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Proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) is a technique commonly used to measure ambient volatile organic compounds (VOCs) in urban, rural, and remote environments. PTR-ToF-MS is known to produce artifacts from ion fragmentation, which complicates the interpretation and quantification of key atmospheric VOCs. This study evaluates the extent to which fragmentation and other ionization processes impacts urban measurements of the PTR-ToF-MS ions typically assigned to isoprene (m/z 69, C5H8H+), acetaldehyde (m/z 45, CH3CHO+), and benzene (m/z 79, C6H6H+). Interferences from fragmentation are identified using gas-chromatography (GC) pre-separation and the impact of these interferences are quantified using ground-based and airborne measurements in a number of US cities, including Las Vegas, Los Angeles, New York City, and Detroit. In urban regions with low biogenic isoprene emissions (e.g., Las Vegas), fragmentation from higher carbon aldehydes and cycloalkanes emitted from anthropogenic sources may contribute to m/z 69 by as much as 50% during the day, while the majority of the signal at m/z 69 is attributed to fragmentation during the night. Interferences are a higher fraction of m/z 69 during airborne studies, which likely results from differences in the reactivity between isoprene and the interfering species along with the subsequent changes to the VOC mixture at higher altitudes. For other PTR masses, including m/z 45 and m/z 79, interferences are observed due to the fragmentation and secondary ionization of VOCs typically used in solvents, which are becoming a more important source of anthropogenic VOCs in urban areas. We present methods to correct these interferences, which provide better agreement with GC measurements of isomer specific molecules. These observations show the utility of deploying GC pre-separation for the interpretation PTR-ToF-MS spectra. [ABSTRACT FROM AUTHOR]

In this study, we describe the characterization and field deployment of a Chemical Ionization Mass Spectrometry (CIMS) using a recently developed focusing ion-molecule reactor (FIMR) and ammonium-water cluster (NH4+·H2O) as the reagent ion (denoted as NH4+ CIMS). We show that NH4+·H2O is a highly versatile reagent ion for measurements of a wide range of oxygenated organic compounds. The major product ion is the cluster with NH4+ produced via ligand-switching reactions. Other product ions (e.g., protonated ion, cluster ion with NH4+·H2O, with H3O+, and with H3O+·H2O) are also produced, but with minor fractions for most of the oxygenated compounds studied here. The instrument sensitivities (counts per second per ppbv, cps ppbv-1) and product distributions are strongly dependent on the instrument operating conditions, including the ratio of ammonia (NH3) and H2O flows and the drift voltages, which should be carefully selected to ensure NH4+·H2O as the predominant reagent ion and to optimize sensitivities. For monofunctional analytes, the NH4+·H2O chemistry exhibits high sensitivity (i.e., > 1000 cps ppbv-1) towards ketones, moderate sensitivity (i.e., between 100 and 1000 cps ppbv-1) towards aldehdyes, alcohols, organic acids, and monoterpenes, low sensitivity (i.e., between 10 and 100 cps ppbv-1) towards isoprene and C1 and C2 organics, and negligible sensitivity (i.e., < 10 cps ppbv-1) towards reduced aromatics. The instrumental sensitivities of analytes depend on the binding energy of the analyte-NH4+ cluster, which can be estimated using voltage scanning. This offers the possibility to constrain the sensitivity of analytes for which no calibration standards exist. This instrument was deployed in the RECAP campaign (Re-Evaluating the Chemistry of Air Pollutants in California) in Pasadena, California during summer 2021. Measurement comparisons against co-located mass spectrometers show that the NH4+ CIMS is capable of detecting compounds from a wide range of chemical classes. The NH4+ CIMS is valuable for quantification of oxygenated VOCs and is complementary to existing chemical ionization schemes. [ABSTRACT FROM AUTHOR]

The chemical composition of aerosol particles is a key aspect in determining their impact on the environment. For example, nitrogen (N)-containing particles impact atmospheric chemistry, air quality, and ecological N-deposition. Instruments that measure total reactive nitrogen (Nr = all nitrogen compounds except for N2 and N2O) focus on gas-phase nitrogen and very few studies directly discuss the instrument capacity to measure the mass of Nr-containing particles. Here, we investigate the mass quantification of particle-bound nitrogen using a custom Nr system that involves total conversion to nitric oxide (NO) across platinum and molybdenum catalysts followed by NO-O3 chemiluminescence detection. We evaluate the particle conversion of the Nr instrument by comparing to mass derived concentrations of size-selected and counted ammonium sulfate ((NH4)2SO4), ammonium nitrate (NH4NO3), ammonium chloride (NH4Cl), sodium nitrate (NaNO3), and ammonium oxalate ((NH4)2C2O4) particles determined using instruments that measure particle number and size. These measurements demonstrate Nr-particle conversion across the Nr catalysts that is independent of particle size with 98 ± 10 % efficiency for 100-600 nm particle diameters. We also show conversion of particle-phase organic carbon species to CO2 across the instrument's platinum catalyst followed by a non-dispersive infrared (NDIR) CO2 detector. We show the Nr system is an accurate particle mass measurement method and demonstrate its ability to calibrate particle mass measurement instrumentation using single component, laboratory generated, Nr-containing particles below 2.5 µm in size. In addition we show agreement with mass measurements of an independently calibrated on-line particle-into-liquid sampler directly coupled to the electrospray ionization source of a quadrupole mass spectrometer (PILS-ESI/MS) sampling in the negative ion mode. We obtain excellent correlations (R² = 0.99) of particle mass measured as Nr with PILS-ESI/MS measurements converted to the corresponding particle anion mass (e.g. nitrate, sulfate, and chloride). The Nr and PILS-ESI/MS are shown to agree to within ~ 6 % for particle mass loadings up to 120 µg m-3. Consideration of all the sources of error in the PILS-ESI/MS technique yields an overall uncertainty of ±20 % for these single component particle streams. These results demonstrate the Nr system is a reliable direct particle mass measurement technique that differs from other particle instrument calibration techniques that rely on knowledge of particle size, shape, density, and refractive index. [ABSTRACT FROM AUTHOR]