Proton-transfer Chemical-ionization Mass Spectrometry Research Articles

Comparison of negative-ion proton-transfer with iodide ion chemical ionization mass spectrometry for quantification of isocyanic acid in ambient air

Isocyanic acid (HNCO) is a trace gas pollutant of potential importance to human health whose measurement has recently become possible through the development of negative-ion proton-transfer chemical ionization mass spectrometry (NI-PT-CIMS) with acetate reagent ion. In this manuscript, an alternative ionization and detection scheme, in which HNCO is quantified by iodide CIMS (iCIMS) as a cluster ion at m/z 170, is described. The sensitivity was inversely proportional to water vapor concentration but could be made independent of humidity changes in the sampled air by humidifying the ion–molecule reaction (IMR) region of the CIMS. The performance of the two ionization schemes was compared and contrasted using ambient air measurements of HNCO mixing ratios in Calgary, AB, Canada, by NI-PT-CIMS with acetate reagent ion from Dec 16 to 20, 2013, and by the same CIMS operated in iCIMS mode from Feb 3 to 7, 2014. The iCIMS exhibited a greater signal-to-noise ratio than the NI-PT-CIMS, not because of its sensitivity, which was lower (∼0.083 normalized counts per second (NCPS) per parts-per-trillion by volume (pptv) compared to ∼9.7 NCPS pptv−1), but because of a much lower and more stable background (3 ± 4 compared to a range of ∼2 × 103 to ∼6 × 103 NCPS). For the Feb 2014 data set, the HNCO mixing ratios in Calgary air ranged from <12 to 94 pptv (median 34 pptv), were marginally higher at night than during day, and correlated with nitrogen oxide (NOx = NO + NO2) mixing ratios and submicron particle volume. The ratios of HNCO to NOx observed are within the range of emission ratios reported for gasoline-powered motor vehicles.

Coupling field and laboratory measurements to estimate the emission factors of identified and unidentified trace gases for prescribed fires

Abstract. An extensive program of experiments focused on biomass burning emissions began with a laboratory phase in which vegetative fuels commonly consumed in prescribed fires were collected in the southeastern and southwestern US and burned in a series of 71 fires at the US Forest Service Fire Sciences Laboratory in Missoula, Montana. The particulate matter (PM2.5) emissions were measured by gravimetric filter sampling with subsequent analysis for elemental carbon (EC), organic carbon (OC), and 38 elements. The trace gas emissions were measured by an open-path Fourier transform infrared (OP-FTIR) spectrometer, proton-transfer-reaction mass spectrometry (PTR-MS), proton-transfer ion-trap mass spectrometry (PIT-MS), negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS), and gas chromatography with MS detection (GC-MS). 204 trace gas species (mostly non-methane organic compounds (NMOC)) were identified and quantified with the above instruments. Many of the 182 species quantified by the GC-MS have rarely, if ever, been measured in smoke before. An additional 153 significant peaks in the unit mass resolution mass spectra were quantified, but either could not be identified or most of the signal at that molecular mass was unaccounted for by identifiable species. In a second, "field" phase of this program, airborne and ground-based measurements were made of the emissions from prescribed fires that were mostly located in the same land management units where the fuels for the lab fires were collected. A broad variety, but smaller number of species (21 trace gas species and PM2.5) was measured on 14 fires in chaparral and oak savanna in the southwestern US, as well as pine forest understory in the southeastern US and Sierra Nevada mountains of California. The field measurements of emission factors (EF) are useful both for modeling and to examine the representativeness of our lab fire EF. The lab EF/field EF ratio for the pine understory fuels was not statistically different from one, on average. However, our lab EF for "smoldering compounds" emitted from the semiarid shrubland fuels should likely be increased by a factor of ~2.7 to better represent field fires. Based on the lab/field comparison, we present emission factors for 357 pyrogenic species (including unidentified species) for 4 broad fuel types: pine understory, semiarid shrublands, coniferous canopy, and organic soil. To our knowledge this is the most comprehensive measurement of biomass burning emissions to date and it should enable improved representation of smoke composition in atmospheric models. The results support a recent estimate of global NMOC emissions from biomass burning that is much higher than widely used estimates and they provide important insights into the nature of smoke. 31–72% of the mass of gas-phase NMOC species was attributed to species that we could not identify. These unidentified species are not represented in most models, but some provision should be made for the fact that they will react in the atmosphere. In addition, the total mass of gas-phase NMOC divided by the mass of co-emitted PM2.5 averaged about three (range ~2.0–8.7). About 35–64% of the NMOC were likely semivolatile or of intermediate volatility. Thus, the gas-phase NMOC represent a large reservoir of potential precursors for secondary formation of ozone and organic aerosol. For the single lab fire in organic soil about 28% of the emitted carbon was present as gas-phase NMOC and ~72% of the mass of these NMOC was unidentified, highlighting the need to learn more about the emissions from smoldering organic soils. The mass ratio of total NMOC to "NOx as NO" ranged from 11 to 267, indicating that NOx-limited O3 production would be common in evolving biomass burning plumes. The fuel consumption per unit area was 7.0 ± 2.3 Mg ha−1 and 7.7 ± 3.7 Mg ha−1 for pine-understory and semiarid shrubland prescribed fires, respectively.

Evidence of rapid production of organic acids in an urban air mass

[1] Gas-phase acids (nitric, formic, acrylic, methacrylic, propionic, and pyruvic/butryic acid) were measured using negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS) in Pasadena, CA as part of the CalNex 2010 (Research at the Nexus of Air Quality and Climate Change) study in May–June 2010. Organic acid concentrations ranged from a few parts per trillion by volume (pptv) to several parts per billion by volume (ppbv), with the largest concentrations observed for formic and propionic acids. Photochemically processed urban emissions transported from Los Angeles were frequently sampled during the day. Analysis of transported emissions demonstrates a strong correlation of organic acid concentrations with both nitric acid and odd oxygen (Ox = O3 + NO2) showing that the organic acids are photochemically and rapidly produced from urban emissions.

Measurement of HONO, HNCO, and other inorganic acids by negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS): application to biomass burning emissions

Abstract. A negative-ion proton-transfer chemical ionization mass spectrometric technique (NI-PT-CIMS), using acetate as the reagent ion, was applied to the measurement of volatile inorganic acids of atmospheric interest: hydrochloric (HCl), nitrous (HONO), nitric (HNO3), and isocyanic (HNCO) acids. Gas phase calibrations through the sampling inlet showed the method to be intrinsically sensitive (6–16 cts/pptv), but prone to inlet effects for HNO3 and HCl. The ion chemistry was found to be insensitive to water vapor concentrations, in agreement with previous studies of carboxylic acids. The inlet equilibration times for HNCO and HONO were 2 to 4 s, allowing for measurement in biomass burning studies. Several potential interferences in HONO measurements were examined: decomposition of HNO3·NO3− clusters within the CIMS, and NO2-water production on inlet surfaces, and were quite minor (≤1%, 3.3%, respectively). The detection limits of the method were limited by the instrument backgrounds in the ion source and flow tube, and were estimated to range between 16 and 50 pptv (parts per trillion by volume) for a 1 min average. The comparison of HONO measured by CIMS and by in situ FTIR showed good correlation and agreement to within 17%. The method provided rapid and accurate measurements of HNCO and HONO in controlled biomass burning studies, in which both acids were seen to be important products.

Development and validation of a portable gas phase standard generation and calibration system for volatile organic compounds

Abstract. We report on the development of an accurate, portable, dynamic calibration system for volatile organic compounds (VOCs). The Mobile Organic Carbon Calibration System (MOCCS) combines the production of gas-phase VOC standards using permeation or diffusion sources with quantitative total organic carbon (TOC) conversion on a palladium surface to CO2 in the presence of oxygen, and the subsequent CO2 measurement. MOCCS was validated using three different comparisons: (1) TOC of high accuracy methane standards compared well to expected concentrations (3% relative error), (2) a gas-phase benzene standard was generated using a permeation source and measured by TOC and gas chromatography mass spectrometry (GC-MS) with excellent agreement (&lt;4% relative difference), and (3) total carbon measurement of 4 known gas phase mixtures were performed and compared to a calculated carbon content to agreement within the stated uncertainties of the standards. Measurements from laboratory biomass burning experiments of formic acid by negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS) and formaldehyde by proton transfer reaction-mass spectrometry (PTR-MS), both calibrated using MOCCS, were compared to open path Fourier transform infrared spectroscopy (OP-FTIR) to validate the MOCCS calibration and were found to compare well (R2 of 0.91 and 0.99, respectively).

Development of negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS) for the measurement of gas-phase organic acids in the atmosphere

We have developed a negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS) technique for on-line analysis of gaseous organic and inorganic acids. In this detection scheme, acetate ions (CH 3C(O)O −) react very selectively with atmospheric trace acids, by proton transfer, to produce unique product ion species. We tested this ion chemistry for 11 species of which only four showed measurable fragmentation. We investigated both the time response of the inlet and humidity dependence for both formic acid and pyruvic acid measurements. A formic acid calibration was performed and found a sensitivity of 21 ± 4.3 counts per second per pptv. Formic acid measurements made during two separate informal ambient air intercomparisons: (1) with a quantum cascade IR laser absorption system (QCL) and (2) a proton-transfer reaction mass spectrometer (PTR-MS) show good agreement validating this measurement technique. The measurements of the NI-PT-CIMS and PTR-MS agree to within 5% with a high degree of correlation ( r 2 > 0.93). We have found the NI-PT-CIMS detection limit for formic acid is approximately 80–90 pptv for a 1 s integration period, and is currently limited by the formate background in the instrument. The fast time response and high sensitivity of the NI-PT-CIMS method make it a promising technique for the measurement of organic acids in ambient conditions.

Determination of Evaporation Rates and Vapor Pressures of Very Low Volatility Compounds: A Study of the C4−C10 and C12 Dicarboxylic Acids

A method for the measurement of evaporation rates and vapor pressures of low volatility compounds was developed and applied to the homologous series of C4-C10 and C12 dicarboxylic acids. Proton-transfer chemical ionization mass spectrometry was used to follow directly the temperature-dependent evaporation rates of aerosol samples collected on a cold plate that could be heated at a known rate. The vapor pressures of the deposited compounds were derived from observed evaporation rates through application of the Hertz-Knudsen equation. Temperature programmed desorption allowed for quantification of the enthalpy (DeltaHsub) and entropy (DeltaSsub) of sublimation of the diacids and is described. A strong odd-even dependence with respect to the total carbon number was observed in the derived diacid vapor pressures, consistent with previous measurements. However, the vapor pressures from this method were systematically lower than previous measurements. Though seen in the vapor pressure, no odd-even carbon chain length dependence was readily discernible in the measured values of DeltaHsub and DeltaSsub. Perhaps most importantly, these experimental results also suggest that residual solvent molecules (from the aerosol generation process) trapped in the diacid samples can have a considerable influence on the measured thermodynamic parameters and, if not properly accounted for, may give erroneous results.

Proton-Transfer Chemical-Ionization Mass Spectrometry Allows Real-Time Analysis of Volatile Organic Compounds Released from Cutting and Drying of Crops

The wounding and drying of plant material during crop harvest could be a significant source of volatile organic compounds (VOCs) that enter the atmosphere. Here, we show that these primarily oxygenated VOCs can be measured using proton-transfer chemical-ionization mass spectrometry (PT-CIMS), a method that allows online and simultaneous monitoring of oxygenated VOC levels. For clover, alfalfa, and corn, leaf wounding and in particular drying were shown to lead to strongly enhanced emissions of a series of C6 aldehydes, alcohols, and esters derived from (Z)-3-hexenal. Additionally, for the forage crops clover and alfalfa, enhanced emissions of methanol, acetaldehyde, acetone, and butanone were observed. The identities of the measured carbonyl compounds were confirmed using high-pressure liquid chromatography. For clover, initial cutting led to a VOC release of about 175 μg of C (g dry wt)-1, while during drying the cut clover released >1000 μg of C (g dry wt)-1; qualitatively, similar amounts of VOCs were ...

Emissions of volatile organic compounds from cut grass and clover are enhanced during the drying process

The release of volatile organic compounds (VOCs) by drying grass and clover leaves and stems was studied in the laboratory using proton‐transfer chemical‐ionization mass spectrometry, which enables the simultaneous, on‐line monitoring of VOC concentrations. A burst of VOC emissions due to cutting the leaves and stems was followed by a second, more intense emission lasting for several hours when the vegetation was starting to dry out. In addition to (Z)‐3‐hexenal, (Z)‐3‐hexenol, and hexenyl acetate, that were emitted by the plant tissue in response to the wounding, enhanced emissions of methanol, acetaldehyde, acetone, butanone, and possibly formaldehyde were observed. These findings may have important implications for regional air quality in agricultural and urban areas.

Degree-of-freedom activation effects in proton-transfer chemical ionization mass spectrometry of open-chain and cyclic alcohols and diols

The fragmentation of homologous 2-alkanols in t-C 4H 9 + and NH 4 + chemical ionization (CI) mass spectra increases with molecular size. Complementarily, the t-C 4H 9 + and OH − CI spectral stereospecificity decreases from methyl- to butylcyclohexanols and cyclic to steroidal diols. These substrate-size phenomena in near thermoneutral proton-transfer CI are based on a molecular degree-of-freedom (DOF) activation effect, which is similar to DOF assisted largest-alkyl loss in M +. ions, but inverse to DOF stabilization of electron-impact fragment ions. A diagram of substrate internal-energy temperature dependence curves Hv(T) and CI reaction enthalpy levels ΔH r and, secondly, a calculation of critical-molecule percentages are useful quantification attempts of the CI DOF activation effect, for its application to CI spectral problems.

Fragmentation process occurring in proton-transfer chemical-ionization mass spectrometry

The isobutane chemical-ionization mass spectra of deuterium-labelled model compounds show that fragmentation can occur at locations remote from the site of protonation.