional University of California Irvine-California Institute of Technology airshed model is used to compare atmospheric concentrations of gas phase MSA, H2SO4, and SO2 under current emissions of fossil fuel-associated SO2 and a best-case futuristic scenario with zero fossil fuel sulfur emissions. Model additions include results from (i) quantum chemical calculations that clarify the previously uncertain gas phase mechanism of formation of MSA and (ii) a combination of published and experimental estimates of OSC emissions, such as those from marine, agricultural, and urban processes, which include pet waste and human breath. Results show that in the zero anthropogenic SO2 emissions case, particle formation potential from H2SO4 will drop by about two orders of magnitude compared with the current situation. However, particles will continue to be generated from the oxidation of natural and anthropogenic sources of OSCs, with contributions from MSA and H2SO4 of a similar order of magnitude. This could be particularly important in agricultural areas where there are significant sources of OSCs.

A cautionary note on the effects of laboratory air contaminants on ambient ionization mass spectrometry measurements.

RATIONALE: Ambient ionization mass spectrometry methods are convenient, sensitive and require little sample preparation. However, they are susceptible to species present in air surrounding the mass spectrometer. This study identifies some challenges associated with the potential impacts of indoor air contaminants on ionization and analysis involving open-air methods. METHODS: Unexpected effects of volatile organic compounds (VOCs) from floor maintenance activities on ambient ionization mass spectrometry were studied using three different ambient ionization techniques. Extractive electrospray ionization (EESI), direct analysis in real time (DART) and ionization by piezoelectric direct discharge (PDD) plasma were demonstrated in this study to be affected by indoor air contaminants. Identification of contaminant vapors was verified by comparison with standards using EESI-MS/MS product ion scans. RESULTS: Emissions of diethylene glycol monoethyl ether and ethylene glycol monobutyl ether are identified from floor stripping and waxing solutions using three ambient ionization mass spectrometry techniques. These unexpected indoor air contaminants are capable of more than 75% ion suppression of target analytes due to their high volatility, proton affinity and solubility compared with the target analytes. The contaminant vapors are also shown to form adducts with one of the target analytes. CONCLUSIONS: The common practice in MS analysis of subtracting a background air spectrum may not be appropriate if the presence of ionizable air contaminants alters the spectrum in unexpected ways. For example, VOCs released into air from floor stripping and waxing are capable of causing ion suppression of target analytes.

Integrating phase and composition of secondary organic aerosol from the ozonolysis of α-pinene.

Airborne particles are important for public health, visibility, and climate. Predicting their concentrations, effects, and responses to control strategies requires accurate models of their formation and growth in air. This is challenging, as a large fraction is formed by complex reactions of volatile organic compounds, generating secondary organic aerosol (SOA), which grows to sizes important for visibility, climate, and deposition in the lung. Growth of SOA is particularly sensitive to the phase/viscosity of the particles and remains poorly understood. We report studies using a custom-designed impactor with a germanium crystal as the impaction surface to study SOA formed from the ozonolysis of α-pinene at relative humidities (RHs) up to 87% at 297 ± 2 K (which corresponds to a maximum RH of 70-86% inside the impactor). The impaction patterns provide insight into changes in phase/viscosity as a function of RH. Attenuated total reflectance-Fourier transform infrared spectroscopy and aerosol mass spectrometry provide simultaneous information on composition changes with RH. The results show that as the RH at which the SOA is formed increases, there is a decrease in viscosity, accompanied by an increasing contribution from carboxylic acids and a decreasing contribution from higher molecular mass products. In contrast, SOA that is formed dry and subsequently humidified remains solid to high RH. The results of these studies have significant implications for modeling the growth, aging, and ultimately, lifetime of SOA in the atmosphere.

Role of the reaction of stabilized Criegee intermediates with peroxy radicals in particle formation and growth in air.

Ozonolysis of alkenes is an important source of secondary organic aerosol (SOA) in the atmosphere. However, the mechanisms by which stabilized Criegee intermediates (SCI) react to form and grow the particles, and in particular the contributions from oligomers, are not well understood. In this study, ozonolysis of trans-3-hexene (C6H12), as a proxy for small alkenes, was investigated with an emphasis on the mechanisms of particle formation and growth. Ozonolysis experiments were carried out both in static Teflon chambers (18-20 min reaction times) and in a glass flow reactor (24 s reaction time) in the absence and presence of OH or SCI scavengers, and under different relative humidity (RH) conditions. The chemical composition of polydisperse and size-selected SOA particles was probed using different mass spectrometric techniques and infrared spectroscopy. Oligomers having SCI as the chain unit are found to be the dominant components of such SOA particles. The formation mechanism for these oligomers suggested by our results follows the sequential addition of SCI to organic peroxy (RO2) radicals, in agreement with previous studies by Moortgat and coworkers. Smaller particles are shown to have a relatively greater contribution from longer oligomers. Higher O/C ratios are observed in smaller particles and are similar to those of oligomers resulting from RO2 + nSCI, supporting a significant role for longer oligomers in particle nucleation and early growth. Under atmospherically relevant RH of 30-80%, water vapor suppresses oligomer formation through scavenging SCI, but also enhances particle nucleation. Under humid conditions, or in the presence of formic or hydrochloric acid as SCI scavengers, peroxyhemiacetals are formed by the acid-catalyzed particle phase reaction between oligomers from RO2 + nSCI and a trans-3-hexene derived carbonyl product. In contrast to the ozonolysis of trans-3-hexene, oligomerization involving RO2 + nSCI does not appear to be prevalent in the ozonolysis of α-cedrene (C15H24), indicating different particle formation mechanisms for small and large complex alkenes that need to be taken into account in atmospheric models.

Isomeric Identification of the Nitroindole Chromophore in Indole + NO3 Organic Aerosol.

Oxidation of indole by nitrate radical (NO3) was previously proposed to form nitroindole, largely responsible for the brown color of indole secondary organic aerosol (SOA). As there are seven known nitroindole isomers, we used chromatographic separation to show that a single nitroindole isomer is produced in the indole + NO3 reaction and definitively assigned it to 3-nitroindole by comparison with chromatograms of nitroindole standards. Mass spectra of aerosolized 3-nitroindole particles were recorded with an aerosol mass spectrometer and directly compared to mass spectra of SOA from smog chamber oxidation of indole by NO3 in order to help identify peaks unique to nitroindole (m/z 162, 132, and 116). Quantum chemical calculations were done to determine the energetics of hypothesized indole + NO3 intermediates and products. The combination of these data suggests a mechanism, wherein a hydrogen atom is first abstracted from the N-H bond in indole, followed by isomerization to a carbon-centered radical in the 3-position and followed by addition of NO2. Alternative mechanisms involving a direct abstraction of a H atom from a C-H bond or a NO3 addition to the ring are predicted to be energetically unfavorable from large barriers for the initial reaction steps.

Predicting the environmental fates of emerging contaminants: Synergistic effects in ozone reactions of nitrogen-containing alkenes.

While nitro and amino alkenes are common in pharmaceuticals, pesticides, and munitions, their environmental fates are not well known. Ozone is a ubiquitous atmospheric oxidant for alkenes, but the synergistic effects of nitrogen-containing groups on the reactions have not been measured. The kinetics and products of ozonolysis of a series of model compounds with different combinations of these functional groups have been measured in the condensed phase using stopped-flow and mass spectrometry methods. Rate constants span about six orders of magnitude with activation energies ranging from 4.3 to 28.2 kJ mol-1. Vinyl nitro groups substantially decrease the reactivity, while amino groups have the opposite effect. The site of the initial ozone attack is highly structure dependent, consistent with local ionization energy calculations. The reaction of the neonicotinoid pesticide nitenpyram, which forms toxic N-nitroso compounds, was consistent with model compounds, confirming the utility of model compounds for assessing environmental fates of these emerging contaminants.

Nitrate ion photolysis in thin water films in the presence of bromide ions.

Nitrate ions commonly coexist with halide ions in aged sea salt particles, as well as in the Arctic snowpack, where NO(3)(-) photochemistry is believed to be an important source of NO(y) (NO + NO(2) + HONO + ...). The effects of bromide ions on nitrate ion photochemistry were investigated at 298 ± 2 K in air using 311 nm photolysis lamps. Reactions were carried out using NaBr/NaNO(3) and KBr/KNO(3) deposited on the walls of a Teflon chamber. Gas phase halogen products and NO(2) were measured as a function of photolysis time using long path FTIR, NO(y) chemiluminescence and atmospheric pressure ionization mass spectrometry (API-MS). Irradiated NaBr/NaNO(3) mixtures show an enhancement in the rates of production of NO(2) and Br(2) as the bromide mole fraction (χ(NaBr)) increased. However, this was not the case for KBr/KNO(3) mixtures where the rates of production of NO(2) and Br(2) remained constant over all values of χ(KBr). Molecular dynamics (MD) simulations show that the presence of bromide in the NaBr solutions pulls sodium toward the solution surface, which in turn attracts nitrate to the interfacial region, allowing for more efficient escape of NO(2) than in the absence of halides. However, in the case of KBr/KNO(3), bromide ions do not appreciably affect the distribution of nitrate ions at the interface. Clustering of Br(-) with NO(3)(-) and H(2)O predicted by MD simulations for sodium salts may facilitate a direct intermolecular reaction, which could also contribute to higher rates of NO(2) production. Enhanced photochemistry in the presence of halide ions may be important for oxides of nitrogen production in field studies such as in polar snowpacks where the use of quantum yields from laboratory studies in the absence of halide ions would lead to a significant underestimate of the photolysis rates of nitrate ions.

Evidence for a kinetically controlled burying mechanism for growth of high viscosity secondary organic aerosol.

Secondary organic aerosol (SOA) particles are ubiquitous in air and understanding the mechanism by which they grow is critical for predicting their effects on visibility and climate. The uptake of three organic nitrates into semi-solid SOA particles formed by α-pinene ozonolysis either with or without an OH scavenger was investigated. Four types of experiments are presented here. In Series A, uptake of the selected organic nitrates (2-ethylhexyl nitrate (2EHN); ß-hydroxypropyl nitrate (HPN); ß-hydroxyhexyl nitrate (HHN)) into impacted SOA particles was interrogated by attenuated total reflectance (ATR)-FTIR. In this case, equilibrium was reached and partition coefficients (KSOA = [-ONO2]SOA/[-ONO2]air) were measured to be K2EHN = (3.2-11) × 104, KHPN = (4.4-5.4) × 105, and KHHN = (4.9-9.0) × 106. In Series B, SOA particles were exposed on-the-fly to gas phase organic nitrates for comparison to Series A, and uptake of organic nitrates was quantified by HR-ToF-AMS analysis, which yielded similar results. In Series C (AMS) and D (ATR-FTIR), each organic nitrate was incorporated into the SOA as the particles formed and grew. The incorporation of the RONO2 was much larger in Series C and D (during growth), exceeding equilibrium values determined in Series A and B (after growth). This suggests that enhanced uptake of organic nitrates during SOA formation and growth is due to a kinetically controlled "burying" mechanism, rather than equilibrium partitioning. This has important implications for understanding SOA formation and growth under conditions where the particles are semi-solid, which is central to accurately predicting properties for such SOA.

Seasonal effects of ambient PM2.5 on the cardiovascular system of hyperlipidemic mice.

People in polluted communities are often exposed to both PM and ozone (O3), albeit not always simultaneously; an important question is whether exposure to particles with seasonal compositional differences can influence biological outcomes. We addressed this question using a mouse model of cardiovascular disease by contrasting the health outcomes of exposures to particles formed or aged during periods of relatively high photochemical activity (i.e. spring/summer), which has increased ambient O3 concentrations, with outcomes of exposures to fall/winter particles which are associated with lower O3 concentrations. Electrocardiographs (ECGs) and blood pressures (BPs) were acquired following exposures to concentrated ambient particles (CAPs). ECGs were analyzed to changes in specific waveform parameters and changes in heart rate variability (HRV). Exposures elicited several types of waveform abnormalities that were associated with seasonal differences in particle constituents. Alterations in R-R interval and P-R interval were seen following exposure to summer CAPs but not fall CAPs and differential responses were seen in the corrected Q-T interval following the two seasonal exposures. Measures of HRV increased after exposure to summer CAPs compared to air-exposed controls but not following the winter CAPs exposure. There were chemical differences with respect to the organic constituents in ambient particles between summer and fall aerosol. The oxygen to carbon ratios (O:C) were generally higher in the spring and summer than in the fall, consistent with seasonal differences in atmospheric photochemical activity. Seasonal differences in atmospheric photochemical activity can modify ambient aerosol composition and can alter biological responses in the cardiovascular system. The results from this study confirm that ambient photochemical activity can alter the toxicity of ambient PM. Regional and seasonal differences in PM2.5 composition should be important considerations when evaluating the effects of PM exposure on cardiovascular health.Implications: Particles formed during periods of high photochemical activity (e.g. spring/summer) elicit more adverse cardiovascular health effects than particles formed during periods of low photochemical activity (e.g. fall/winter). Seasonal differences in atmospheric photochemical activity modified ambient aerosol composition and worsened cardiovascular responses. These results can inform regulatory agencies and may help design air quality regulations for PM2.5 that consider seasonal and regional variations.

Enhanced surface photochemistry in chloride-nitrate ion mixtures.

Heterogeneous reactions of sea salt aerosol with various oxides of nitrogen lead to replacement of chloride ion by nitrate ion. Studies of the photochemistry of a model system were carried out using deliquesced mixtures of NaCl and NaNO3 on a Teflon substrate. Varying molar ratios of NaCl to NaNO3 (1 : 9 Cl- : NO3-, 1 : 1 Cl- : NO3-, 3 : 1 Cl- : NO3-, 9 : 1 Cl- : NO3-) and NaNO3 at the same total concentration were irradiated in air at 299 +/- 3 K and at a relative humidity of 75 +/- 8% using broadband UVB light (270-380 nm). Gaseous NO2 production was measured as a function of time using a chemiluminescence NO(y) detector. Surprisingly, an enhanced yield of NO2 was observed as the chloride to nitrate ratio increased. Molecular dynamics (MD) simulations show that as the Cl- : NO3- ratio increases, the nitrate ions are drawn closer to the interface due to the existence of a double layer of interfacial Cl- and subsurface Na+. This leads to a decreased solvent cage effect when the nitrate ion photodissociates to NO2+O*-, increasing the effective quantum yield and hence the production of gaseous NO2. The implications of enhanced NO2 and likely OH production as sea salt aerosols become processed in the atmosphere are discussed.