High-resolution Time-of-flight Chemical Ionization Mass Spectrometer Research Articles

Sources of elevated organic acids in the mountainous background atmosphere of southern China

Formic acid (FA) and acetic acid (AA) are pivotal organic acids in the troposphere, significantly influencing atmospheric chemistry. However, their abundance and sources in the mountainous background atmosphere remain underexplored. We undertook continuous measurements of FA and AA in Nanling mountains, southern China, during autumn 2020 using a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS). Both acids registered higher concentrations than in other global high-altitude or forested locations, averaging at 0.89 (max: 3.91) and 0.95 (max: 3.52) ppbv for FA and AA, respectively. High concentrations of FA and AA in this forested background area arose from secondary formation and biomass burning, collectively contributing 71 % to 89 %. During episodes, FA and AA concentrations surged 2–3 times, owing to the enhanced atmospheric oxidation capacity. The secondary FA production was predominantly due to isoprene oxidation among the VOC precursors studied. However, observed inconsistencies between calculated and actual FA concentrations suggest overlooked precursors or mechanisms warranting further investigation. Our findings can enhance the understanding of organic acid characteristics and the interplay of biogenic and anthropogenic sources in the background atmosphere.

Technical note: Gas-phase nitrate radical generation via irradiation of aerated ceric ammonium nitrate mixtures

Abstract. We present a novel photolytic source of gas-phase NO3 suitable for use in atmospheric chemistry studies that has several advantages over traditional sources that utilize NO2 + O3 reactions and/or thermal dissociation of dinitrogen pentoxide (N2O5). The method generates NO3 via irradiation of aerated aqueous solutions of ceric ammonium nitrate (CAN, (NH4)2Ce(NO3)6) and nitric acid (HNO3) or sodium nitrate (NaNO3). We present experimental and model characterization of the NO3 formation potential of irradiated CAN / HNO3 and CAN / NaNO3 mixtures containing [CAN] = 10−3 to 1.0 M, [HNO3] = 1.0 to 6.0 M, [NaNO3] = 1.0 to 4.8 M, photon fluxes (I) ranging from 6.9 × 1014 to 1.0 × 1016 photons cm−2 s−1, and irradiation wavelengths ranging from 254 to 421 nm. NO3 mixing ratios ranging from parts per billion to parts per million by volume were achieved using this method. At the CAN solubility limit, maximum [NO3] was achieved using [HNO3] ≈ 3.0 to 6.0 M and UVA radiation (λmax⁡ = 369 nm) in CAN / HNO3 mixtures or [NaNO3] ≥ 1.0 M and UVC radiation (λmax⁡ = 254 nm) in CAN / NaNO3 mixtures. Other reactive nitrogen (NO2, N2O4, N2O5, N2O6, HNO2, HNO3, HNO4) and reactive oxygen (HO2, H2O2) species obtained from the irradiation of ceric nitrate mixtures were measured using a NOx analyzer and an iodide-adduct high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS). To assess the applicability of the method for studies of NO3-initiated oxidative aging processes, we generated and measured the chemical composition of oxygenated volatile organic compounds (OVOCs) and secondary organic aerosol (SOA) from the β-pinene + NO3 reaction using a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to the HR-ToF-CIMS.

Field observations of C2 and C3 organosulfates and insights into their formation mechanisms at a suburban site in Hong Kong

Organosulfates (OSs) are formed from volatile organic compounds (VOCs) and their oxidation products in the presence of sulfate particles. While OSs represent an important component in secondary organic aerosol, the knowledge of their formation driving force, mechanisms, and environmental impact remain inadequately understood. In this study, we report ambient observations of C2–3 oxygenated VOCs derived OSs (C2–3 OSs) at a suburban location of Hong Kong during autumn 2016. The C2–3 OSs, including glycolaldehyde sulfate (GS), hydroxyacetone sulfate (HAS), glycolic acid sulfate (GAS), and lactic acid sulfate (LAS), were quantified/semi-quantified using offline liquid chromatography-mass spectrometry analysis of aerosol filter samples. The average sum concentration of C2–3 OSs was 36 ng/m3. Correlation analysis revealed that sulfate, surface area, and liquid water content were important factors influencing C2–3 OS formation. Online measurement with an iodide High-Resolution Time-of-Flight Chemical-Ionization Mass Spectrometer (HR-ToF-CIMS) coupled with the Filter Inlet for Gases and AEROsols (FIGAERO) was also conducted to monitor C2–3 OSs, and their potential oxygenated VOC precursors in both gas- and particle-phase, and aerosol acidity tracer simultaneously. Our measurements support that glycolaldehyde/glyoxal, hydroxyacetone, glycolic acid/glyoxal, and lactic acid/methylglyoxal are likely precursors for GS, HAS, GAS, and LAS, respectively. Additionally, we found strong correlation between C2–3 OSs and H3S2O8−, a marker for aerosol acidity, providing field observational evidence for acid-catalyzed formation of small OSs. Based on both online and offline measurements, acid-catalyzed formation mechanisms in particle/aqueous phase are proposed. Specifically, the unique structure of adjacent carbonyl and hydroxyl groups in the C2–3 oxygenated VOC precursors can facilitate the formation of (1) a five-member ring intermediate via intramolecular hydrogen bond to react with sulfur trioxide through heterogenous reaction or (2) cyclic sulfate intermediate via particle-phase reaction with sulfuric acid to generate C2–3 OSs. These proposed mechanisms provide an alternative pathway for the liquid-phase production of C2–3 OSs.

An intercomparison study of four different techniques for measuring the chemical composition of nanoparticles

Abstract. Currently, the complete chemical characterization of nanoparticles (< 100 nm) represents an analytical challenge, since these particles are abundant in number but have negligible mass. Several methods for particle-phase characterization have been recently developed to better detect and infer more accurately the sources and fates of sub-100 nm particles, but a detailed comparison of different approaches is missing. Here we report on the chemical composition of secondary organic aerosol (SOA) nanoparticles from experimental studies of α-pinene ozonolysis at −50, −30, and −10 ∘C and intercompare the results measured by different techniques. The experiments were performed at the Cosmics Leaving OUtdoor Droplets (CLOUD) chamber at the European Organization for Nuclear Research (CERN). The chemical composition was measured simultaneously by four different techniques: (1) thermal desorption–differential mobility analyzer (TD–DMA) coupled to a NO3- chemical ionization–atmospheric-pressure-interface–time-of-flight (CI–APi–TOF) mass spectrometer, (2) filter inlet for gases and aerosols (FIGAERO) coupled to an I− high-resolution time-of-flight chemical ionization mass spectrometer (HRToF-CIMS), (3) extractive electrospray Na+ ionization time-of-flight mass spectrometer (EESI-TOF), and (4) offline analysis of filters (FILTER) using ultra-high-performance liquid chromatography (UHPLC) and heated electrospray ionization (HESI) coupled to an Orbitrap high-resolution mass spectrometer (HRMS). Intercomparison was performed by contrasting the observed chemical composition as a function of oxidation state and carbon number, by estimating the volatility and comparing the fraction of volatility classes, and by comparing the thermal desorption behavior (for the thermal desorption techniques: TD–DMA and FIGAERO) and performing positive matrix factorization (PMF) analysis for the thermograms. We found that the methods generally agree on the most important compounds that are found in the nanoparticles. However, they do see different parts of the organic spectrum. We suggest potential explanations for these differences: thermal decomposition, aging, sampling artifacts, etc. We applied PMF analysis and found insights of thermal decomposition in the TD–DMA and the FIGAERO.

A Coupled Volatility and Molecular Composition Based Source Apportionment of Atmospheric Organic Aerosol

We apply non-negative matrix factorization (NNMF) to molecular composition and volatility measurements of ambient sub-micrometer particles made using a high-resolution time of flight chemical ionization mass spectrometer (HRToF-CIMS) equipped with a custom filter inlet for gases and aerosols (FIGAERO) as part of the Southern Oxidant and Aerosol Study (SOAS). The resulting factors have a representative thermogram, which carries information on the factor volatility and unique weights for individual ions corresponding to molecular components of measured organic aerosol (OA). These properties and the diurnal patterns of factor weights are used to assign a specific source to each factor. With no a priori information used as input, the routine produces a set of factors with spectra that align well with those previously determined from several laboratory chamber experiments. The factorization routine gains relevance and separation of OA composition when using resolved thermograms as input rather than integrated thermogram time series. Of the seven factors produced by NNMF using the thermogram data, three are attributed to monoterpene-derived OA with extremely low, low, and semivolatile volatility. These three factors together represent 68% of the total organic aerosol mass examined, consistent with previous studies using a spectral basis set. Additionally, two factors were sourced to isoprene chemistry, one representing IEPOX-derived SOA, and the other relating to other oxidation products exhibiting relatively low volatility. The two isoprene-related factors account for 22% of OA mass. Notably absent is a category exclusively capturing the behavior of particulate organic nitrates (PON), which may be consistent with the relatively low local concentrations of PON observed and points to limitations of factorization to fully characterize OA. However, NNMF applied to the volatility and molecular level information from the FIGAERO HRToF-CIMS can resolve dominant precursors and chemical properties of ambient OA components with minimal assumptions.

Molecular characterization and optical properties of primary emissions from a residential wood burning boiler

Modern small-scale biomass burners have been recognized as an important renewable energy source because of the economic and environmental advantages of biomass over fossil fuels. However, the characteristics of their gas and particulate emissions remain incompletely understood, and there is substantial uncertainty concerning their health and climate impacts. Here, we present online measurements conducted during the operation of a residential wood-burning boiler. The measured parameters include gas and particle concentrations, optical absorption and chemical characteristics of gases and particles. Positive matrix factorization was performed to analyze data from a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) equipped with a filter inlet for gases and aerosols (FIGAERO). Six factors were identified and interpreted. Three factors were related to the chemical composition of the fuel representing lignin pyrolysis products, cellulose/hemicellulose pyrolysis products, and nitrogen-containing organics, while three factor were related to the physical characteristics of the emitted compounds: volatile compounds, semi-volatile compounds, and filter-derived compounds. An ordinal analysis was performed based on the factor fractions to identify the most influential masses in each factor, and by deconvoluting high-resolution mass spectra fingerprint molecules for each factor were identified. Results from the factor analysis were linked to the optical properties of the emissions, and lignin and cellulose/hemicellulose pyrolysis products appeared to be the most important sources of brown carbon under the tested burning conditions. It is concluded that the emissions from the complex combustion process can be described by a limited set of physically meaningful factors, which will help to rationalize subsequent transformation and tracing of emissions in the atmosphere and associated impacts on health and climate.

Mechanism of the atmospheric chemical transformation of acetylacetone and its implications in night-time second organic aerosol formation

Recently, a high concentration of acetylacetone (AcAc) has been measured in China, and its day-time chemistry with OH reaction has been evaluated. The phenomenon has profound implications in air pollution, human health and climate change. To systematically understand the atmospheric chemistry of AcAc and its role in the atmosphere, the night-time chemistry of AcAc with O3 and NO3 radical were investigated in this work in detail using density functional theory. The results show that for O3- and NO3-initiated atmospheric oxidation reactions of AcAc, the barrier energies of O3/NO3-addition are found to be much lower than those of H-abstraction, suggesting that O3/NO3-addition to AcAc is a major contributing pathway in the atmospheric chemical transformation reactions. The total degradation rate constants were calculated to be 2.36 × 10−17 and 1.92 × 10−17 cm3 molecule−1 s−1 for the O3- and NO3-initiated oxidation of AcAc at 298 K, respectively. The half-life of AcAc+O3 in some polluted areas (such as, Pearl River Delta and Yangtze River Delta) is close to 3 h under typical tropospheric conditions. Due to its short half-life, the ozonolysis of AcAc plays a more significant role in the night-time hours, leading to fast transformations to form primary ozonides (POZs). A prompt, thermal decomposition of POZs occurred to yield methylglyoxal, acetic acid and Criegee intermediates, which mainly contributed to the formation of secondary organic aerosol (SOA). Subsequently, using the high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS), a non-negligible concentration of AcAc was measured in the field observation during the night-time in Nanjing, China. The obtained results reveal that the atmospheric oxidation of AcAc can successively contribute to the formation of SOA under polluted environments regardless of the time (day-time or night-time). This is due to its high reactivity to tropospheric oxidant species (such as, O3 and NO3 radicals at night-time).

A method for extracting calibrated volatility information from the FIGAERO-HR-ToF-CIMS and its experimental application

Abstract. The Filter Inlet for Gases and AEROsols (FIGAERO) is an inlet specifically designed to be coupled with the Aerodyne High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (HR-ToF-CIMS). The FIGAERO-HR-ToF-CIMS provides simultaneous molecular information relating to both the gas- and particle-phase samples and has been used to extract vapour pressures (VPs) of the compounds desorbing from the filter whilst giving quantitative concentrations in the particle phase. However, such extraction of vapour pressures of the measured particle-phase components requires use of appropriate, well-defined, reference compounds. Vapour pressures for the homologous series of polyethylene glycols (PEG) ((H-(O-CH2-CH2)n-OH) for n=3 to n=8), covering a range of vapour pressures (VP) (10−1 to 10−7 Pa) that are atmospherically relevant, have been shown to be reproduced well by a range of different techniques, including Knudsen Effusion Mass Spectrometry (KEMS). This is the first homologous series of compounds for which a number of vapour pressure measurement techniques have been found to be in agreement, indicating the utility as a calibration standard, providing an ideal set of benchmark compounds for accurate characterization of the FIGAERO for extracting vapour pressure of measured compounds in chambers and the real atmosphere. To demonstrate this, single-component and mixture vapour pressure measurements are made using two FIGAERO-HR-ToF-CIMS instruments based on a new calibration determined from the PEG series. VP values extracted from both instruments agree well with those measured by KEMS and reported values from literature, validating this approach for extracting VP data from the FIGAERO. This method is then applied to chamber measurements, and the vapour pressures of known products are estimated.

Elucidating real-world vehicle emission factors from mobile measurements over a large metropolitan region: a focus on isocyanic acid, hydrogen cyanide, and black carbon

Abstract. A mobile laboratory equipped with state-of-the-art gaseous and particulate instrumentation was deployed across the Greater Toronto Area (GTA) during two seasons. A high-resolution time-of-flight chemical ionization mass spectrometer (HR-TOF-CIMS) measured isocyanic acid (HNCO) and hydrogen cyanide (HCN), and a high-sensitivity laser-induced incandescence (HS-LII) instrument measured black carbon (BC). Results indicate that on-road vehicles are a clear source of HNCO and HCN and that their impact is more pronounced in the winter, when influences from biomass burning (BB) and secondary photochemistry are weakest. Plume-based and time-based algorithms were developed to calculate fleet-average vehicle emission factors (EFs); the algorithms were found to yield comparable results, depending on the pollutant identity. With respect to literature EFs for benzene, toluene, C2 benzene (sum of m-, p-, and o-xylenes and ethylbenzene), nitrogen oxides, particle number concentration (PN), and black carbon, the calculated EFs were characteristic of a relatively clean vehicle fleet dominated by light-duty vehicles (LDV). Our fleet-average EF for BC (median: 25 mg kgfuel-1; interquartile range, IQR: 10–76 mg kgfuel-1) suggests that overall vehicular emissions of BC have decreased over time. However, the distribution of EFs indicates that a small proportion of high-emitters continue to contribute disproportionately to total BC emissions. We report the first fleet-average EF for HNCO (median: 2.3 mg kgfuel-1, IQR: 1.4–4.2 mg kgfuel-1) and HCN (median: 0.52 mg kgfuel-1, IQR: 0.32–0.88 mg kgfuel-1). The distribution of the estimated EFs provides insight into the real-world variability of HNCO and HCN emissions and constrains the wide range of literature EFs obtained from prior dynamometer studies. The impact of vehicle emissions on urban HNCO levels can be expected to be further enhanced if secondary HNCO formation from vehicle exhaust is considered.

Flight Deployment of a High‐Resolution Time‐of‐Flight Chemical Ionization Mass Spectrometer: Observations of Reactive Halogen and Nitrogen Oxide Species

AbstractWe describe the University of Washington airborne high‐resolution time‐of‐flight chemical ionization mass spectrometer (HRToF‐CIMS) and evaluate its performance aboard the NCAR‐NSF C‐130 aircraft during the recent Wintertime INvestigation of Transport, Emissions and Reactivity (WINTER) experiment in February–March of 2015. New features include (i) a computer‐controlled dynamic pinhole that maintains constant mass flow‐rate into the instrument independent of altitude changes to minimize variations in instrument response times; (ii) continuous addition of low flow‐rate humidified ultrahigh purity nitrogen to minimize the difference in water vapor pressure, hence instrument sensitivity, between ambient and background determinations; (iii) deployment of a calibration source continuously generating isotopically labeled dinitrogen pentoxide (15N2O5) for in‐flight delivery; and (iv) frequent instrument background determinations to account for memory effects resulting from the interaction between sticky compounds and instrument surface following encounters with concentrated air parcels. The resulting improvements to precision and accuracy, along with the simultaneous acquisition of these species and the full set of their isotopologues, allow for more reliable identification, source attribution, and budget accounting, for example, by speciating the individual constituents of nocturnal reactive nitrogen oxides (NOz = ClNO2 + 2 × N2O5 + HNO3 + etc.). We report on an expanded set of species quantified using iodide‐adduct ionization such as sulfur dioxide (SO2), hydrogen chloride (HCl), and other inorganic reactive halogen species including hypochlorous acid, nitryl chloride, chlorine, nitryl bromide, bromine, and bromine chloride (HOCl, ClNO2, Cl2, BrNO2, Br2, and BrCl, respectively).

Characterization of organic nitrate constituents of secondary organic aerosol (SOA) from nitrate-radical-initiated oxidation of limonene using high-resolution chemical ionization mass spectrometry

Abstract. The gas-phase nitrate radical (NO3⚫) initiated oxidation of limonene can produce organic nitrate species with varying physical properties. Low-volatility products can contribute to secondary organic aerosol (SOA) formation and organic nitrates may serve as a NOx reservoir, which could be especially important in regions with high biogenic emissions. This work presents the measurement results from flow reactor studies on the reaction of NO3⚫ with limonene using a High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (HR-ToF-CIMS) combined with a Filter Inlet for Gases and AEROsols (FIGAERO). Major condensed-phase species were compared to those in the Master Chemical Mechanism (MCM) limonene mechanism, and many non-listed species were identified. The volatility properties of the most prevalent organic nitrates in the produced SOA were determined. Analysis of multiple experiments resulted in the identification of several dominant species (including C10H15NO6, C10H17NO6, C8H11NO6, C10H17NO7, and C9H13NO7) that occurred in the SOA under all conditions considered. Additionally, the formation of dimers was consistently observed and these species resided almost completely in the particle phase. The identities of these species are discussed, and formation mechanisms are proposed. Cluster analysis of the desorption temperatures corresponding to the analyzed particle-phase species yielded at least five distinct groupings based on a combination of molecular weight and desorption profile. Overall, the results indicate that the oxidation of limonene by NO3⚫ produces a complex mixture of highly oxygenated monomer and dimer products that contribute to SOA formation.

Uptake of Gaseous Alkylamides by Suspended Sulfuric Acid Particles: Formation of Ammonium/Aminium Salts.

Amides represent an important class of nitrogen-containing compounds in the atmosphere that can in theory interact with atmospheric acidic particles and contribute to secondary aerosol formation. In this study, uptake coefficients (γ) of six alkylamides (C1 to C3) by suspended sulfuric acid particles were measured using an aerosol flow tube coupled to a high resolution time-of-flight chemical ionization mass spectrometer (HRToF-CIMS). At 293 K and < 3% relative humidity (RH), the measured uptake coefficients for six alkylamides were in the range of (4.8-23) × 10-2. A negative dependence upon RH was observed for both N-methylformamide and N,N-dimethylformamide, likely due to decreased mass accommodation coefficients (α) at lower acidities. A negative temperature dependence was observed for N,N-dimethylformamide under < 3% RH, also consistent with the mass accommodation-controlled uptake processes. Chemical analysis of reacted sulfuric acid particles indicates that alkylamides hydrolyzed in the presence of water molecules to form ammonium or aminium. Our results suggest that multiphase uptake of amides will contribute to growth of atmospheric acidic particles and alter their chemical composition.

Controlled nitric oxide production via O(&amp;lt;sup&amp;gt;1&amp;lt;/sup&amp;gt;D) + N&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;O reactions for use in oxidation flow reactor studies

Abstract. Oxidation flow reactors that use low-pressure mercury lamps to produce hydroxyl (OH) radicals are an emerging technique for studying the oxidative aging of organic aerosols. Here, ozone (O3) is photolyzed at 254 nm to produce O(1D) radicals, which react with water vapor to produce OH. However, the need to use parts-per-million levels of O3 hinders the ability of oxidation flow reactors to simulate NOx-dependent secondary organic aerosol (SOA) formation pathways. Simple addition of nitric oxide (NO) results in fast conversion of NOx (NO + NO2) to nitric acid (HNO3), making it impossible to sustain NOx at levels that are sufficient to compete with hydroperoxy (HO2) radicals as a sink for organic peroxy (RO2) radicals. We developed a new method that is well suited to the characterization of NOx-dependent SOA formation pathways in oxidation flow reactors. NO and NO2 are produced via the reaction O(1D) + N2O → 2NO, followed by the reaction NO + O3 → NO2 + O2. Laboratory measurements coupled with photochemical model simulations suggest that O(1D) + N2O reactions can be used to systematically vary the relative branching ratio of RO2 + NO reactions relative to RO2 + HO2 and/or RO2 + RO2 reactions over a range of conditions relevant to atmospheric SOA formation. We demonstrate proof of concept using high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) measurements with nitrate (NO3−) reagent ion to detect gas-phase oxidation products of isoprene and α-pinene previously observed in NOx-influenced environments and in laboratory chamber experiments.

Gas-Phase Carboxylic Acids in a University Classroom: Abundance, Variability, and Sources

Gas-phase carboxylic acids are ubiquitous in ambient air, yet their indoor occurrence and abundance are poorly characterized. To fill this gap, we measured gas-phase carboxylic acids in real-time inside and outside of a university classroom using a high-resolution time-of-flight chemical ionization mass spectrometer (HRToF-CIMS) equipped with an acetate ion source. A wide variety of carboxylic acids were identified indoors and outdoors, including monoacids, diacids, hydroxy acids, carbonyl acids, and aromatic acids. An empirical parametrization was derived to estimate the sensitivity (ion counts per ppt of the analytes) of the HRToF-CIMS to the acids. The campaign-average concentration of carboxylic acids measured outdoors was 1.0 ppb, with the peak concentration occurring in daytime. The average indoor concentration of carboxylic acids was 6.8 ppb, of which 87% was contributed by formic and lactic acid. While carboxylic acids measured outdoors displayed a single daytime peak, those measured indoors displayed a daytime and a nighttime peak. Besides indoor sources such as off-gassing of building materials, evidence for acid production from indoor chemical reactions with ozone was found. In addition, some carboxylic acids measured indoors correlated to CO2 in daytime, suggesting that human occupants may contribute to their abundance either through direct emissions or surface reactions.

Molecular composition and volatility of isoprene photochemical oxidation secondary organic aerosol under low- and high-NO&amp;lt;sub&amp;gt;&amp;lt;i&amp;gt;x&amp;lt;/i&amp;gt;&amp;lt;/sub&amp;gt; conditions

Abstract. We present measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation in an environmental simulation chamber at a variety of oxidant conditions and using dry neutral seed particles to suppress acid-catalyzed multiphase chemistry. A high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) utilizing iodide-adduct ionization coupled to the Filter Inlet for Gases and Aerosols (FIGAERO) allowed for simultaneous online sampling of the gas and particle composition. Under high-HO2 and low-NO conditions, highly oxygenated (O : C ≥ 1) C5 compounds were major components (∼ 50 %) of SOA. The SOA composition and effective volatility evolved both as a function of time and as a function of input NO concentrations. Organic nitrates increased in both the gas and particle phases as input NO increased, but the dominant non-nitrate particle-phase components monotonically decreased. We use comparisons of measured and predicted gas-particle partitioning of individual components to assess the validity of literature-based group-contribution methods for estimating saturation vapor concentrations. While there is evidence for equilibrium partitioning being achieved on the chamber residence timescale (5.2 h) for some individual components, significant errors in group-contribution methods are revealed. In addition, &gt; 30 % of the SOA mass, detected as low-molecular-weight semivolatile compounds, cannot be reconciled with equilibrium partitioning. These compounds desorb from the FIGAERO at unexpectedly high temperatures given their molecular composition, which is indicative of thermal decomposition of effectively lower-volatility components such as larger molecular weight oligomers.

Detection of atmospheric gaseous amines and amides by a high-resolution time-of-flight chemical ionization mass spectrometer with protonated ethanol reagent ions

Abstract. Amines and amides are important atmospheric organic-nitrogen compounds but high time resolution, highly sensitive, and simultaneous ambient measurements of these species are rather sparse. Here, we present the development of a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) method, utilizing protonated ethanol as reagent ions to simultaneously detect atmospheric gaseous amines (C1 to C6) and amides (C1 to C6). This method possesses sensitivities of 5.6–19.4 Hz pptv−1 for amines and 3.8–38.0 Hz pptv−1 for amides under total reagent ion signals of ∼ 0.32 MHz. Meanwhile, the detection limits were 0.10–0.50 pptv for amines and 0.29–1.95 pptv for amides at 3σ of the background signal for a 1 min integration time. Controlled characterization in the laboratory indicates that relative humidity has significant influences on the detection of amines and amides, whereas the presence of organics has no obvious effects. Ambient measurements of amines and amides utilizing this method were conducted from 25 July to 25 August 2015 in urban Shanghai, China. While the concentrations of amines ranged from a few parts per trillion by volume to hundreds of parts per trillion by volume, concentrations of amides varied from tens of parts per trillion by volume to a few parts per billion by volume. Among the C1- to C6-amines, the C2-amines were the dominant species with concentrations up to 130 pptv. For amides, the C3-amides (up to 8.7 ppb) were the most abundant species. The diurnal and backward trajectory analysis profiles of amides suggest that in addition to the secondary formation of amides in the atmosphere, industrial emissions could be important sources of amides in urban Shanghai. During the campaign, photo-oxidation of amines and amides might be a main loss pathway for them in daytime, and wet deposition was also an important sink.

Clustering, methodology, and mechanistic insights into acetate chemical ionization using high-resolution time-of-flight mass spectrometry

Abstract. We present a comprehensive characterization of cluster control and transmission through the Tofwerk atmospheric pressure interface installed on various chemical ionization time-of-flight mass spectrometers using authentic standards. This characterization of the atmospheric pressure interface allows for a detailed investigation of the acetate chemical ionization mechanisms and the impact of controlling these mechanisms on sensitivity, selectivity, and mass spectral ambiguity with the aim of non-targeted analysis. Chemical ionization with acetate reagent ions is controlled by a distribution of reagent ion-neutral clusters that vary with relative humidity and the concentration of the acetic anhydride precursor. Deprotonated carboxylic acids are primarily detected only if sufficient declustering is employed inside the atmospheric pressure interface. The configuration of a high-resolution time-of-flight chemical ionization mass spectrometer (HR-TOF-CIMS) using an acetate chemical ionization source for non-targeted analysis is discussed. Recent approaches and studies characterizing acetate chemical ionization as it applies to the HR-TOF-CIMS are evaluated in light of the work presented herein.

A new technique for the direct detection of HO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; radicals using bromide chemical ionization mass spectrometry (Br-CIMS): initial characterization

Abstract. Hydroperoxy radicals (HO2) play an important part in tropospheric photochemistry, yet photochemical models do not capture ambient HO2 mixing ratios consistently. This is likely due to a combination of uncharacterized chemical pathways and measurement limitations. The indirect nature of current HO2 measurements introduces challenges in accurately measuring HO2; therefore a direct technique would help constrain HOx chemistry in the atmosphere. In this work we evaluate the feasibility of using chemical ionization mass spectrometry (CIMS) and propose a direct HO2 detection scheme using bromide as a reagent ion. Ambient observations were made with a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) in Atlanta over the month of June 2015 to demonstrate the capability of this direct measurement technique. Observations displayed expected diurnal profiles, reaching daytime median values of ∼ 5 ppt between 2 and 3 p.m. local time. The HO2 diurnal profile was found to be influenced by morning-time vehicular NOx emissions and shows a slow decrease into the evening, likely from non-photolytic production, among other factors. Measurement sensitivities of approximately 5.1 ± 1.0 cps ppt−1 for a bromide ion (79Br−) count rate of 106 cps were observed. The relatively low instrument background allowed for a 3σ lower detection limit of 0.7 ppt for a 1 min integration time. Mass spectra of ambient measurements showed the 79BrHO2− peak was the major component of the signal at nominal mass-to-charge 112, suggesting high selectivity for HO2 at this mass-to-charge. More importantly, this demonstrates that these measurements can be achieved using instruments with only unit mass resolution capability.

Online molecular characterization of fine particulate matter in Port Angeles, WA: Evidence for a major impact from residential wood smoke

We present on-line molecular composition measurements of wintertime particulate matter (PM) during 2014 using an iodide-adduct high-resolution, time-of-flight chemical ionization mass spectrometer (HR-TOF-CIMS) coupled to a Filter Inlet for Gases and AEROsols (FIGAERO). These measurements were part of an intensive effort to characterize PM in the region with a focus on ultrafine particle sources. The technique was used to detect and quantify different classes of wood burning tracers, including levoglucosan, methoxyphenols, and nitrocatechols, among other compounds in near real-time. During the campaign, particulate mass concentrations of compounds with the same molecular composition as levoglucosan ranged from 0.002 to 19 μg/m3 with a median mass concentration of 0.9 μg/m3. Wood burning markers, in general, showed a strong diurnal pattern peaking at night and in the early morning. This diurnal profile combined with cold, stagnant conditions, wind directions from predominantly residential areas, and observations of lower combustion efficiency at night support residential wood burning as a dominant source of wintertime PM in Port Angeles. This finding has implications for improving wintertime air quality in the region by encouraging the use of high efficiency wood-burning stoves or other cleaner home heating options throughout the relevant domain.

Modeling the Detection of Organic and Inorganic Compounds Using Iodide-Based Chemical Ionization.

Iodide-based chemical ionization mass spectrometry (CIMS) has been used to detect and measure concentrations of several atmospherically relevant organic and inorganic compounds. The significant electronegativity of iodide and the strong acidity of hydroiodic acid makes electron transfer and proton abstraction essentially negligible, and the soft nature of the adduct formation ionization technique reduces the chances of sample fragmentation. In addition, iodide has a large negative mass defect, which, when combined with the high resolving power of a high resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS), provides good selectivity. In this work, we use quantum chemical methods to calculate the binding energies, enthalpies and free energies for clusters of an iodide ion with a number of atmospherically relevant organic and inorganic compounds. Systematic configurational sampling of the free molecules and clusters was carried out at the B3LYP/6-31G* level, followed by subsequent calculations at the PBE/SDD and DLPNO-CCSD(T)/def2-QZVPP//PBE/aug-cc-pVTZ-PP levels. The binding energies, enthalpies, and free energies thus obtained were then compared to the iodide-based University of Washington HR-ToF-CIMS (UW-CIMS) instrument sensitivities for these molecules. We observed a reasonably linear relationship between the cluster binding enthalpies and logarithmic instrument sensitivities already at the PBE/SDD level, which indicates that relatively simple quantum chemical methods can predict the sensitivity of an iodide-based CIMS instrument toward most molecules. However, higher level calculations were needed to treat some outlier molecules, most notably oxalic acid and methylerythritol. Our calculations also corroborated the recent experimental findings that the molecules that the UW-CIMS detects at maximum sensitivity usually have binding enthalpies to iodide which are higher than about 26 kcal/mol, depending slightly on the level of theory.