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Given the extent to which per- and polyfluoroalkyl substances (PFAS) are used in commercial and industrial applications, the need to evaluate treatment options that reduce environmental emissions and human and ecological exposures of PFAS is becoming more necessary. One specific chemical class of PFAS, fluorotelomer alcohols (FTOHs), have vapor pressures such that a significant fraction is expected to be present in the gas-phase even at ambient temperatures. FTOHs are used in a variety of PFAS applications, including synthesis and material coatings. Using two complementary mass spectrometric methods, the use of calcium oxide (CaO) was examined as a low temperature and potentially low-cost thermal treatment media for removal and destruction of four gas-phase FTOHs of varying molecular weights. This was accomplished by assessing the removal/destruction efficiency of the FTOHs and the formation of fluorinated byproducts as a function of treatment temperature (200–800 °C) in the presence of CaO compared to thermal-only destruction. During the treatment process, there is evidence that other PFAS compounds are produced at low temperatures (200–600 °C) as the primary FTOH partially degrades. At temperatures above 600 °C, thermal treatment with CaO prevented the formation or removed nearly all these secondary products.

This paper uses a machine learning model called a relevance vector machine (RVM) to quantify ozone (O(3)) and nitrogen oxides (NO(x)) formation under wintertime conditions. Field study measurements were based on previous work described by Olson et al. (2019), where continuous measurements were reported from a wintertime field study in Utah. RVMs were formulated using either O(3) or nitrogen dioxide (NO(2)) as the output variable. Values of the correlation coefficient (r(2)) between predicted and measured concentrations were 0.944 for O(3) and 0.931 for NO(2). RVMs are constructed from the observed measurements and result in sparse model formulations, meaning that only a subset of the data is used to approximate the entire dataset. For this study, the RVM with O(3) as the output variable used only 20% of the measurement data while the RVM with NO(2) used 16%. RVMs were then used as a predictive model to assess the importance of individual precursors. Using O(3) as the output variable, increases in three species resulted in increased O(3) concentrations: hydrogen peroxide (H(2)O(2)), dinitrogen pentoxide (N(2)O(5)), and molecular chlorine (Cl(2)). For the two termination products measured during the study, nitric acid (HNO(3)) and formic acid (CH(2)O(2)), no change in O(3) concentration was observed. Using NO(2) as the output variable, only increases in N(2)O(5) resulted in increased NO(2) concentrations.

Per- and polyfluoroalkyl substances (PFAS) are incorporated into an ever-increasing number of modern products and inevitably enter the environment and ultimately human bodies. Herein, we show that chemical ionization mass spectrometry with iodide reagent ion chemistry is a useful technique for the detection of fluorotelomer alcohols (FTOHs) and other oxygenated PFAS, including per- and polyfluoro carboxylic acids such as hexafluoropropylene oxide dimer acid. This technique offers direct, high-time resolution measurement capability with parts per trillion by volume (nanograms per cubic meter) gas-phase detection limits. Measurements were taken by direct volatilization of samples without prior processing, allowing for fast measurements and reduced sample treatment compared to established PFAS methods. We demonstrate the utility of this technique by sampling volatile and semivolatile PFAS from fluoro additives and fluoro products to quantify levels of FTOHs and identify additional fluorinated compounds for which standards were unavailable.

Recently, we identified seven novel hydroxy-carboxylic acids resulting from gas-phase reactions of isoprene in the presence of nitrogen oxides (NO(x)), ozone (O(3)), and/or hydroxyl radicals (OH). In the present study, we provide evidence that hydroxy-carboxylic acids, namely methyltartaric acids (MTA) are: (1) reliable isoprene tracers, (2) likely produced via rapid peroxy radical hydrogen atom (H) shift reactions (autoxidation mechanism) and analogous alkoxy radical H shifts in low and high NO(x) environments respectively and (3) representative of aged ambient aerosol in the low NO(x) regime. Firstly, MTA are reliable tracers of isoprene aerosol because they have been identified in numerous chamber experiments involving isoprene conducted under a wide range of conditions and are absent in the oxidation of mono- and sesquiterpenes. They are also present in numerous samples of ambient aerosol collected during the past 20 years at several locations in the U.S. and Europe. Furthermore, MTA concentrations measured during a year-long field study in Research Triangle Park (RTP), NC in 2003 show a seasonal trend consistent with isoprene emissions and photochemical activity. Secondly, an analysis of chemical ionization mass spectrometer (CIMS) data of several chamber experiments in low and high NO(x) environments show that highly oxidized molecules (HOMs) derived from isoprene that lead to MTAs may be produced rapidly and considered as early generation isoprene oxidation products in the gas phase. Density functional theory calculations show that rapid intramolecular H shifts involving peroxy and alkoxy radicals possess low barriers for methyl-hydroxy-butenals (MHBs) that may represent precursors for MTA. From these results, a viable rapid H shift mechanism is proposed to occur that produces isoprene derived HOMs like MTA. Finally, an analysis of the mechanism shows that autoxidation-like pathways in low and high NO(x) may produce HOMs in a few OH oxidation steps like commonly detected methyl tetrol (MT) isoprene tracers. The ratio of MTA/MT in isoprene aerosol is also shown to be significantly greater in field versus chamber samples indicating the importance of such pathways in the atmosphere even for smaller hydrocarbons like isoprene.

This paper uses a machine learning model called a relevance vector machine (RVM) to quantify ozone (O3) and nitrogen oxides (NOx) formation under wintertime conditions. Field study measurements were based on previous work described by Olson et al. (2019), where continuous measurements were reported from a wintertime field study in Utah. RVMs were formulated using either O3 or nitrogen dioxide (NO2) as the output variable. Values of the correlation coefficient (r2) between predicted and measured concentrations were 0.944 for O3 and 0.931 for NO2. RVMs are constructed from the observed measurements and result in sparse model formulations, meaning that only a subset of the data is used to approximate the entire dataset. For this study, the RVM with O3 as the output variable used only 20% of the measurement data while the RVM with NO2 used 16%. RVMs were then used as a predictive model to assess the importance of individual precursors. Using O3 as the output variable, increases in three species resulted in increased O3 concentrations: hydrogen peroxide (H2O2), dinitrogen pentoxide (N2O5), and molecular chlorine (Cl2). For the two termination products measured during the study, nitric acid (HNO3) and formic acid (CH2O2), no change in O3 concentration was observed. Using NO2 as the output variable, only increases in N2O5 resulted in increased NO2 concentrations.

Volume concentrations of steady-state secondary organic aerosol (SOA) were measured in 139 steady- state single precursor hydrocarbon oxidation experiments after passing through a temperature controlled inlet tube. Higher temperatures resulted in greater loss of particle volume, with all experiments following linear relationships between natural log of concentration vs. temperature−1. Negatives of observed slopes are converted to effective enthalpies of vaporization (ΔHeff) which range from 6 to 67 kJ mol−1. These values depend upon the properties of the parent hydrocarbon (e.g. number of carbon atoms, number of internal or external double bonds, presence of aromatic or non-aromatic ring structures), as well as conditions of the experiment (relative humidity, oxidant system, oxidant concentrations) and the products of the complex reactions (e.g. aerosol loading). The observed response to change in temperature can be well predicted through a feedforward Artificial Neural Network. The most parsimonious model, as indicated by consensus of several Information Criteria, is comprised of 13 input variables, a single hidden layer of 3 tanh activation function nodes, and a single linear output function. This model predicts the thermal behavior of single precursor aerosols to less than +/− 5%, which is within the laboratory measurement uncertainty, while limiting the problem of overfitting. The selected model reveals that prediction of the thermal behavior of SOA can be performed by a concise number of molecular descriptors of the reactant hydrocarbon, and a general description of the conditions of laboratory oxidation, namely the oxidant in the experiment and the mass of SOA formed. The inclusion of detailed experimental conditions, such as reacted hydrocarbon concentration (Δ HC), chamber relative humidity, chamber volumetric residence time, and/or initial oxidant concentration lead to over-fitted models. Additional input variables are not necessary for an efficient, accurate predictive model of the thermal behavior of the SOA produced. This work indicates that similar predictive modelling methods may be advantageous over current descriptive techniques for assignment of input parameters into air quality models.

We present measurements utilizing the Filter Inlet for Gases and Aerosols (FIGAERO) applied to chamber measurements of isoprene-derived epoxydiol (IEPOX) reactive uptake to aqueous acidic particles and associated SOA formation. Similar to recent field observations with the same instrument, we detect two molecular components desorbing from the IEPOX SOA in high abundance: C5H12O4 and C5H10O3. The thermal desorption signal of the former, presumably 2-methyltetrols, exhibits two distinct maxima, suggesting it arises from at least two different SOA components with significantly different effective volatilities. Isothermal evaporation experiments illustrate that the most abundant component giving rise to C5H12O4 is semi-volatile, undergoing nearly complete evaporation within 1 hour, while the second, less volatile, component remains unperturbed and even increases in abundance. We thus confirm, using controlled laboratory studies, recent analyses of ambient SOA measurements showing that IEPOX SOA is of very low volatility and commonly measured IEPOX SOA tracers, such as 2-methyltetrols and C5-alkene triols, result predominantly from artifacts of measurement techniques associated with thermal decomposition and/or hydrolysis. We further show that IEPOX SOA volatility continues to evolve via acidity enhanced accretion chemistry on the timescale of hours, potentially involving both 2-methyltetrols and organosulfates.

This research used data mining approaches to better understand factors affecting the formation of secondary organic aerosol (SOA). Although numerous laboratory and computational studies have been completed on SOA formation, it is still challenging to determine factors that most influence SOA formation. Experimental data were based on previous work described by Offenberg et al. (2017), where volume concentrations of SOA were measured in 139 laboratory experiments involving the oxidation of single hydrocarbons under different operating conditions. Three different data mining methods were used, including nearest neighbor, decision tree, and pattern mining. Both decision tree and pattern mining approaches identified similar chemical and experimental conditions that were important to SOA formation. Among these important factors included the number of methyl groups for the SOA precursor, the number of rings for the SOA precursor, and the presence of dinitrogen pentoxide (N2O5).

We present measurements as part of the Southern Oxidant and Aerosol Study (SOAS) during which atmospheric aerosol particles were comprehensively characterized. We present results utilizing a Filter Inlet for Gases and AEROsol coupled to a chemical ionization mass spectrometer (CIMS). We focus on the volatility and composition of isoprene derived organic aerosol tracers and of the bulk organic aerosol. By utilizing the online volatility and molecular composition information provided by the FIGAERO-CIMS, we show that the vast majority of commonly reported molecular tracers of isoprene epoxydiol (IEPOX) derived secondary organic aerosol (SOA) is derived from thermal decomposition of accretion products or other low volatility organics having effective saturation vapor concentrations10(-3) μg m(-3). In addition, while accounting for up to 30% of total submicrometer organic aerosol mass, the IEPOX-derived SOA has a higher volatility than the remaining bulk. That IEPOX-SOA, and more generally bulk organic aerosol in the Southeastern U.S. is comprised of effectively nonvolatile material has important implications for modeling SOA derived from isoprene, and for mechanistic interpretations of molecular tracer measurements. Our results show that partitioning theory performs well for 2-methyltetrols, once accretion product decomposition is taken into account. No significant partitioning delays due to aerosol phase or viscosity are observed, and no partitioning to particle-phase water or other unexplained mechanisms are needed to explain our results.

Isomeric epoxydiols from isoprene photooxidation (IEPOX) have been shown to produce substantial amounts of secondary organic aerosol (SOA) mass and are therefore considered a major isoprene-derived SOA precursor. Heterogeneous reactions of IEPOX on atmospheric aerosols form various aerosol-phase components or "tracers" that contribute to the SOA mass burden. A limited number of the reaction rate constants for these acid-catalyzed aqueous-phase tracer formation reactions have been constrained through bulk laboratory measurements. We have designed a chemical box model with multiple experimental constraints to explicitly simulate gas- and aqueous-phase reactions during chamber experiments of SOA growth from IEPOX uptake onto acidic sulfate aerosol. The model is constrained by measurements of the IEPOX reactive uptake coefficient, IEPOX and aerosol chamber wall losses, chamber-measured aerosol mass and surface area concentrations, aerosol thermodynamic model calculations, and offline filter-based measurements of SOA tracers. By requiring the model output to match the SOA growth and offline filter measurements collected during the chamber experiments, we derive estimates of the tracer formation reaction rate constants that have not yet been measured or estimated for bulk solutions.

Although many volatile organic compounds (VOCs) are regulated to limit air pollution and the consequent health effects, the photooxidation products generally are not. Thus, we examined the mutagenicity in Salmonella TA100 of photochemical atmospheres generated in a steady-state atmospheric simulation chamber by irradiating mixtures of single aromatic VOCs, NOx, and ammonium sulfate seed aerosol in air. The 10 VOCs examined were benzene; toluene; ethylbenzene; o-, m-, and p-xylene; 1,2,4- and 1,3,5-trimethylbenzene; m-cresol; and naphthalene. Salmonella were exposed at the air-agar interface to the generated atmospheres for 1, 2, 4, 8, or 16 h. Dark-control exposures produced non-mutagenic atmospheres, illustrating that the gas-phase precursor VOCs were not mutagenic at the concentrations tested. Under irradiation, all but m-cresol and naphthalene produced mutagenic atmospheres, with potencies ranging from 2.0 (p-xylene) to 10.4 (ethylbenzene) revertants m3 mgC−1 h−1. The mutagenicity was due exclusively to direct-acting late-generation products of the photooxidation reactions. Gas-phase chemical analysis showed that a number of oxidized organic chemical species enhanced during the irradiated exposure experiments correlated (r ≥ 0.81) with the mutagenic potencies of the atmospheres. Molecular formulas assigned to these species indicated that they likely contained peroxy acid, aldehyde, alcohol, and other functionalities.

A combination of flow reactor studies and chamber modeling is used to constrain two uncertain parameters central to the formation of secondary organic aerosol (SOA) from isoprene-derived epoxides: (1) the rate of heterogeneous uptake of epoxide to the particle phase and (2) the molar fraction of epoxide reactively taken up that contributes to SOA, the SOA yield (ϕSOA). Flow reactor measurements of the trans-β-isoprene epoxydiol (trans-β-IEPOX) and methacrylic acid epoxide (MAE) aerosol reaction probability (γ) were performed on atomized aerosols with compositions similar to those used in chamber studies. Observed γ ranges for trans-β-IEPOX and MAE were 6.5 × 10–4−0.021 and 4.9–5.2 × 10–4, respectively. Through the use of a time-dependent chemical box model initialized with chamber conditions and γ measurements, ϕSOA values for trans-β-IEPOX and MAE on different aerosol compositions were estimated between 0.03–0.21 and 0.07–0.25, respectively, with the MAE ϕSOA showing more uncertainty.

We present OH observation results during the NACHTT-11 field campaign at the Boulder Atmospheric Observatory in Weld County, Colorado. The observed OH levels during the daytime (at noon) were ~ 2.7 × 106 molecules cm-3 at the ground level (2 m above ground level, AGL). HONO and ozone photolysis were the two dominant photochemical OH production pathways during the field campaign. However, alkene ozonolysis, found an important source for OH by two previous winter season OH observations, was a minor contribution to OH primary production (~5 %). To evaluate recycling sources of OH from HO2 and RO2, an observation constrained University of Washington Chemical Mechanism (UWCM) box model is employed to simulated ambient OH levels with different model scenarios. For the base run without constraining observed HONO, the model simulated OH significantly underestimates the observed OH level (20.8 times in the morning and 7.2 times in the daytime). This indicates that the known HONO sources incorporated in the UWCM model cannot explain the observed HONO level. Once HONO is constrained by the observation, the discrepancy between observation and model simulation improves (5.1 times in the morning and 2.1 times in the daytime) but still out of the measurement uncertainty rangemore » (35 %). We explore two possible reasons for the observed unexplainably high wintertime OH levels. First, potential roles of Cl atoms produce organic peroxy radicals from the reactions between Cl atmos and alkane compounds. However, the Cl levels during the observation period are estimated very low (~ 103 atoms cm-3) to explain the enhanced OH levels. Second, Impacts of higher HONO levels on the ground was evaluated. Strong HONO gradient towards ground was observed especially during the early morning (6 am to 8 am) was observed and the lowest level available for the HONO observation during the campaign is 5 m AGL. Once we assume the twice of the observed HONO levels averaged between 5 m to 15 m at 2 m AGL, model predicted OH levels agree well within the observation uncertainty range. Wintertime photochemistry has not been investigated as much as the summer season. The results of this study along with a limited number of winter OH observations clearly urge further investigation on tropospheric oxidation capacity in the winter season considering implications of tropospheric oxidation capacity to the short-lived climate forcers especially methane.« less

Nitryl chloride (ClNO2) is produced at night by reactions of dinitrogen pentoxide (N2O5) on chloride containing surfaces. ClNO2 is photolyzed during the morning hours after sunrise to liberate highly reactive chlorine atoms (Cl·). This chemistry takes place primarily in polluted environments where the concentrations of N2O5 precursors (nitrogen oxide radicals and ozone) are high, though it likely occurs in remote regions at lower intensities. Recent field measurements have illustrated the potential importance of ClNO2 as a daytime Cl· source and a nighttime NOx reservoir. However, the fate of the Cl· and the overall impact of ClNO2 on regional photochemistry remain poorly constrained by measurements and models. To this end, we have incorporated ClNO2 production, photolysis, and subsequent Cl· reactions into an existing master chemical mechanism (MCM version 3.2) box model framework using observational constraints from the CalNex 2010 field study. Cl· reactions with a set of alkenes and alcohols, and the simplified multiphase chemistry of N2O5, ClNO2, HOCl, ClONO2, and Cl2, none of which are currently part of the MCM, have been added to the mechanism. The presence of ClNO2 produces significant changes to oxidants, ozone, and nitrogen oxide partitioning, relative to model runs excluding ClNO2 formation. From a nighttime maximum of 1.5 ppbv ClNO2, the daytime maximum Cl· concentration reaches 1 × 105 atoms cm−3 at 07:00 model time, reacting mostly with a large suite of volatile organic compounds (VOC) to produce 2.2 times more organic peroxy radicals in the morning than in the absence of ClNO2. In the presence of several ppbv of nitrogen oxide radicals (NOx = NO + NO2), these perturbations lead to similar enhancements in hydrogen oxide radicals (HOx = OH + HO2). Neglecting contributions from HONO, the total integrated daytime radical source is 17% larger when including ClNO2, which leads to a similar enhancement in integrated ozone production of 15%. Detectable levels (tens of pptv) of chlorine containing organic compounds are predicted to form as a result of Cl· addition to alkenes, which may be useful in identifying times of active Cl· chemistry.

Concentrations of 11 species are reported from continuous measurements taken during a wintertime field study in Utah. Time series data for measured species generally displayed strong diurnal patterns. Six species show a diurnal pattern of daytime maximums (NO, NO(y), O(3), H(2)O(2), CH(2)O(2), and Cl(2)), while five species show a diurnal pattern of night time maximums (NO(2), HONO, ClNO(2), HNO(3), and N(2)O(5)). Vector autoregression analyses were completed to better understand important species influencing the formation of O(3) and NO(x). For the species studied, r(2) values of predicted versus measured concentrations ranged from 0.82–0.99. Fitting parameters for the autoregressive matrix, Π, indicated the importance of species precursors. In addition, values of fitting parameters for Π were relatively insensitive to data size, with variations generally

[1] During the Nitrogen, Aerosol Composition, and Halogens on a Tall Tower campaign at the National Oceanic and Atmospheric Administration Boulder Atmospheric Observatory tower, Erie, CO, USA, in winter 2011, soluble trace gases, the ionic composition of size-resolved aerosols, and the associated meteorological conditions were measured. Median gas-phase mixing ratios of HCl, HNO3, and NH3 were 0.072, 0.202, and 5.79 nmol mol−1, respectively. Most aerosol Cl− was associated with supermicrometer size fractions whereas NO3− and NH4+ were associated primarily with submicrometer size fractions. Aerosol pHs inferred from the measured phase partitioning and thermodynamic properties of HNO3 and NH3 were similar both in terms of absolute values and variability as a function of size. Aerosols were acidic across all size fractions and throughout the duration of the campaign (mostly in the pH range of 2 to 3). The pHs inferred from the HCl/Cl− couple were consistently higher by about 1 to 2 pH units, suggesting possible bias in the associated thermodynamic evaluation of HCl. Specifically, relative to those for HNO3 and NH3, the Henry's law constant for HCl is associated with much greater uncertainty. Condensation of HCl replaced Cl− consumed in the production of ClNO2. Additionally, total Cl (HCl + Cl−) was greater than ClNO2 in sampled air parcels, suggesting that Cl availability was not the limiting factor in ClNO2 production. Median ClNO2 yields from N2O5 reaction with particulate Cl− associated with all size fractions were greater than 0.9.

[1] Heterogeneous N2O5 uptake onto aerosol is the primary nocturnal path for removal of NOx (= NO + NO2) from the atmosphere and can also result in halogen activation through production of ClNO2. The N2O5 uptake coefficient has been the subject of numerous laboratory studies; however, only a few studies have determined the uptake coefficient from ambient measurements, and none has been focused on winter conditions, when the portion of NOx removed by N2O5 uptake is the largest. In this work, N2O5 uptake coefficients are determined from ambient wintertime measurements of N2O5 and related species at the Boulder Atmospheric Observatory in Weld County, CO, a location that is highly impacted by urban pollution from Denver, as well as emissions from agricultural activities and oil and gas extraction. A box model is used to analyze the nocturnal nitrate radical chemistry and predict the N2O5 concentration. The uptake coefficient in the model is iterated until the predicted N2O5 concentration matches the measured concentration. The results suggest that during winter, the most important influence that might suppress N2O5 uptake is aerosol nitrate but that this effect does not suppress uptake coefficients enough to limit the rate of NOx loss through N2O5 hydrolysis. N2O5 hydrolysis was found to dominate the nocturnal chemistry during this study consuming ~80% of nocturnal gas phase nitrate radical production. Typically, less than 15% of the total nitrate radical production remained in the form of nocturnal species at sunrise when they are photolyzed and reform NO2.

[1] Nitryl chloride (ClNO2) is a chlorine atom source and reactive nitrogen reservoir formed during the night by heterogeneous reactions of dinitrogen pentoxide on chloride-containing aerosol particles. The main factors that influence ClNO2 production include nitrogen oxides, ozone, aerosol surface area, soluble chloride, and ambient relative humidity. Regions with strong anthropogenic activity therefore have large ClNO2 formation potential even inland of coastal regions due to transport or local emissions of soluble chloride. As part of the Nitrogen, Aerosol Composition, and Halogens on a Tall Tower field study, we report wintertime vertically resolved ClNO2 and molecular chlorine (Cl2) measurements taken on a 300 m tall tower located at NOAA's Boulder Atmospheric Observatory in Weld County, CO, during February and March of 2011. Gas and particle phase measurements aboard the tower carriage allowed for a detailed description of the chemical state of the nocturnal atmosphere as a function of height. These observations show significant vertical structure in ClNO2 and Cl2 mixing ratios that undergo dynamic changes over the course of a night. Using these measurements, we focus on two distinct combustion plume events where ClNO2 mixing ratios reached 600 and 1300 parts per trillion by volume, respectively, aloft of the nocturnal surface layer. We infer ClNO2 yields from N2O5-aerosol reactions using both observational constraints and box modeling. The derived yields in these plumes suggest efficient ClNO2 production compared to the campaign average, where in-plume yields range from 0.3 to 1; the campaign average yield in the boundary layer is 0.05 ± 0.15, with substantial night-to-night and within night variability similar to previous measurements in this region.

The magnitude and sources of chlorine atoms in marine air remain highly uncertain but have potentially important consequences for air quality in polluted coastal regions. We made continuous measurements of ambient ClNO(2) and Cl(2) concentrations from May 15 to June 8 aboard the Research Vessel Atlantis during the CalNex 2010 field study. In the Los Angeles region, ClNO(2) was more ubiquitous than Cl(2) during most nights of the study period. ClNO(2) and Cl(2) ranged from detection limits at midday to campaign maximum values at night reaching 2100 and 200 pptv, respectively. The maxima were observed in Santa Monica Bay when sampling the Los Angeles urban plume. Cl(2) at times appeared well correlated with ClNO(2), but at other times, there was little to no correlation implying distinct and varying sources. Well-confined Cl(2) plumes were observed, largely independent of ClNO(2), providing support for localized industrial emissions of reactive chlorine. Observations of ClNO(2), Cl(2), and HCl are used to constrain a simple box model that predicts their relative importance as chlorine atom sources in the polluted marine boundary layer. In contrast to the emphasis in previous studies, ClNO(2) and HCl are dominant primary chlorine atom sources for the Los Angeles basin.

Direct measurements of N2O5 reactivity on ambient aerosol particles were made during September 2009 at the Scripps Institution of Oceanography (SIO) Pier facility located in La Jolla, CA. N2O5 reactivity measurements were made using a custom flow reactor and the particle modulation technique alongside measurements of aerosol particle size distributions and non-refractory composition. The pseudo-first order rate coefficients derived from the particle modulation technique and the particle surface area concentrations were used to determine the population average N2O5 reaction probability, γ(N2O5), approximately every 50 min. Insufficient environmental controls within the instrumentation trailer led us to restrict our analysis primarily to nighttime measurements. Within this subset of data, γ(N2O5) ranged from

Chlorine atoms can profoundly affect the composition of the atmosphere. Notoriously, as chlorofluorocarbons, they were implicated in ozone depletion in the stratosphere. New observations suggest that chlorine may be a more potent force lower down in the atmosphere than was thought. The presence of gaseous chlorine atom precursors in the troposphere is generally considered a marine air phenomenon. But measurements made near Boulder, Colorado, reveal significant production of atmospheric nitryl chloride (ClNO2) in a continental setting, 1,400 km from the nearest coastline. This finding, incorporated into model studies, suggests that nitryl chloride production in the contiguous United States alone — probably arising from anthropogenic pollutants — is at a level similar to previous global estimates for marine regions. The presence of gaseous chlorine atom precursors within the troposphere was thought only to occur in marine areas but now nitryl chloride has been found at a distance of 1,400 km from the nearest coastline. A model study shows that the amount of nitryl chloride production in the continental USA alone is similar to previous global estimates for marine regions. A significant fraction of tropospheric chlorine atoms may arise directly from anthropogenic pollutants. Halogen atoms and oxides are highly reactive and can profoundly affect atmospheric composition. Chlorine atoms can decrease the lifetimes of gaseous elemental mercury1 and hydrocarbons such as the greenhouse gas methane2. Chlorine atoms also influence cycles that catalytically destroy or produce tropospheric ozone3, a greenhouse gas potentially toxic to plant and animal life. Conversion of inorganic chloride into gaseous chlorine atom precursors within the troposphere is generally considered a coastal or marine air phenomenon4. Here we report mid-continental observations of the chlorine atom precursor nitryl chloride at a distance of 1,400 km from the nearest coastline. We observe persistent and significant nitryl chloride production relative to the consumption of its nitrogen oxide precursors. Comparison of these findings to model predictions based on aerosol and precipitation composition data from long-term monitoring networks suggests nitryl chloride production in the contiguous USA alone is at a level similar to previous global estimates for coastal and marine regions5. We also suggest that a significant fraction of tropospheric chlorine atoms6 may arise directly from anthropogenic pollutants.

An experimental approach for the direct measurement of trace gas reactivity on ambient aerosol particles has been developed. The method utilizes a newly designed entrained aerosol flow reactor coupled to a custom-built chemical ionization mass spectrometer. The experimental method is described via application to the measurement of the N2O5 reaction probability, γ (N2O5). Laboratory investigations on well characterized aerosol particles show that measurements of γ (N2O5) observed with this technique are in agreement with previous observations, using conventional flow tube methods, to within ±20% at atmospherically relevant particle surface area concentrations (0–1000 μm2 cm−3). Uncertainty in the measured γ (N2O5) is discussed in the context of fluctuations in potential ambient biases (e.g., temperature, relative humidity and trace gas loadings). Under ambient operating conditions we estimate a single-point uncertainty in γ (N2O5) that ranges between ± (1.3×10-2 + 0.2×γ (N2O5)), and ± (1.3×10-3 + 0.2×γ (N2O5)) for particle surface area concentrations of 100 to 1000 μm2 cm−3, respectively. Examples from both laboratory investigations and field observations are included alongside discussion of future applications for the reactivity measurement and optimal deployment locations and conditions.

We report a new method for the simultaneous in situ detection of nitryl chloride (ClNO2) and dinitrogen pentoxide (N2O5) using chemical ionization mass spectrometry (CIMS). The technique relies on the formation and detection of iodide ion-molecule clusters, I(ClNO2)− and I(N2O5)−. The novel N2O5 detection scheme is direct. It does not suffer from high and variable chemical interferences, which are associated with the typical method of nitrate anion detection. We address the role of water vapor, CDC electric field strength, and instrument zero determinations, which influence the overall sensitivity and detection limit of this method. For both species, the method demonstrates high sensitivity (>1 Hz/pptv), precision (~10% for 100 pptv in 1 s), and accuracy (~20%), the latter ultimately determined by the nitrogen dioxide (NO2) cylinder calibration standard and characterization of inlet effects. For the typically low background signals (

The rates of heterogeneous reactions of trace gases with aerosol particles are complex functions of particle chemical composition, morphology, and phase state. Currently, the majority of model parametrizations of heterogeneous reaction kinetics focus on the population average of aerosol particle mass, assuming that individual particles have the same chemical composition as the average state. Here we assess the impact of particle mixing state on heterogeneous reaction kinetics using the N2O5 reactive uptake coefficient, γ(N2O5), and dependence on the particulate chloride-to-nitrate ratio (nCl(-)/nNO3(-)). We describe the first simultaneous ambient observations of single particle chemical composition and in situ determinations of γ(N2O5). When accounting for particulate nCl(-)/nNO3(-) mixing state, model parametrizations of γ(N2O5) continue to overpredict γ(N2O5) by more than a factor of 2 in polluted coastal regions, suggesting that chemical composition and physical phase state of particulate organics likely control γ(N2O5) in these air masses. In contrast, direct measurement of γ(N2O5) in air masses of marine origin are well captured by model parametrizations and reveal limited suppression of γ(N2O5), indicating that the organic mass fraction of fresh sea spray aerosol at this location does not suppress γ(N2O5). We provide an observation-based framework for assessing the impact of particle mixing state on gas-particle interactions.

WOS:000323120800051 The Nitrogen, Aerosol Composition, and Halogens on a Tall Tower (NACHTT) field experiment took place during late winter, 2011, at a site 33km north of Denver, Colorado. The study included fixed-height measurements of aerosols, soluble trace gases, and volatile organic compounds near surface level, as well as vertically resolved measurements of nitrogen oxides, aerosol composition, soluble gas-phase acids, and halogen species from 3 to 270m above ground level. There were 1928 individual profiles during the three-week campaign to characterize trace gas and aerosol distributions in the lower levels of the boundary layer. Nitrate and ammonium dominated the ionic composition of aerosols and originated primarily from local or regional sources. Sulfate and organic matter were also significant and were associated primarily with longer-range transport to the region. Aerosol chloride was associated primarily with supermicron size fractions and was always present in excess of gas-phase chlorine compounds. The nighttime radical reservoirs, nitryl chloride, ClNO2, and nitrous acid, HONO, were both consistently present in nighttime urban air. Nitryl chloride was especially pronounced in plumes from large point sources sampled aloft at night. Nitrous acid was typically most concentrated near the ground surface and was the dominant contributor (80%) to diurnally averaged primary OH radical production in near-surface air. Large observed mixing ratios of light alkanes, both in near-surface air and aloft, were attributable to local emissions from oil and gas activities.

[1] The sea breeze/land breeze diurnal circulation within the Los Angeles Basin and adjacent waters transports marine air into the basin during the day and urban air to Santa Monica Bay during the night. Nitryl chloride, ClNO2 is a nocturnal trace gas formed from the heterogeneous reaction of dinitrogen pentaoxide (N2O5) with chloride containing aerosol. Its photolysis after sunrise produces atomic chlorine radicals and regenerates NO2, both of which may increase ozone production. Mixing of the chloride source from marine sea salt with the urban NOx source in Los Angeles provides conditions ideal for the production of ClNO2. This paper presents an analysis using a wind profiler on the coast and measurements of ClNO2 and its precursors made from both ship and aircraft to assess the prevailing meteorological conditions important for ClNO2 production in this region, with a particular focus on the production over water within the land breeze phase of the circulation. A box model is used to calculate an upper limit to the amount of ClNO2 capable of being produced strictly over Santa Monica Bay during the land breeze. On three out of the four nights of ClNO2 measurements in Santa Monica Bay, the ClNO2 exceeds the upper limit calculated using the box model and shows that the majority of the ClNO2 is produced over the city and transported to Santa Monica Bay by the land breeze. This ClNO2 transport suggests the sea breeze more efficiently transports aerosol chloride inland than land breeze transports NOx offshore.

[1] N2O5 reactivity has been measured directly for the first time on ambient aerosol particles using an entrained aerosol flow reactor coupled to a custom-built chemical ionization mass spectrometer at two urban locations during summer. The observed N2O5 reactivity is a strong function of both relative humidity (RH) and particle chemical composition. We show that particulate organic mass loadings, together with ambient relative humidity, play a leading role in determining the reaction rate of N2O5 with particles. Our observed reactivity values are both more variable and, at times, as much as a factor of ten lower than currently implemented large-scale model parameterizations would predict. Such discrepancies have likely consequences for predictions of NOx availability and ozone production, and the sensitivity of these quantities to aerosol particle loadings.

Methanobactin (mb) is a novel chromopeptide that appears to function as the extracellular component of a copper acquisition system in methanotrophic bacteria. To examine this potential physiological role, and to distinguish it from iron binding siderophores, the spectral (UV-visible absorption, circular dichroism, fluorescence, and X-ray photoelectron) and thermodynamic properties of metal binding by mb were examined. In the absence of Cu(II) or Cu(I), mb will bind Ag(I), Au(III), Co(II), Cd(II), Fe(III), Hg(II), Mn(II), Ni(II), Pb(II), U(VI), or Zn(II), but not Ba(II), Ca(II), La(II), Mg(II), and Sr(II). The results suggest metals such as Ag(I), Au(III), Hg(II), Pb(II) and possibly U(VI) are bound by a mechanism similar to Cu, whereas the coordination of Co(II), Cd(II), Fe(III), Mn(II), Ni(II) and Zn(II) by mb differs from Cu(II). Consistent with its role as a copper-binding compound or chalkophore, the binding constants of all the metals examined were less than those observed with Cu(II) and copper displaced other metals except Ag(I) and Au(III) bound to mb. However, the binding of different metals by mb suggests that methanotrophic activity also may play a role in either the solubilization or immobilization of many metals in situ.

[1] A negative-ion proton-transfer chemical ionization mass spectrometer was deployed on a mobile tower-mounted platform during Nitrogen, Aerosol Composition, and Halogens on a Tall Tower (NACHTT) to measure nitrous acid (HONO) in the winter of 2011. High resolution vertical profiles revealed (i) HONO gradients in nocturnal boundary layers, (ii) ground surface dominates HONO production by heterogeneous uptake of NO2, (iii) significant quantities of HONO may be deposited to the ground surface at night, (iv) daytime gradients indicative of ground HONO production or emission, and (v) an estimated surface HONO reservoir comparable or larger than integrated daytime HONO surface production. Nocturnal integrated column observations of HONO and NO2 allowed direct evaluation of nocturnal ground surface uptake coefficients for these species (γNO2, surf = 2 × 10−6 to 1.6 × 10−5 and γHONO, surf = 2 × 10−5 to 2 × 10−4). A chemical model showed that the unknown source of HONO was highest in the morning, 4 × 106 molecules cm−3 s−1 (600 pptv h−1), declined throughout the day, and minimized near 1 × 106 molecules cm−3 s−1 (165 pptv h−1). The quantity of surface-deposited HONO was also modeled, showing that HONO deposited to the surface at night was at least 25%, and likely in excess of 100%, of the calculated unknown daytime HONO source. These results suggest that if nocturnally deposited HONO forms a conservative surface reservoir, which can be released the following day, a significant fraction of the daytime HONO source can be explained for the NACHTT observations.