Characterization of a bipolar near-infrared laser desorption/ionization aerosol mass spectrometer

A novel method of soft ionization aerosol mass spectrometry (AMS), bipolar near-infrared laser desorption/ionization AMS (BP-NIR-LDI-AMS), has been developed for the on-line, real-time analysis of organic aerosols. Use of a single NIR laser pulse to desorb/ionize aerosols deposited onto an aluminum probe results in minimal analyte fragmentation to produce exclusively intact pseudomolecular ions at [M–H]^? for acidic organic analytes and [M+H]⁺ for basic organic analytes. Incorporation of a bipolar mass spectrometer with the NIR-LDI source enables simultaneous detection of acidic and basic species in organic particles. Limits of detection (total particulate mass sampled) for amino acids common to the organic fraction of atmospheric aerosols ranged from 69.1 pg for ornithine to 197 pg for serine on the positive channel, and from 17.0 pg for glycine to 100 pg for ornithine on the negative channel. From studies of the laser energy dependence of the NIR-LDI mechanism, it was found that [M–H]^? formation for oleic acid proceeds through simultaneous action of two 1064 nm photons, suggesting a surface-assisted process rather than direct photoionization, for which photon energy is insufficient. For acidic aerosol species, sensitivity was found to increase as a function of analyte acidity, while for basic species, [M+H]⁺ ion signals were detected only in the presence of a labile proton source, with the intensity of the ion signals scaling with the acidity of the proton source. The sensitivity of BP-NIR-LDI-AMS to the amino acids was rationalized in terms of their acidic/basic character, as measured by isoelectric point (pI), with the cationic sensitivity scaling proportionally with pI and the anionic sensitivity scaling inversely with pI.

© 2016 American Association for Aerosol Research     

Electrochemical dithiothreitol assay for large-scale particulate matter studies

Particulate matter (PM) air pollution is associated with human morbidity and mortality. Measuring PM oxidative potential has been shown to provide a predictive measurement between PM exposure and adverse health impacts. The dithiothreitol (DTT) assay is commonly used to measure the oxidative potential of PM_2.5 (PM less than 2.5?µm aerodynamic diameter). In the common, kinetic form of this assay, the decay of DTT is quantified over time (indirectly) using 5,5′-dithiobis(2-nitrobenzoic acid) (DTNB, Ellman’s reagent) via UV/vis absorbance spectroscopy. The loss of DTT can also be quantified directly using electrochemical detection. The objectives of this work were (1) to evaluate the electrochemical assay, using commercially available equipment, relative to the UV/vis absorbance assay and (2) to apply the electrochemical method to a large (>100) number of PM_2.5 filter samples. Also presented here is the comparison of an endpoint assay to the kinetic assay, in an attempt to reduce the time, labor, and materials necessary to quantify PM oxidative potential. The endpoint, electrochemical assay gave comparable results to the UV/vis absorbance assay for PM_2.5 filter sample analysis. Finally, high filter mass loadings (higher than about 0.5?µg PM per mm² filter) lead to suboptimal DTT assay performance, which suggests future studies should limit particle mass loadings on filters.

Copyright © 2019 American Association for Aerosol Research     

More unsaturated,cooking-type hydrocarbon-like organic aerosol particle emissions from renewable diesel compared to ultra low sulfur diesel in at-sea operations of a research vessel

The aerosol particle emissions from R/V Robert Gordon Sproul were measured during two 5-day research cruises (29 September–3 October 2014; 4–7 and 26–28 September 2015) at four engine speeds (1600 rpm, 1300 rpm, 1000 rpm, and 700 rpm) to characterize the emissions under different engine conditions for ultra low sulfur diesel (ULSD) and hydrogenation derived renewable diesel (HDRD) fuels. Organic aerosol composition and mass distribution were measured on the aft deck of the vessel directly behind the exhaust stack to intercept the ship plume. The ship emissions for both fuels were composed of alkane-like compounds (H/C = 1.94 ± 0.003, O/C = 0.04 ± 0.001, C_nH_2n) with mass spectral fragmentation patterns consistent with hydrocarbon-like organic aerosol (HOA). Single-particle mass spectra from emissions for both fuels showed two distinct HOA compositions, with one HOA type containing more saturated alkane fragments (C_nH_2n+1) and the other HOA type containing more monounsaturated fragments (C_nH_2n?1). The particles dominated by the C_nH_2n?1 fragment series are similar to mass spectra previously associated with cooking emissions. More cooking-type organic particles were observed in the ship emissions for HDRD than for ULSD (45% and 38%, respectively). Changes in the plume aerosol composition due to photochemical aging in the atmosphere were also characterized. The higher fraction of alkene or aromatic (C_nH_2n?m, m ≥ 3) fragments in aged compared to fresh plume emissions suggest that some of the semivolatile alkane-like components partition back to the vapor phase as dilution increases, while alkene or aromatic hydrocarbons contribute more mass to the particle phase due to continuing photochemical oxidation and subsequent condensation from the vapor phase.

Copyright © 2017 American Association for Aerosol Research     

Development and field evaluation of an online monitor for near-continuous measurement of iron,manganese, and chromium in coarse airborne particulate matter (PM)

A novel air sampling monitor was developed for near-continuous (i.e., 2-h time resolution) measurement of iron (Fe), manganese (Mn), and chromium (Cr) concentrations in ambient coarse particulate matter (PM) (i.e., PM_10–2.5). The developed monitor consists of two modules: (1) the coarse PM collection module, utilizing two virtual impactors (VIs) connected to a modified BioSampler to collect ambient coarse PM into aqueous slurry samples; (2) the metal concentration measurement module, which quantifies the light absorption of colored complexes formed through the reactions between the soluble and solubilized target metals and pertinent analytical reagents in the collected slurries using a micro volume flow cell (MVFC) coupled with UV/VIS spectrophotometry. The developed monitor was deployed in the field for continuous ambient PM collection and measurements from January to April 2016 to evaluate its performance and reliability. Overall, the developed monitor could achieve accurate and reliable measurements of the trace metals Fe, Mn, and Cr over long sampling periods, based on the agreement between the metal concentrations measured via this online monitor and off-line parallel measurements obtained using filter samplers. Based on our results, it can be concluded that the developed monitor is a promising technology for near-continuous measurements of metal concentrations in ambient coarse PM. Moreover, this monitor can be readily configured to measure the speciation (i.e., water-soluble portion as well as specific oxidation states) of these metal species. These unique abilities are essential tools in investigations of sources and atmospheric processes influencing the concentrations of these redox-active metals in coarse PM.

Copyright © 2016 American Association for Aerosol Research     

Wall effects in smog chamber experiments: A model study

Wall losses of condensable organic vapors are a significant complication for smog-chamber experiments designed to constrain production of Secondary Organic Aerosols (SOA). Here we develop a dynamical mass-balance model based on the Volatility Basis Set (VBS) to explore various pathways for mass transfer between the bulk of a smog-chamber volume (the vapors and suspended particles) and reservoirs near the chamber walls (deposited and/or nucleated particles on the walls, adsorption to the walls, and sorption into Teflon walls). We consider various limiting cases and explore the sensitivity of inferred SOA yields to assumptions about the actual parameters in a given SOA experiment. We also present data suggesting that adsorptive uptake to Teflon for typical SOA is modest. Broadly, we find that walls become a sink for condensable vapors when those vapors interact with either deposited particles of the Teflon walls, with qualitatively similar effects on the suspended particles. Finally, we show that having a relatively high seed condensation sink is vital to reliable chamber mass balances.

Copyright © 2016 American Association for Aerosol Research     

Particle size and chemical composition effects on elemental analysis with the nano aerosol mass spectrometer

In the Nano Aerosol Mass Spectrometer (NAMS), particles are irradiated with a high energy laser pulse to produce a plasma that quantitatively disintegrates each particle into positively charged atomic ions. Previous work with this method used electrodynamic focusing and trapping of particles 30 nm dia. and below. In the current work, an aerodynamic focusing inlet was used to study particles between 40 and 150 nm dia. The distribution of atomic ion charge states was found to be particle size dependent, shifting toward lower charges with increasing size. This shift also affected the calibration by which elemental composition was determined from atomic ion signal intensities. Size independent calibration could be achieved by restricting the analysis to particles that gave more than 90% of the total signal intensity as multiply charged ions. This approach worked best for particles smaller than about 100 nm dia. since most spectra met this criterion. For the nanoparticles studied, the elemental mole fractions of Group I and II metals, halogens, and low atomic mass nonmetals could be determined within 10% or less of the expected value when the mole fraction was at the 1% level or greater. Some transition and heavy metals could not be quantified, while others could. Quantification appeared to be dependent on the ability of the element to be vaporized. Elements with high melting and boiling points gave particle mass spectra similar to those obtained by laser desorption ionization—mostly singly charged ions with relative intensities strongly biased toward atoms with low ionization energies.

Copyright © 2017 American Association for Aerosol Research     

A diethylene glycol condensation particle counter for rapid sizing of sub-3 nm atmospheric clusters

Abstract

This article describes the modification of a laminar flow, thermally diffusive universal-fluid condensation particle counter (standard operation: 50% detection efficiency at 5?nm) to rapidly measure the size distribution of sub 3?nm aerosol. Sub 3?nm detection was achieved by using diethylene glycol as the working fluid, which enabled high instrument super-saturations while minimizing homogenous nucleation of the working fluid; a detection efficiency of 50% was achieved at 1.6?nm with laboratory-generated ammonium sulfate (AS) aerosol. Rapid aerosol sizing beneath 3?nm was achieved by inverting the measured grown droplet size distribution (1?s sampling) to recover the sampled aerosol size distribution. The developed inversion algorithm utilizes analytical kernel functions determined from the instrument response to pseudo-monodisperse AS aerosol from 1.5?nm to 20?nm, generated by a high-resolution DMA and a nano DMA. The inversion algorithm was tested numerically with assumed, idealized aerosol size distributions consistent with observed new particle formation events, yielding a reasonable agreement between inverted and assumed aerosol size distributions below 3?nm. This technique provides a measure of the aerosol size assuming an aerosol composition identical to that of the aerosol used to generate the experimentally determined kernel function.

Copyright © 2018 American Association for Aerosol Research     

Field intercomparison of the gas/particle partitioning of oxygenated organics during the Southern Oxidant and Aerosol Study (SOAS) in 2013

We present results of the first intercomparison of real-time instruments for gas/particle partitioning of organic species. Four recently-developed instruments that directly measure gas/particle partitioning in near-real time were deployed in Centreville, Alabama during the Southern Oxidant Aerosol Study (SOAS) in 2013. Two instruments were filter inlet for gases and aerosols high-resolution chemical ionization mass spectrometers (FIGAERO-HRToF-CIMS) with acetate (A-CIMS) and iodide (I-CIMS) ionization sources, respectively; the third was a semi-volatile thermal desorption aerosol GC-MS (SV-TAG); and the fourth was a high-resolution thermal desorption proton-transfer reaction mass spectrometer (HR-TD-PTRMS). Signals from these instruments corresponding to several organic acids were chosen for comparison. The campaign average partitioning fractions show good correlation. A similar level of agreement with partitioning theory is observed. Thus the intercomparison exercise shows promise for these new measurements, as well as some confidence on the measurement of low versus high particle-phase fractions. However, detailed comparison show several systematic differences that lie beyond estimated measurement errors. These differences may be due to at least eight different effects: (1) underestimation of uncertainties under low signal-to-noise; (2) inlet and/or instrument adsorption/desorption of gases; (3) differences in particle size ranges sampled; (4) differences in the methods used to quantify instrument backgrounds; (5) errors in high-resolution fitting of overlapping ion groups; (6) differences in the species included in each measurement due to different instrument sensitivities; and differences in (7) negative or (8) positive thermal decomposition (or ion fragmentation) artifacts. The available data are insufficient to conclusively identify the reasons, but evidence from these instruments and available data from an ion mobility spectrometer shows the particular importance of effects 6–8 in several cases. This comparison highlights the difficulty of this measurement and its interpretation in a complex ambient environment, and the need for further improvements in measurement methodologies, including isomer separation, and detailed study of the possible factors leading to the observed differences. Further intercomparisons under controlled laboratory and field conditions are strongly recommended.

Copyright © 2017 American Association for Aerosol Research     

Computer-controlled Raman microspectroscopy (CC-Raman): A method for the rapid characterization of individual atmospheric aerosol particles

The ability of an atmospheric aerosol particle to impact climate by acting as a cloud condensation nucleus (CCN) or an ice nucleus (IN), as well as scatter and absorb solar radiation is determined by its physicochemical properties at the single particle level, specifically size, morphology, and chemical composition. The identification of the secondary species present in individual aerosol particles is important as aging, which leads to the formation of these species, can modify the climate relevant behavior of particles. Raman microspectroscopy has a great deal of promise for identifying secondary species and their mixing with primary components, as it can provide detailed information on functional groups present, morphology, and internal structure. However, as with many other detailed spectroscopic techniques, manual analysis by Raman microspectroscopy can be slow, limiting single particle statistics and the number of samples that can be analyzed. Herein, the application of computer-controlled Raman (CC-Raman) for detailed physicochemical analysis that increases throughput and minimizes user bias is described. CC-Raman applies automated mapping to increase analysis speed allowing for up to 100 particles to be analyzed in an hour. CC-Raman is applied to both laboratory and ambient samples to demonstrate its utility for the analysis of both primary and, most importantly, secondary components (sulfate, nitrate, ammonium, and organic material). Reproducibility and precision are compared to computer controlled-scanning electron microscopy (CCSEM). The greater sample throughput shows the potential for CC-Raman to improve particle statistics and advance our understanding of aerosol particle composition and mixing state, and, thus, climate-relevant properties.

© 2017 American Association for Aerosol Research     

Ionization efficiency of evolved gas molecules from aerosol particles in a thermal desorption aerosol mass spectrometer: Laboratory experiments

Thermal desorption aerosol mass spectrometers (TDAMSs) with electron ionization are widely used for quantitative analysis of aerosol chemical composition, and the ionization efficiency of evolved gas molecules from aerosol particles is an important parameter for such analysis. We performed laboratory experiments using a custom-made TDAMS to investigate the key factors affecting ionization efficiency. Ammonium chloride (NH₄Cl) and ammonium iodide (NH₄I) were used as test compounds because their thermal decomposition products are expected to be simple (dominated by ammonia (NH₃) and hydrogen halide (HX)). The ion signals originating from NH₃ and HX were measured by altering the position of the ionizer relative to the vaporization point. The ratio of ion signal from NH₃ to that from HX increased with increasing divergence angle of evolved gas plumes, which suggests that the angular distribution of gas molecules could be an important factor affecting the ionization efficiency.

Copyright © 2018 American Association for Aerosol Research     

Size resolved chemical composition of nanoparticles from reactions of sulfuric acid with ammonia and dimethylamine

Abstract

Nanoparticle formation and growth driven by acid-base chemistry was investigated by introducing gas-phase sulfuric acid (H₂SO₄) with ammonia (NH₃) or dimethylamine (DMA) into a flow tube reactor. A thermal desorption chemical Ionization mass spectrometer was used to measure the size-resolved chemical composition of H₂SO₄-DMA and H₂SO₄- NH₃ nanoparticles formed under dry conditions and at 60% relative humidity. In contrast with predictions for bulk aqueous systems, nanoparticles showed a strong size-dependent composition gradient and did not always reach a fully neutralized state in excess of gas-phase base. Smaller particles were more acidic, with an acid:base ratio of 0.7?±?0.1 and 1.3?±?0.3 for 8.6 and 9.5?nm H₂SO₄-DMA particles formed under dry and humid conditions, respectively, and 3.1?±?0.6 and 3.4?±?0.3 for 7.5?nm H₂SO₄-NH₃ particles formed under dry and humid conditions, respectively. The acidity of particles generally decreased as particles grew. H₂SO₄-DMA particles became fully neutralized as they grew to 14?nm, but H₂SO₄-NH₃ particles at 12?nm were still acidic and were never observed to reach bulk sample thermodynamic equilibrium for the experimental conditions in this study. Thermodynamic modeling demonstrated that the observed trends can be reproduced by modifying acid dissociation constants to minimize acid-base chemistry, which may be caused by steric or mixing effects, and by considering volatilization of the neutral base.

Copyright © 2018 American Association for Aerosol Research     

Cloud condensation nuclei activity and droplet formation of primary and secondary organic aerosol mixtures

Understanding the mixing behavior of anthropogenic primary and biogenic secondary organic aerosol (POA and SOA) is important for characterizing their interactions with water vapor. The following work expands upon previous studies and investigates cloud condensation nuclei (CCN) activity and droplet kinetics of α-pinene SOA formed in an environmental chamber and mixed with diesel or motor oil-diesel fuel POA. The changes in the aerosol mixing are similar to previously published work but this study provides new CCN activity and droplet information. The CCN activity of the unmixed aerosol systems are measured separately; κ = 0.15, 0.11, 0.022 for α-pinene SOA, diesel POA and motor oil-diesel fuel POA, respectively. In the α-pinene SOA + diesel POA mixture, the CCN activity, characterized by κ-hygroscopicity, decreases from κ = 0.15 to 0.06 after an initial injection of the POA but increases to κ = 0.12. The increase in CCN activity occurs after particle collision (coagulation and wall-loss) rates dominate aerosol processes in the chamber. The α-pinene SOA + motor oil-fuel POA does not readily mix and the CCN activity of the complex system increases with time (from κ = 0.022 to 0.10). An empirical equation using unit mass resolution (UMR) AMS data of two different ion fragments reasonably predicts CCN activity of the POA and SOA mixtures. CCN measurement may be a promising tool to gain additional insight into the complex mixtures of organic aerosol and subsequent interactions with water vapor.

Copyright © 2018 American Association for Aerosol Research