A Rapid Derivatization for Quantitation of Perfluorinated Carboxylic Acids from Aqueous Matrices by Gas Chromatography-Mass Spectrometry.

Ultrashort-chain perfluorinated carboxylic acids (PFCAs) are receiving more attention due to their ever-increasing presence in the environment. Methods have been established for the analysis of short- and long-chain PFCAs, while robust quantitation of ultrashort-chain species is scarce. Here, we develop a novel derivatization method using diphenyl diazomethane for quantitation of C2-C14 PFCAs in aqueous matrices. The method is highlighted by rapid completion of derivatization (<1 min) and retention and separation of ultrashort-chain (C2/C3) PFCA derivatives using H2 carrier gas (R > 1.5). A weak anion exchange solid-phase extraction procedure for analyte recovery from representative aqueous samples was developed and validated by spike and recovery from ultrapure water, synthetic ocean water, and simulated denuder extracts used for collecting gaseous PFCAs. Recoveries for PFCAs ranged from 83 to 130% for the majority of analytes and matrices. The instrument detection limits (IDLs) range from 8 to 220 fg per injection, and method detection limits (MDLs) range from 0.06 to 14.6 pg/mL for 500 mL aqueous samples, which are within an order of magnitude to conventional LC-MS/MS methods. The method was applied to the analysis of real samples of tap water, rainwater, ocean water, and annular denuder extracts. The overall method provides a cost-effective alternative to conventional LC-MS/MS methods, overcoming the typical GC-MS drawbacks of high detection limits and long sample preparation times while being able to simultaneously analyze the complete spectrum of environmentally relevant PFCAs.

Chemical Fate of Oils on Indoor Surfaces: Ozonolysis and Peroxidation.

Unsaturated triglycerides found in food and skin oils are reactive in ambient air. However, the chemical fate of such compounds has not been well characterized in genuine indoor environments. Here, we monitored the aging of oil coatings on glass surfaces over a range of environmental conditions, using mass spectrometry, nuclear magnetic resonance (NMR), and electron paramagnetic resonance (EPR) techniques. Upon room air exposure (up to 17 ppb ozone), the characteristic ozonolysis products, secondary ozonides, were observed on surfaces near the cooking area of a commercial kitchen, along with condensed-phase aldehydes. In an office setting, ozonolysis is also the dominant degradation pathway for oil films exposed to air. However, for indoor enclosed spaces such as drawers, the depleted air flow makes lipid autoxidation more favorable after an induction period of a few days. Forming hydroperoxides as the major primary products, this radical-mediated peroxidation behavior is accelerated by indoor direct sunlight, but the initiation step in dark settings is still unclear. These results are in accord with radical measurements, indicating that indoor photooxidation facilitates radical formation on surfaces. Overall, many intermediate and end products observed are reactive oxygen species (ROS) that may induce oxidative stress in human bodies. Given that these species can be widely found on both food and household surfaces, their toxicological properties are worth further attention.

Reactive Chlorine Emissions from Cleaning and Reactive Nitrogen Chemistry in an Indoor Athletic Facility.

Indoor gas-phase radical sources are poorly understood but expected to be much different from outdoors. Several potential radical sources were measured in a windowless, light-emitting diode (LED)-lit room in a college athletic facility over a 2 week period. Alternating measurements between the room air and the supply air of the heating, ventilation, and air-conditioning system allowed an assessment of sources. Use of a chlorine-based cleaner was a source of several photolabile reactive chlorine compounds, including ClNO2 and Cl2. During cleaning events, photolysis rates for these two compounds were up to 0.0023 pptv min-1, acting as a source of chlorine atoms even in this low-light indoor environment. Unrelated to cleaning events, elevated ClNO2 was often observed during daytime and lost to ventilation. The nitrate radical (NO3), which is rapidly photolyzed outdoors during daytime, may persist in low-light indoor environments. With negligible photolysis, loss rates of NO3 indoors were dominated by bimolecular reactions. At times with high NO2 and O3 ventilated from outdoors, N2O5 was observed. Elevated ClNO2 measured concurrently suggests the formation through heterogeneous reactions, acting as an additional source of reactive chlorine within the athletic facility and outdoors.

A boron dipyrromethene (BODIPY) based probe for selective passive sampling of atmospheric nitrous acid (HONO) indoors.

People spend up to 90% of their time indoors, and yet our understanding of indoor air quality and the chemical processes driving it are poorly understood, despite levels of key pollutants typically being higher indoors compared to outdoors. Nitrous acid (HONO) is a species that drives these indoor chemical processes, with potentially detrimental health effects. In this work, a BODIPY-based probe was synthesized with the aim of developing the first selective passive sampler for atmospheric HONO. Our probe and its products are easily detected by UV-Vis spectroscopy with molar extinct coefficients of 37 863 and 33 787 M-1 cm-1, respectively, and a detection limit of 14.8 ng mL-1. When protonated, the probe fluoresces with a quantum yield of 33%, which is turned off upon reaction. The synthesized BODIPY probe was characterized using NMR and UV-Vis spectroscopy. Products were characterized by UV-Vis and ultra high-resolution mass spectrometry. The reaction kinetics of the probe with nitrite was studied using UV-Vis spectroscopy, which had a pseudo-first-order rate of k = 7.7 × 10-4 s-1. The rapid reaction makes this probe suitable for targeted ambient sampling of HONO. This was investigated through a proof-of-concept experiment with gaseous HONO produced by a custom high-purity calibration source delivering the sample to the BODIPY probe in an acidic aqueous solution in clean air and a real indoor air matrix. The probe showed quantitative uptake of HONO in both cases to form the same products observed from reaction with nitrite, with no indication of interferences from ambient NO or NO2. The chemical and physical characteristics of the probe therefore make it ideal for use in passive samplers for selective sampling of HONO from the atmosphere.

Hydrogen Peroxide Emission and Fate Indoors during Non-bleach Cleaning: A Chamber and Modeling Study.

Activities such as household cleaning can greatly alter the composition of air in indoor environments. We continuously monitored hydrogen peroxide (H2O2) from household non-bleach surface cleaning in a chamber designed to simulate a residential room. Mixing ratios of up to 610 ppbv gaseous H2O2 were observed following cleaning, orders of magnitude higher than background levels (sub-ppbv). Gaseous H2O2 levels decreased rapidly and irreversibly, with removal rate constants (kH2O2) 17-73 times larger than air change rate (ACR). Increasing the surface-area-to-volume ratio within the room caused peak H2O2 mixing ratios to decrease and kH2O2 to increase, suggesting that surface uptake dominated H2O2 loss. Volatile organic compound (VOC) levels increased rapidly after cleaning and then decreased with removal rate constants 1.2-7.2 times larger than ACR, indicating loss due to surface partitioning and/or chemical reactions. We predicted photochemical radical production rates and steady-state concentrations in the simulated room using a detailed chemical model for indoor air (the INDCM). Model results suggest that, following cleaning, H2O2 photolysis increased OH concentrations by 10-40% to 9.7 × 105 molec cm-3 and hydroperoxy radical (HO2) concentrations by 50-70% to 2.3 × 107 molec cm-3 depending on the cleaning method and lighting conditions.

Formation and emission of hydrogen chloride in indoor air.

To improve our understanding of chlorine chemistry indoors, reactive chlorine species such as hydrogen chloride (HCl) must be analyzed using fast time-response measurement techniques. Although well studied outdoors, sources of HCl indoors are unknown. In this study, mixing ratios of gaseous HCl were measured at 0.5 Hz in the indoor environment using a cavity ring-down spectroscopy (CRDS) instrument. The CRDS measurement rate provides a major advance in observational capability compared to other established techniques. Measurements of HCl were performed during three types of household activities: (a) floor exposure to bleach, (b) chlorinated and nonchlorinated detergent use in household dishwashers, and (c) cooking events. Surface application of bleach resulted in a reproducible increase of 0.1 ppbv in the affected room. Emissions of HCl from automated dishwashers were observed only when chlorinated detergents were used, with additional HCl emitted during the drying cycle. Increased mixing ratios of HCl were also observed during meal preparation on an electric element stovetop. These observations of HCl derived from household activities indicate either direct emission or secondary production of HCl via chlorine atoms is possible. Calculations of photolysis rate constants of chlorine atom precursors provide evidence that photolysis may contribute to indoor HCl levels.

Time-Resolved Measurements of Nitric Oxide, Nitrogen Dioxide, and Nitrous Acid in an Occupied New York Home.

Indoor oxidizing capacity in occupied residences is poorly understood. We made simultaneous continuous time-resolved measurements of ozone (O3), nitric oxide (NO), nitrogen dioxide (NO2), and nitrous acid (HONO) for two months in an occupied detached home with gas appliances in Syracuse, NY. Indoor NO and HONO mixing ratios were higher than those outdoors, whereas O3 was much lower (sub-ppbv) indoors. Cooking led to peak NO, NO2, and HONO levels 20-100 times greater than background levels; HONO mixing ratios of up to 50 ppbv were measured. Our results suggest that many reported NO2 levels may have a large positive bias due to HONO interference. Nitrous acid, NO2, and NO were removed from indoor air more rapidly than CO2, indicative of reactive removal processes or surface uptake. We measured spectral irradiance from sunlight entering the residence through glass doors; hydroxyl radical (OH) production rates of (0.8-10) × 107 molecules cm-3 s-1 were calculated in sunlit areas due to HONO photolysis, in some cases exceeding rates expected from ozone-alkene reactions. Steady-state nitrate radical (NO3) mixing ratios indoors were predicted to be lower than 1.65 × 104 molecules cm-3. This work will help constrain the temporal nature of oxidant concentrations in occupied residences and will improve indoor chemistry models.

Development of a gas phase source for perfluoroalkyl acids to examine atmospheric sampling methods.

An inability to produce environmentally relevant gaseous mixing ratios of perfluoroalkyl acids (PFAAs), ubiquitous global contaminants, limits the analytical reliability of atmospheric chemists to make accurate gas and particulate measurements that are demonstrably free of interferences due to sampling artefacts. A gas phase source for PFAAs based on the acid displacement mechanism using perfluoropropionate (PFPrA), perfluorobutanoate (PFBA), perfluorohexanoate (PFHxA), and perfluorooctanoate (PFOA) has been constructed. The displacement efficiency of gas phase perfluorocarboxylic acids (PFCAs) is inversely related to chain length. Decreasing displacement efficiencies for PFPrA, PFBA, PFHxA, and PFOA were 90% ± 20%, 40% ± 10%, 40% ± 10%, 9% ± 4%, respectively. Generating detectable amounts of gas phase perfluorosulfonic acids (PFSAs) was not possible. It is likely that lower vapour pressure and much higher acidity play a role in this lack of emission. PFCA emission rates were not elevated by increasing relative humidity (25%-75%), nor flow rate of carrier gas from 33-111 sccm. Overall, reproducible gaseous production of PFCAs was within the error of the production of hydrochloric acid (HCl) as a displacing acid (±20%) and was accomplished using a dry nitrogen flow of 33 ± 2 sccm. A reproducible mass emission rate of 0.97 ± 0.10 ng min(-1) (n = 8) was observed for PFBA. This is equivalent to an atmospheric mixing ratio of 12 ppmv, which is easily diluted to environmentally relevant mixing ratios of PFBA. Conversely, generating gas phase perfluorononanoic acid (PFNA) by sublimating the solid acid under the same conditions produced a mass emission rate of 2800 ng min(-1), which is equivalent to a mixing ratio of 18 ppthv and over a million times higher than suspected atmospheric levels. Thus, for analytical certification of atmospheric sampling methods, generating gas phase standards for PFCAs is best accomplished using acid displacement under dry conditions. This yields quickly stabilized, reproducible emissions and mixing ratios that are easily diluted to environmentally relevant levels. Gas phase PFBA from this source has also been shown to be quantitatively collected using an annular denuder coated with sodium carbonate (Na2CO3) according to Environmental Protection Agency (EPA) method Compendium I.O-4.2. Overall, producing gas phase PFAAs at constant atmospherically-relevant levels will enable the development of standard approaches in certifying gas and particle collection efficiencies for instruments interrogating the gas-particle partitioning and long-range transport of PFCAs in the atmosphere.

An Atmospheric Constraint on the NO2 Dependence of Daytime Near-Surface Nitrous Acid (HONO).

Recent observations suggest a large and unknown daytime source of nitrous acid (HONO) to the atmosphere. Multiple mechanisms have been proposed, many of which involve chemistry that reduces nitrogen dioxide (NO2) on some time scale. To examine the NO2 dependence of the daytime HONO source, we compare weekday and weekend measurements of NO2 and HONO in two U.S. cities. We find that daytime HONO does not increase proportionally to increases in same-day NO2, i.e., the local NO2 concentration at that time and several hours earlier. We discuss various published HONO formation pathways in the context of this constraint.

Insights into secondary organic aerosol formation mechanisms from measured gas/particle partitioning of specific organic tracer compounds.

In situ measurements of organic compounds in both gas and particle phases were made with a thermal desorption aerosol gas chromatography (TAG) instrument. The gas/particle partitioning of phthalic acid, pinonaldehyde, and 6,10,14-trimethyl-2-pentadecanone is discussed in detail to explore secondary organic aerosol (SOA) formation mechanisms. Measured fractions in the particle phase (f(part)) of 6,10,14-trimethyl-2-pentadecanone were similar to those expected from the absorptive gas/particle partitioning theory, suggesting that its partitioning is dominated by absorption processes. However, f(part) of phthalic acid and pinonaldehyde were substantially higher than predicted. The formation of low-volatility products from reactions of phthalic acid with ammonia is proposed as one possible mechanism to explain the high f(part) of phthalic acid. The observations of particle-phase pinonaldehyde when inorganic acids were fully neutralized indicate that inorganic acids are not required for the occurrence of reactive uptake of pinonaldehyde on particles. The observed relationship between f(part) of pinonaldehyde and relative humidity suggests that the aerosol water plays a significant role in the formation of particle-phase pinonaldehyde. Our results clearly show it is necessary to include multiple gas/particle partitioning pathways in models to predict SOA and multiple SOA tracers in source apportionment models to reconstruct SOA.

Suppressor and calibration standard limitations in cation chromatography of ammonium and 10 alkylamines in atmospheric samples.

Ammonia (NH3) and alkylamines are ubiquitous in the atmosphere and have been suggested to play important global roles through new particle formation and aerosol growth. In this work, we optimized an ion-chromatographic (IC) method to separate and quantify the ten most abundant atmospheric alkylamines with high selectivity and separation efficiency, using 4 µm packed columns and resin-based suppressors, alongside stabilizing amine standards. Modern resin suppressors operating on a gradient elution program affected the linear response of this IC technique. Calibration statistical analyses found a loss of analytes in these cation-exchange devices. Suppressor operational longevity was optimized by using a stepped current and an external water supply, which improved precision, accuracy, and LODs compared to other suppression modes. When this new method was applied to real samples, amines were found ubiquitously in size-resolved marine aerosol samples; monopropylamine, isomonopropylamine, and monobutylamine were detected and quantified, which have not been reported before. The molar ratio of the sum of aminium to ammonium ranged from 0.02 to 0.2, showcasing the application of the developed method towards studying the diversity and importance of alkylamines in coastal marine particle composition. The new analytical method also found NH3 present in a suite of new homes with a mean mixing ratio of 25 ± 15 ppbv; a common level reached between homes across the study during the first year of occupation which can then be transported outdoors.

Emerging investigator series: an instrument to measure and speciate the total reactive nitrogen budget indoors: description and field measurements.

Reactive nitrogen species (Nr), defined here as all N-containing compounds except N2 and N2O, have been shown to be important drivers for indoor air quality. Key Nr species include NOx (NO + NO2), HONO and NH3, which are known to have detrimental health effects. In addition, other Nr species that are not traditionally measured may be important chemical actors for indoor transformations (e.g. amines). Cooking and cleaning are significant sources of Nr, whose emission will vary depending on the type of activity and materials used. Here we present a novel instrument that measures the total gas-phase reactive nitrogen (tNr) budget and key species NOx, HONO, and NH3 to demonstrate its suitability for indoor air quality applications. The tNr levels were measured using a custom-built heated platinum (Pt) catalytic furnace to convert all Nr species to NOx, called the tNr oven. The measurement approach was validated through a series of control experiments, such that quantitative measurement and speciation of the total Nr budget are demonstrated. The optimum operating conditions of the tNr oven were found to be 800 °C with a sampling flow rate of 630 cubic centimetres per minute (ccm). Oxidized nitrogen species are known to be quantitatively converted under these conditions. Here, the efficiency of the tNr oven to convert reduced Nr species to NOx was found to reach a maximum at 800 °C, with 103 ± 13% conversion for NH3 and 79-106% for selected relevant amines. The observed variability in the conversion efficiency of reduced Nr species demonstrates the importance of catalyst temperature characterization for the tNr oven. The instrument was deployed successfully in a commercial kitchen, a complex indoor environment with periods of rapidly changing levels, and shown to be able to reliably measure the tNr budget during periods of longer-lived oscillations (>20 min), typical of indoor spaces. The measured NOx, HONO and basic Nr (NH3 and amines) were unable to account for all the measured tNr, pointing to a substantial missing fraction (on average 18%) in the kitchen. Overall, the tNr instrument will allow for detailed survey(s) of the key gaseous Nr species across multiple locations and may also identify missing Nr fractions, making this platform capable of stimulating more in-depth analysis in indoor atmospheres.

Exploring controls on perfluorocarboxylic acid (PFCA) gas-particle partitioning using a model with observational constraints.

The atmospheric fate of perfluorocarboxylic acids (PFCAs) has attracted much attention in recent decades due to the role of the atmosphere in global transport of these persistent chemicals. There is a gap in our understanding of gas-particle partitioning, limited by availability of reliable atmospheric measurements, partitioning properties, and models of gas-particle interactions. The gas-particle equilibrium phase partitioning of C2-C16 PFCAs in the atmosphere were modeled here by taking account of both deprotonation and phase partitioning equilibria among air, aerosol liquid water, and particulate water-insoluble organic matter using a range of available PFCA partitioning properties. We systematically varied water and organic matter content to simulate the full range of atmospheric conditions. Except in severe organic matter pollution episodes, shorter-chain PFCAs are predicted to mainly partition between air and aqueous phase, while for PFCAs with carbon chains longer than 12, organic matter is more likely to be the dominant particle phase reservoir. The model framework underestimated the particle fraction of C2-C8 PFCAs compared with several ambient observations, with larger discrepancies observed for longer-chain PFCAs. The discrepancy could result from externally mixed dust components, non-ideality of aerosol liquid water, surfactant descriptions at phase boundaries, and missed interactions between organic matter and charged PFCA molecules. Reliable measurements of ambient PFCAs with high time resolution and the measurement of uptake parameters by particle-relevant components will be beneficial to more reliable environmental fate modeling of ambient PFCAs.

Near-source hypochlorous acid emissions from indoor bleach cleaning.

Cleaning surfaces with sodium hypochlorite (NaOCl) bleach can lead to high levels of gaseous chlorine (Cl2) and hypochlorous acid (HOCl); these have high oxidative capacities and are linked to respiratory issues. We developed a novel spectral analysis procedure for a cavity ring-down spectroscopy (CRDS) hydrogen peroxide (H2O2) analyzer to enable time-resolved (3 s) HOCl quantification. We measured HOCl levels in a residential bathroom while disinfecting a bathtub and sink, with a focus on spatial and temporal trends to improve our understanding of exposure risks during bleach use. Very high (>10 ppmv) HOCl levels were detected near the bathtub, with lower levels detected further away. Hypochlorous acid concentrations plateaued in the room at a level that depended on distance from the bathtub. This steady-state concentration was maintained until the product was removed by rinsing. Mobile experiments with the analyzer inlet secured to the researcher's face were conducted to mimic potential human exposure to bleach emissions. The findings from mobile experiments were consistent with the spatial and temporal trends observed in the experiments with fixed inlet locations. This work provides insight on effective strategies to reduce exposure risk to emissions from bleach and other cleaning products.

Elevated levels of chloramines and chlorine detected near an indoor sports complex.

Chloramines (NH2Cl, NHCl2, and NCl3) are toxic compounds that can be created during the use of bleach-based disinfectants that contain hypochlorous acid (HOCl) and the hypochlorite ion (OCl-) as their active ingredients. Chloramines can then readily transfer from the aqueous-phase to the gas-phase. Atmospheric chemical ionization mass spectrometry using iodide adduct chemistry (I-CIMS) made observations across two periods (2014 and 2016) at an urban background site on the University of Leicester campus (Leicester, UK). Both monochloramine (NH2Cl) and molecular chlorine (Cl2) were detected and positively identified from calibrated mass spectra during both sampling periods and to our knowledge, this is the first detection of NH2Cl outdoors. Mixing ratios of NH2Cl reached up to 2.2 and 4.0 parts per billion by volume (ppbv), with median mixing ratios of 30 and 120 parts per trillion by volume (pptv) during the 2014 and 2016 sampling periods, respectively. Levels of Cl2 were observed to reach up to 220 and 320 pptv. Analysis of the NH2Cl and Cl2 data pointed to the same local source, a nearby indoor sports complex with a swimming pool and a cleaning product storage shed. No appreciable levels of NHCl2 and NCl3 were observed outdoors, suggesting the indoor pool was not likely to be the primary source of the observed ambient chloramines, as prior measurements made in indoor pool atmospheres indicate that NCl3 would be expected to dominate. Instead, these observations point to indoor cleaning and/or cleaning product emissions as the probable source of NH2Cl and Cl2 where the measured levels provide indirect evidence for substantial amounts transported from indoors to outdoors. Our upper estimate for total NH2Cl emissions from the University of Leicester indoor sports complexes scaled for similar sports complexes across the UK is 3.4 × 105 ± 1.1 × 105 µg h-1 and 0.0017 ± 0.00034 Gg yr-1, respectively. The Cl-equivalent emissions in HCl are only an order of magnitude less to those from hazardous waste incineration and iron and steel sinter production in the UK National Atmospheric Emissions Inventory (NAEI).

Indoor and outdoor air quality impacts of cooking and cleaning emissions from a commercial kitchen.

Gas and particulate emissions from commercial kitchens are important contributors to urban air quality. Not only are these emissions important for occupational exposure of kitchen staff, but they can also be vented to outdoors, causing uncertain health and environmental impacts. In this study, we chemically speciated volatile organic compounds and measured particulate matter mass concentrations in a well-ventilated commercial kitchen for two weeks, including during typical cooking and cleaning operations. From cooking, we observed a complex mixture of volatile organic gases dominated by oxygenated compounds commonly associated with the thermal degradation of cooking oils. Gas-phase chemicals existed at concentrations 2-7 orders of magnitude lower than their exposure limits, due to the high ventilation in the room (mean air change rate of 28 h-1 during operating hours). During evening kitchen cleaning, we observed an increase in the signal of chlorinated gases from 1.1-9.0 times their values during daytime cooking. Particulate matter mass loadings tripled at these times. While exposure to cooking emissions in this indoor environment was reduced effectively by the high ventilation rate, exposure to particulate matter and chlorinated gases was elevated during evening cleaning periods. This emphasizes the need for careful consideration of ventilation rates and methods in commercial kitchen environments during all hours of kitchen operation.

Vertically resolved measurements of nighttime radical reservoirs in Los Angeles and their contribution to the urban radical budget.

Photolabile nighttime radical reservoirs, such as nitrous acid (HONO) and nitryl chloride (ClNO(2)), contribute to the oxidizing potential of the atmosphere, particularly in early morning. We present the first vertically resolved measurements of ClNO(2), together with vertically resolved measurements of HONO. These measurements were acquired during the California Nexus (CalNex) campaign in the Los Angeles basin in spring 2010. Average profiles of ClNO(2) exhibited no significant dependence on height within the boundary layer and residual layer, although individual vertical profiles did show variability. By contrast, nitrous acid was strongly enhanced near the ground surface with much smaller concentrations aloft. These observations are consistent with a ClNO(2) source from aerosol uptake of N(2)O(5) throughout the boundary layer and a HONO source from dry deposition of NO(2) to the ground surface and subsequent chemical conversion. At ground level, daytime radical formation calculated from nighttime-accumulated HONO and ClNO(2) was approximately equal. Incorporating the different vertical distributions by integrating through the boundary and residual layers demonstrated that nighttime-accumulated ClNO(2) produced nine times as many radicals as nighttime-accumulated HONO. A comprehensive radical budget at ground level demonstrated that nighttime radical reservoirs accounted for 8% of total radicals formed and that they were the dominant radical source between sunrise and 09:00 Pacific daylight time (PDT). These data show that vertical gradients of radical precursors should be taken into account in radical budgets, particularly with respect to HONO.

Characterization and optimization of an online system for the simultaneous measurement of atmospheric water-soluble constituents in the gas and particle phases.

In this work we present the results of extensive characterization and optimization of the Ambient Ion Monitor-Ion Chromatograph (AIM-IC) system, an instrument developed by URG Corp. and Dionex Inc. for simultaneous hourly measurements of the water-soluble chemical composition of atmospheric fine particulate matter (PM(2.5)) and associated precursor gases. The sampling assembly of the AIM-IC consists of an inertial particle size-selection assembly, a parallel-plate wet denuder (PPWD) for the collection of soluble gases, and a particle supersaturation chamber (PSSC) for collection of particles, in series. The analytical assembly of the AIM-IC consists of anion and cation IC units. The system detection limits were determined to be 41 ppt, 5 ppt, and 65 ppt for gas phase NH(3(g)), SO(2(g)), and HNO(3(g)) and 29 ng m(-3), 3 ng m(-3), and 45 ng m(-3) for particle phase NH(4)(+), SO(4)(2-), and NO(3)(-) respectively. From external trace gas calibrations with permeation sources, we determined that the AIM-IC is biased low for NH(3(g)) (11%), SO(2(g)) (19%), and HNO(3(g)) (12%). The collection efficiency of SO(2(g)) was found to strongly depend on the composition of the denuder solution and was found to be the most quantitative with 5 mM H(2)O(2) solution for mixing ratios as high as 107 ppb. Using a cellulose membrane in the PPWD, the system responded to changes in SO(2(g)) and HNO(3(g)) within an hour, however for NH(3(g)), the timescale can be closer to 20 h. With a nylon membrane, the instrument response time for NH(3(g)) was significantly improved, becoming comparable to the responses for SO(2(g)) and HNO(3(g)). Performance of the AIM-IC for collection and analysis of PM(2.5) was evaluated by generating known number concentrations of ammonium sulfate and ammonium nitrate particles (with an aerodynamic diameter of 300 nm) under laboratory conditions and by comparing AIM-IC measurements to measurements from a collocated Aerosol Mass Spectrometer (AMS) during a field-sampling campaign. On average, the AIM-IC and AMS measurements agreed well and captured rapid ambient concentration changes at the same time. In this work we also present a novel inlet configuration and plumbing for the AIM-IC which minimizes sampling inlet losses, reduces peak smearing due to sample carryover, and allows for tower-height sampling from the base of a research tower.

Emerging investigator series: ozone uptake by urban road dust and first evidence for chlorine activation during ozone uptake by agro-based anti-icer: implications for wintertime air quality in high-latitude urban environments.

High-latitude urban regions provide a unique and complex range of environmental surfaces for uptake of trace pollutant gases, including winter road maintenance materials (e.g., gravel, rock salts, and anti-icer, a saline solution applied to roads during winter). In an effort to reduce the negative environmental and economic impacts of road salts, many municipalities have turned to agro-based anti-icing materials that are rich in organic material. To date, the reactivity of both anti-icer and saline road dust with pollutant gases remain unexplored, which limits our ability to assess the potential impacts of these materials on air quality in high-latitude regions. Here, we used a coated-wall flow tube to investigate the uptake of ozone, an important air pollutant, by road dust collected in Edmonton, Canada. At 25% relative humidity (RH) and 50 ppb ozone, γBET for ozone uptake by this sample is (8.0 ± 0.7) × 10-8 under dark conditions and (2.1 ± 0.1) × 10-7 under illuminated conditions. These values are 2-4× higher than those previously obtained by our group for natural mineral dusts, but are not large enough for suspended road dust to influence local ozone mixing ratios. In a separate set of experiments, we also investigated the uptake of ozone by calcium chloride (i.e., road salt) and commercial anti-icer solution. Although ozone uptake by pure calcium chloride was negligible, ozone uptake by anti-icer was significant, which implies that the reactivity of anti-icer is conferred by its organic content. Importantly, ozone uptake by anti-icer-and, to a lesser extent, road dust doped with anti-icer-leads to the release of inorganic chlorine gas, which we collected using inline reductive trapping and quantified using ion chromatography. To explain these results, we propose a novel pathway for chlorine activation: here, ozone oxidation of the anti-icer organic fraction (in this case, molasses) yields reactive OH radicals that can oxidize chloride. In summary, this study demonstrates the ability of road dust and anti-icer to influence atmospheric oxidant mixing ratios in cold-climate urban areas, and highlights previously unidentified air quality impacts of winter road maintenance decisions.

Hydrogen chloride (HCl) at ground sites during CalNex 2010 and insight into its thermodynamic properties.

Gas phase hydrogen chloride (HCl) was measured at Pasadena and San Joaquin Valley (SJV) ground sites in California during May and June 2010 as part of the CalNex study. Observed mixing ratios were on average 0.83 ppbv at Pasadena, ranging from below detection limit (0.055 ppbv) to 5.95 ppbv, and were on average 0.084 ppbv at SJV with a maximum value of 0.776 ppbv. At both sites, HCl levels were highest during midday and shared similar diurnal variations with HNO3. Coupled phase partitioning behavior was found between HCl/Cl- and HNO3/NO3 - using thermodynamic modelling and observations. Regional modeling of Cl- and HCl using CMAQ captures some of the observed relationships but underestimates measurements by a factor of 5 or more. Chloride in the 2.5-10 µm size range in Pasadena was sometimes higher than sea salt abundances, based on co-measured Na+, implying that sources other than sea salt are important. The acid-displacement of HCl/Cl- by HNO3/NO3 - (phase partitioning of semi-volatile acids) observed at the SJV site can only be explained by aqueous phase reaction despite low RH conditions and suggests the temperature dependence of HCl phase partitioning behavior was strongly impacted by the activity coefficient changes under relevant aerosol conditions (e.g., high ionic strength). Despite the influence from activity coefficients, the gas-particle system was found to be well constrained by other stronger buffers and charge balance so that HCl and Cl- concentrations were reproduced well by thermodynamic models.