Instrument Busy Time and Mass Measurement using Aerosol Time-of-Flight Mass Spectrometry

Aerosol Time-of-Flight Mass Spectrometry (ATOFMS) instruments have been used widely to measure the size and composition of single ambient aerosol particles. ATOFMS data do not directly and quantitatively represent aerosol composition because the instruments exhibit non-linear response to particle concentration, size, and composition. Our approach is to analyze separately the components of non-linear ATOFMS response using field sampling data in order to understand ATOFMS response to ambient aerosols so that ATOFMS data can be scaled to more closely represent ambient aerosols. In this work we examine the effect of instrument busy time, mainly the time to process and save data, on ATOFMS response to ambient aerosols sampled during the 1999 Bakersfield Instrument Intercomparison Study (BIIS). During this study an ATOFMS instrument was operated alternately in normal and fast scatter data acquisition modes. In fast scatter mode, the instrument does not record mass spectra, minimizing instrument busy time; these data were used to determine particle arrival rates. Busy time in normal mode was found by a comparison of the number of particles detected to that expected for a Poisson process modified to include busy time. During the BIIS experiment, the ATOFMS instrument was busy between 5 and 95% of the nominal sampling time; thus busy time cannot be ignored for accurate quantitative analysis of ATOFMS data. ATOFMS data were scaled for on-line time and transmission efficiency, found by comparison with reference aerosol measurements, in order to estimate fine particle mass concentrations. Fine aerosol mass concentrations from scaled ATOFMS data demonstate semi-quantitative agreement with independent measurements using Beta Attenuation Monitors. We recommend that ATOFMS instruments be modified to measure busy time directly.     

Impacts of Aerosol Aging on Laser Desorption/Ionization in Single-Particle Mass Spectrometers

Single-particle mass spectrometry (SPMS) has been widely used for characterizing the chemical mixing state of ambient aerosol particles. However, processes occurring during particle ablation and ionization can influence the mass spectra produced by these instruments. These effects remain poorly characterized for complex atmospheric particles. During the 2005 Study of Organic Aerosols in Riverside (SOAR), a thermodenuder was used to evaporate the more volatile aerosol species in sequential temperature steps up to 230°C; the residual aerosol particles were sampled by an aerosol mass spectrometer (AMS) and a single-particle aerosol time-of-flight mass spectrometer (ATOFMS). Removal of the secondary species (e.g., ammonium nitrate/sulfate) through heating permitted assessment of the change in ionization patterns as the composition changed for a given particle type. It was observed that a coating of secondary species can reduce the ionization efficiency by changing the degree of laser absorption or particle ablation, which significantly impacted the measured ion peak areas. Nonvolatile aerosol components were used as pseudo-internal standards (or “reference components”) to correct for this LDI effect. Such corrected ATOFMS ion peak areas correlated well with the AMS measurements of the same species up to 142°C. This work demonstrates the potential to accurately relate SPMS peak areas to the mass of specific aerosol components.

Copyright 2014 American Association for Aerosol Research     

Reproducibility of Single Particle Chemical Composition during a Heavy Duty Diesel Truck Dynamometer Study

The chemical reproducibility of single particle mass spectrometry (SPMS) instruments is complicated by numerous factors, including uncertainties in the laser desorption/ionization process leading to shot-to-shot variability in single particle mass spectra, excessive fragmentation of carbonaceous species, as well as a relatively low duty cycle (1-10 Hz). With source apportionment being a major application for these instruments, proper source profiles must be determined from major aerosol sources. This brief communication illustrates, for the first time, the chemical reproducibility of an aerosol time-of-flight mass spectrometer (ATOFMS) sampling highly transient heavy duty diesel (HDD) truck exhaust emissions from a transportable heavy duty vehicle emissions testing laboratory, which includes a dilution tunnel as well as a residence chamber.In addition to examining the reproducibility of ATOFMS using a complex mixture of "real" aerosol particles, the chemical reproducibility of a dynamometer system at the single particle level is tested. The results presented indicate that for future studies, truck-to-truck and source-to-source variations can be attributed to chemical differences and not just to innate variations due to instrumental variability.     

Carbonaceous Aerosol Sources in Rio de Janeiro

Aerosol carbon concentrations, organic / elemental speciation, and carbon isotopic composition data (¹³C/¹²C ratios and ¹⁴C content) are reported from the second Rio de Janeiro Aerosol Characterization Study (RIO-JACS II), along with supplemental meteorologic and inorganic aerosol data. These data and their diurnal and weekday / weekend variability are used to identify sources of carbonaceous aerosols in the urban Rio air basin. Specifically, contributions from biogenic sources, anthropogenic emissions (principally transportation sources), and sugar cane-derived alcohol-fueled vehicular emissions to aerosol carbon levels in Rio are estimated from measurements of carbon-14, organic and elemental carbon, and ¹³C/¹²C isotopic composition in total aerosol samples collected at two ambient Rio sites and in a heavily traveled tunnel. The major source of elemental (soot) carbon appears to be diesel vehicles, but secondary sources of both biogenic and fossil organic aerosol carbon are indicated.     

A single-particle characterization of a mobile Versatile Aerosol Concentration Enrichment System for exposure studies

Background  

An Aerosol Time-of-Flight Mass Spectrometer (ATOFMS) was used to investigate the size and chemical composition of fine concentrated ambient particles (CAPs) in the size range 0.2–2.6 μm produced by a Versatile Aerosol Concentration Enrichment System (VACES) contained within the Mobile Ambient Particle Concentrator Exposure Laboratory (MAPCEL). The data were collected during a study of human exposure to CAPs, in Edinburgh (UK), in February-March 2004. The air flow prior to, and post, concentration in the VACES was sampled in turn into the ATOFMS, which provides simultaneous size and positive and negative mass spectral data on individual fine particles.     

Effects of Vehicle Cabin Filter Efficiency on Ultrafine Particle Concentration Ratios Measured In-Cabin and On-Roadway

Understanding the in-cabin microenvironment of vehicles is important for assessing human exposure to ultrafine particles (UFPs) of vehicular origin. Filtration through the cabin filter is one of the processes that determine the ratio of in-cabin to on-roadway (I/O) UFP concentrations. In this study, two filter test systems were used to measure the particle filtration efficiencies of fine, ultrafine, and coarse particles. Two types of particles (diesel exhaust UFPs and Arizona test particles) were used to represent the particle types expected in the on-roadway environment. The most penetrating particle size was around 300 nm with filtration efficiency lower than 20%. As the filter face velocity increased from 0.1 to 0.5 m s^?1, the filtration efficiency decreased by 10–20%. For vehicles that were frequently driven under heavy traffic conditions (65,000–72,000 vehicles day^?1) the pressure drop across the cabin filter increased up to 45 Pa within 10 months. It took 20 months to achieve the same pressure drop under moderate traffic conditions (10,000–24,000 vehicles day^?1) and 30 months under light conditions (700–2,000 vehicles day^?1). When the vehicle ventilation fan was on and the recirculation was off, it took approximately 10 months under heavy traffic conditions for UFP I/O ratios to increase by 40%. Explicit relationships between UFP I/O ratios and filter usage under various conditions were derived to facilitate cabin filter change decisions based on individual preferences.     

Characterization of an Ambient Coarse Particle Concentrator Used for Human Exposure Studies: Aerosol Size Distributions,Chemical Composition,and Concentration Enrichment

The goals of the experiments described herein involve determining in real time the size, concentration enrichment, and chemical composition of coarse-mode (<2.5 μm) and fine-mode (>2.5 μm) particles within the nonconcentrated and concentrated flows of a coarse particle concentrator used for human exposure studies. The coarse particle concentrator was intended to concentrate ambient particles in the PM_10–2.5 size range before sending them into a human exposure chamber. The aerodynamic size and chemical composition of particles in the upstream and downstream flows of the concentrator were monitored with an aerosol time-of-f1ight mass spectrometer (ATOFMS) for fixed time intervals over the course of three days. Based on the ATOFMS results, it was found that there was no change in the composition of the ten major particle types observed in the upstream and downstream flows of the concentrator under normal operating conditions. Furthermore, no new particle types were detected downstream that were not detected upstream of the concentrator. A characterization of the aerosol chemical composition and its dependence on sampling conditions is also discussed. Aerosol size distributions were measured with three aerodynamic particle-sizing (APS) instruments sampling simultaneously from different regions of the concentrator. The APS size distributions were used to scale ATOFMS data and measure the ambient concentration factors for the coarse particle concentrator and the exposure chamber. The average concentration factor (ratio of inlet number concentration to the outlet number concentration) for the particle concentrator was 60 + 17 for the 2.5–7.2 μm size range before dilution and transport to the exposure chamber. It was observed that not only were coarse particles being concentrated but fine (<2.5 μm) particles were being concentrated as well, with concentration factors ranging from 2–46 for aerodynamic particle sizes from 0.54–2.5 μm.     

Composition and Morphology of Individual Combustion,Biomass Burning,and Secondary Organic Particle Types Obtained Using Urban and Coastal ATOFMS and STXM-NEXAFS Measurements

Complementary single particle measurements of organic aerosols using aerosol time-of-flight mass spectrometry (ATOFMS) and Scanning Transmission X-ray Microscopy—Near Edge X-ray Absorption Fine Structure (STXM-NEXAFS) are compared to examine the relationships between particle morphologies and chemical composition of particles having similar sources. ATOFMS measurements provide size-resolved chemical composition information for single particles. Measurements from field campaigns in polluted or urban (Riverside/SOAR 2005; Mexico City/MILAGRO 2006; Port of Long Beach 2007) and clean or marine (Arabian Sea/INDOEX 1999; Sea of Japan/ACE-Asia 2001; Trinidad Head/CIFEX 2004) locations illustrate regional differences. The majority (≥ 85 %) of the number of submicron particles are carbonaceous (including elemental and organic carbon), but represent less than 10% of the number of supermicron particles. Organic carbon (OC) particles are classified into three meta-classes corresponding to (1) combustion generated OC/EC internal mixtures, (2) biomass burning generated K/OC mixtures, and (3) OC/High Mass OC (HMOC) mixtures containing secondary markers of atmospheric processing. Normalized dot products are used to quantify similarity among fragment spectra and indicate that OC particle types are consistent across (and within) platforms. Single particle carbon STXM-NEXAFS measurements during ACE-Asia 2001 and MILAGRO 2006 yield similar source categories based on relative abundances of aromatic, alkane, and carboxylic acid functional groups. All three organic particle types correspond to a variety of very heterogeneous particle morphologies, although the highly oxygenated OC particles with likely secondary organic contributions frequently are nearly spherical, liquid-like particles. Size-resolved number fractions of the major ATOFMS OC particle types show qualitative agreement with OC particle types from STXM-NEXAFS analysis, indicating a correspondence of the OC/EC type with the presence of strong aromatic groups, of the OC/HMOC type with high carboxylic acid groups, and of the biomass burning OC type with aromatic and carbonyl groups. ATOFMS measurements can be used to establish robust statistics for offline single particle techniques, providing the atmospheric context for the functional group and morphological information obtained from STXM-NEXAFS for an improved understanding of the climate impact of organic aerosols.     

Real-Time Measurements of Nonmetallic Fine Particulate Matter Adjacent to a Major Integrated Steelworks

A campaign took place in Wales (UK) in the spring of 2006 to characterize emissions from a major steelworks through atmospheric measurements. At no time during the measurements was the 24-h air quality standard for PM₁₀ exceeded. However, real-time measurements of single particles by aerosol time-of-flight mass spectrometry (ATOFMS) allowed detection of particulate matter from the steelworks, which could be associated with specific emission areas within the works from measurements of wind direction. Three main wind sectors were identified with possible sources of emissions of fine nonmetallic particulate matter (PM < 1 μm). Characterization of the aerosol composition by a high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) of the nonrefractory material associated with the specific plumes is also reported, along with results from other real-time techniques. The ATOFMS detected for the first time a unique elemental sulfur-rich particle type, likely to originate from the blast furnaces. AMS results, supported also by laboratory studies, confirm this finding by reporting elevated mass ratios m/z 64/48 and m/z 64/80. Two other novel ATOFMS particulate types were found to be associated with steelworks emissions. One was characterized by nitrogen-containing organic species, aromatic compounds, and high-molecular-weight (MW) polycyclic aromatic hydrocarbons (PAHs) and was associated with the sources in the area of the hot and cold mills. The second was found to be rich in organic carbon internally mixed with elemental carbon, nitrate, sulfate, and PAHs with lower MW. These particle types were likely related to the coke ovens and the basic oxygen steelmaking plant.

Copyright 2012 American Association for Aerosol Research     

Organic PM Emissions from Vehicles: Composition,O/C Ratio,and Dependence on PM Concentration

A suite of real-time instruments was used to sample vehicle emissions at the California Air Resources Board Haagen-Smit facility. Eight on-road, spark-ignition gasoline and three alternative vehicles were tested on a chassis dynamometer and the emissions were diluted to atmospherically relevant concentrations (0.5–30 μg/m³). An Aerodyne high resolution time-of-flight aerosol mass spectrometer (HR-ToF-MS) characterized the real-time behavior of the nonrefractory organic and inorganic particulate matter (PM) in vehicle emissions. It was found that the emission of particulate organic matter (POM) was strongly affected by engine temperature and engine load and that the emission concentrations could vary significantly by vehicle. Despite the small sample size, consistent trends in chemical characteristics were observed. The composition of vehicle POM was found to be related to overall PM mass concentration where the oxygen-to-carbon (O/C) ratio tended to increase at lower concentration and had an average value of 0.057 ± 0.047, with a range from 0.022 to 0.15. The corresponding fraction of particle-phase CO₂⁺, or f₄₄, ranged from 1.1% to 8.6% (average = 2.1%) and exhibited a linear variation with O/C. The average mass spectrum from all vehicles tested was also compared to those of hydrocarbon-like organic aerosol (HOA) observed in ambient air and the agreement is very high. The results of these tests offer the vehicle emissions community a first glimpse at the real-time chemical composition and variation of vehicle PM emissions for a variety of conditions and vehicle types at atmospherically relevant conditions and without chemical interferences from other primary or secondary aerosol sources.

Copyright 2015 American Association for Aerosol Research     

An Aerosol Wind Tunnel for Evaluation of Massive-Flow Air Samplers and Calibration of Snow White Sampler

Massive-flow air samplers are being deployed around the world to collect aerosol samples for analysis of radioactivity as a result of nuclear tests and nuclear accidents. An aerosol wind tunnel capable of an 1100 m³ min^?1 flow rate was built at Lovelace Respiratory Research Institute (LRRI) to test the sampling efficiency of these samplers. This aerosol wind tunnel uses a stationary air blender to enhance mixing, and therefore it achieves the required uniform distribution of wind speed and aerosol concentration in the test section. The test section of the wind tunnel has a cross section that is 4.3 m × 3.7 m. The aerosol wind tunnel was tested for performance in terms of distribution of wind speed, turbulent intensity, SF₆ tracer gas concentration, and aerosol concentration. Test criteria consistent with U.S. Environmental Protection Agency (EPA) and American National Standards Institute (ANSI) standards were adopted as the guidelines for the aerosol wind tunnel. Additional criteria for aerosol wind tunnel were also recommended. Initial test of the aerosol wind tunnel showed that the wind tunnel could be operated in a wind speed range of 2 to 24 km h^?1. Within this range, the distribution of wind speed SF⁶ trace gas concentration and aerosol concentration in two-thirds of the central area of the test section showed coefficient of variances (COVs) of less than 10% for the range of wind speeds. This met the stringent guidelines for aerosol wind tunnel performance set by EPA and ANSI standards.

The LRRI wind tunnel was used to evaluate the collection efficiency of the sampling head of massive-volume air samplers, including the Snow White sampler. The sampler was tested in this aerosol wind tunnel for particles between 2 and 20 μm. The sampling flow rates were 500 and 700 m³ h^?1 for the tested wind speeds of 2.2 and 6.6 m S^?1, respectively. The results showed that sampling efficiency was influenced by both sampling flow rate and wind speed. The sampling efficiency decreased with an increase in particle size of between 2 and 20 μm. The sampling efficiency also decreased as the wind speed was increased from 2.2 to 6.6 m S^?1.     

Development of a High-Pressure Aerodynamic Lens for Focusing Large Particles (4–10 μm) into the Aerosol Time-of-Flight Mass Spectrometer

A new aerodynamic lens system for an online aerosol time-of-flight mass spectrometer (ATOFMS) has been designed and constructed to transmit and allow the analysis of individual particles in the 4–10-μm-size range. Modeling was used to help design the lens within the bounds of ATOFMS instrumental constraints. The aerodynamic lens operates at a high inlet pressure, 3066 Pa (23 Torr), with a unique tapered relaxation region to improve large particle transmission. Every stage of the lens was tested empirically using a combination of particle deposition and light scattering experiments. The critical orifice was found to significantly impact large particle transmission, with orifices <200 μm in diameter completely suppressing large particle transmission. The addition of a virtual impactor allowed for the use of large orifices without any loss of functionality in the ATOFMS. The detection efficiency of the ATOFMS was >10% for particles from 4–10 μm with a peak efficiency of 74 ± 9% for 6-μm particles. With the extended size range provided by this inlet, the ATOFMS can now be extended to investigate single cell metabolomics.

Copyright 2014 American Association for Aerosol Research     

Physical and Chemical Characteristics and Volatility of PM in the Proximity of a Light-Duty Vehicle Freeway

Abstract

Volatility properties of ultrafine particles were analyzed next to State Route 110 (Pasadena freeway CA), a light-duty vehicle freeway where heavy-duty traffic is prohibited. In addition, mass concentration and chemical composition of particulate matter (PM) were measured in coarse, accumulation, and ultrafine modes. On weekdays from 17 May to 4 June 2004, measurements were performed in two locations, one very close to the freeway (within 2.5 m from the curb) and one at a distance of about 50 m from the freeway. For measurement of mass and chemical composition, the study employed in each location a micro-orifice uniform deposit impactor (MOUDI) and a modified high-volume sampler. Both instruments sampled with the same size cutpoints: a coarse mode from 2.5 to 10 μm, an accumulation mode from 0.18 to 2.5 μm, and an ultrafine mode of particles less than 0.18 μm in aerodynamic diameter. Alternately, a tandem differential mobility analyzer (TDMA) was used at the two sites. A heater between the two DMAs evaporated volatile material from the monodisperse aerosol, size selected by the first DMA. The second DMA analyzed the losses of volatile components. The ultrafine number concentrations next to the freeway were 46,000 cm^?3 on average during the sampling period. The MOUDI ultrafine mass concentration, nitrate, and EC were higher next to the freeway than at the background site farther from the freeway. The other components analyzed in the ultrafine mode had similar concentrations next to the freeway and at the background site. Volatility ranged from about 65% volume losses of 120 nm particles heated to 110°C to 95% of 20 nm particles. The 20 nm aerosol was only internally mixed, whereas increasing nonvolatile fractions were found for 40 nm (6% next to the freeway), 80 nm (20%), and 120 nm (28%) aerosols.     

Investigating the chemical species in submicron particles emitted by city buses

Detailed chemical characterization of exhaust particles from 23 individual city buses was performed in Helsinki, Finland. Investigated buses represented different technologies in terms of engines, exhaust after-treatment systems (e.g., diesel particulate filter, selective catalytic reduction, and three-way catalyst) and fuels (diesel, diesel-electric (hybrid), ethanol, and compressed natural gas). Regarding emission standards, the buses operated at EURO III, EURO IV, and EEV (enhanced environmentally friendly vehicle) emission levels. The chemical composition of exhaust particles was determined by using a soot particle aerosol mass spectrometer (SP-AMS). Based on the SP-AMS results, the bus emission particles were dominated by organics and refractory black carbon (rBC). The mass spectra of organics consisted mostly of hydrocarbon fragments (54–86% of total organics), the pattern of hydrocarbon fragments being rather similar regardless of the bus type. Regarding oxygenated organic fragments, ethanol-fueled buses had unique mass-to-charge ratios (m/z) of 45, 73, 87, and 89 (mass fragments of C₂H₅O⁺, C₃H₅O₂⁺, C₄H₇O₂⁺, and C₄H₉O₂⁺, respectively) that were not detected for the other bus types at the same level. For rBC, there was a small difference in the ratio of C₄⁺ and C₅⁺ to C₃⁺ for different bus types but also for the individual buses of the same type. In addition to organics and rBC, the presence of trace metals in the bus emission particles was investigated.

Copyright © 2017 American Association for Aerosol Research     

A Field Intercomparison of Three Cascade Impactors

ABSTRACT

Cascade impactors separate aerosol particles inertially and collect them for later analysis. While laboratory calibrations typically indicate performance close to design specifications, during field operation impactors are subject to a number of sampling artifacts, including particle bounce, inlet and internal losses, and particle size changes as pressure drops within the impactor.

To test the vulnerability of some commonly used impactors to these problems under Held conditions, we participated in a shipboard intercomparison off the coast of Washington state between a micro-orifice uniform deposit impactor (MOUDI), a Berner low-pressure impactor, and a Sierra high-volume slotted impactor. Since there were some inconsistencies in the results, a second intercomparison was performed at Bellows Beach, Hawaii, between two MOUDIs and the Berner impactor.

Impactor samples were analyzed for soluble inorganic ions including Na⁺, K⁺, Cl^?, and NO^? ₃, primarily from large (>1 μm) sea salt particles and NH⁺ ₄, nonsea salt sulfate (NSS), and methanesulfonate (MS^?), found primarily in smaller aerosols.

The Sierra collected sea salt particles far more efficiently than the other impactors, which had severe inlet losses for 7 μm and larger particles. The MOUDI and Berner showed insignificant differences in the mass median diameter of accumulation mode particles (～0.34 μm), whereas the Sierra indicated almost twice the diameter (0.58 μm) of the others.     

Effective density of airborne particles in a railway tunnel from field measurements of mobility and aerodynamic size distributions

The objective of this study is to investigate the particle effective density of aerosol measurements in a railway tunnel environment. Effective density can serve as a parameter when comparing and calibrating different aerosol measurements. It can also be used as a proxy parameter reflecting the source of particles. Effective density was determined using two different methods. Method one defined it by the ratio of mass concentration to apparent volume size distribution. Method two relied on a comparison of aerodynamic and mobility diameter size distribution measurements. The aerodynamic size range for method one was 0.006–10?µm, and for method two, it was 10–660?nm. Using the first method, a diurnal average value of about 1.87?g/cm³ was observed for the measurements with tapered element oscillating microbalance (TEOM) in tandem with aerodynamic particle sizer?+?scanning mobility particle sizer (SMPS), and 1.2?g/cm³ for the combination of TEOM with electrical low pressure impactor plus (ELPI+) in the presence of traffic. With method two, the effective density was 1.45?g/cm³ estimated from the size distribution measurements with ELPI?+?and fast mobility particle sizer (FMPS), and 1.35?g/cm³ from ELPI?+?in tandem with SMPS. With both calculation methods, the effective density varied for conditions with and without traffic, indicating different sources of particles. The proportion of particles with small sizes (10–660?nm) had a significant effect on the value of the effective density when no traffic was operating. The responses of different instruments to the railway particle measurements were also compared.

Copyright © 2018 The Authors. Published with license by Taylor &; Francis Group, LLC     

Dependence of Real Refractive Indices on O:C,H:C and Mass Fragments of Secondary Organic Aerosol Generated from Ozonolysis and Photooxidation of Limonene and α-Pinene

The refractive index is a fundamental property controlling aerosol optical properties. Secondary organic aerosols have variable refractive indices, presumably reflecting variations in their chemical composition. Here, we investigate the real refractive indices (m_r) and chemical composition of secondary organic aerosols (SOA) generated from the oxidation of α-pinene and limonene with ozone and NO_x/sunlight at different HC/NO_x ratios. Refractive indices were retrieved from polar nephelometer measurements using parallel and perpendicular polarized 532-nm light. Particle chemical composition was monitored with a high-resolution time-of-flight aerosol mass spectrometer (HR-Tof-AMS). For photochemically generated SOA, the values of refractive indices are consistent with prior results, and ranged from about 1.34 to 1.55 for limonene and from 1.44 to 1.47 for α-pinene, generally increasing as the particles grew. While AMS fragments are strongly correlated to the refractive index for each type of SOA, the relationships are in most cases quite different for different SOA types. Consistent with its wide range of refractive index, limonene SOA shows larger variations compared to α-pinene SOA for most parameters measured with the AMS, including H:C, O:C, f₄₃ (m/z 43/organic), f_C4H7 ⁺, and others. Refractive indices for α-pinene ozonolysis SOA also fell in narrow ranges; 1.43–1.45 and 1.46–1.53 for particles generated at 19–22 and 23–29°C, respectively, with corresponding small changes of f₄₃ and H:C ratio and other parameters. Overall, H:C ratio, m/z 43 and 55 (C₂H₃O⁺, C₄H₇ ⁺) were the best correlated with refractive index for all aerosol types investigated. The relationships between m_r and most fragments support the notion that increasing condensation of less oxygenated semivolatile species (with a possible role for a concomitant decrease in low refractive index water) is responsible for the increasing m_rs observed as the experiments progress. However, the possibility that oligomerization reactions play a role cannot be ruled out.     

Quantitative Analysis of the Parameters Affecting In-Cabin to On-Roadway (I/O) Ultrafine Particle Concentration Ratios

Given growing concerns over the observed relationship between ultrafine particles and adverse human health effects, there is a major need in the community performing human/animal exposure studies for methods that can be used for the generation of high concentrations of ultrafine particles (<100 nm) with controllable compositions. The Palas spark discharge generator (Palas GFG 1000) is commonly used to generate “soot-like” particles for such studies. However, before such methods can be used routinely in the lab, it is important to assess the chemical variability and reproducibility of the ultrafine particles produced using such techniques. The goal of this study involves performing the on-line assessment of the chemical variability of individual ultrafine and fine (50–300 nm) particles produced by a Palas generator. The aerodynamic size and chemical composition of ¹²C and ¹³C elemental carbon (EC), composite iron–carbon (Fe-¹²C), and welding particles were analyzed using aerosol time-of-flight mass spectrometry, and in general highly reproducible single-particle mass spectra were obtained. When using pure graphite (¹²C) electrodes, EC particles were produced with sizes peaking in the ultrafine mode and 96% of the mass spectra containing distinct C_n ⁺ (n = 1–3) envelopes at m/z 12, 24, and 36. In contrast, the size mode of the particles generated from isotopically labeled ¹³C graphite electrodes peaked in the accumulation mode, with 73% of the particles producing EC carbon ion cluster patterns at m/z 13 (¹³C⁺), 26(¹³C₂ ⁺), and 39 (¹³C₃ ⁺), with additional organic carbon species at m/z 15 (CH₃ ⁺), 27 (C₂H₃ ⁺/CHN⁺), 43 (C₃H₇ ⁺/CH₃CO⁺), m/z 58 (C₃H₈N⁺), and 86 (C₅H₁₂N⁺). Observed differences between the ¹²C and ¹³C particle spectra are most likely due to their different surface properties, with ¹³C particles more effectively adsorbing semivolatile organic species originating in the particle-free dilution air. Homogeneous metal particles were also generated from Fe-¹²C and welding rods with almost all (92% and 97%, respectively) of the spectra showing reproducible Fe/Mn/Cr and Fe/¹²C ion ratios.     

In situ aerosol acidity measurements using a UV–Visible micro-spectrometer and its application to the ambient air

Abstract

An in situ analytical method was demonstrated to measure the proton concentration ([H⁺]_C-RUV) of an aerosol particle by using colorimetry integrated with a Reflectance UV-Visible spectrometer (C-RUV). Acidic particles comprising ammonium, sulfate, and water were generated in a flow tube under varying humidity and employed to calibrate the method using the inorganic thermodynamic models (i.e., E-AIM and ISORROPIA). The predictive [H⁺]_C-RUV equation derived using strongly acidic compositions was then extended to ammonia-rich aerosols, which were lacking in the database of the thermodynamic models. The predictive [H⁺]_C-RUV equation was also expanded to aerosols composed of sodium, ammonium, and sulfate. [H⁺]_C-RUV generally agrees with both E-AIM predicted [H⁺] and ISORROPIA predicted [H⁺] for highly acidic aerosols, or aerosols at high humidity. For ammonia-rich aerosols under low humidity, [H⁺]_C-RUV disagrees with that predicted from inorganic thermodynamic models. C-RUV was feasible for ambient aerosols because colorimetry is specific to aerosol acidity. Most aerosols collected at the University of Florida between 2018 and 2019 were acidic. Sodium ions appeared during the spring and summer, as coastal sea breezes traveled inland. The concentrations of ammonium and nitrate were high in the winter due to the phase partitioning of nitric acid and ammonia gases. The fraction of non-electrolytic dialkyl-organosulfate (diOS) to total sulfate is estimated by comparing the actual particle [H⁺] measured by C-RUV to the [H⁺] predicted using the inorganic composition and the inorganic thermodynamic models. The diOS fraction varied from 0% to 60% and was higher in the summer months when [H⁺] is high.

Copyright © 2020 American Association for Aerosol Research     

Real-Time Characterization of the Composition of Individual Particles Emitted From Ultrafine Particle Concentrators

Particle concentrators are commonly used for controlling exposure levels to ambient ultrafine, fine, and coarse aerosols over a broad range of concentrations. For ultrafine aerosols, these concentrators require water condensation technology to grow and enrich these smaller sized particles (D _a < 100 nm). Because the chemistry of the particles is directly related to their toxicity, any changes induced by ultrafine concentrators on ambient particles need to be better characterized in order to fully understand the results obtained in health exposure studies. Using aerosol time-of-flight mass spectrometry (ATOFMS), the size-resolved chemistry was measured of concentrated ultrafine and accumulation mode (50–300 nm) particles from several particle concentrators with different designs. This is the first report detailing the size-resolved distributions of elemental carbon (EC) and organic carbon (OC) particles sampled from concentrators. Experimental measurements of the single particle mixing state of particles in concentrated versus non-concentrated ambient air show transformations of ultrafine EC particles occur as they become coated with organic carbon (OC) species during the concentration process. Based on relative ion intensities, concentrated ultrafine particles showed a 30% increase in the amount of OC on the EC particles for the same aerodynamic size. An increase in the number fraction of aromatic- and polycyclic aromatic hydrocarbon-containing particles was also observed in both the ultrafine and fine size modes. The most likely explanation for such changes is gas-to-particle partitioning of organic components (e.g., water-soluble organic compounds) from the high volume of air used in the concentrator into aqueous phase ultrafine and fine aqueous particles created during the particle enrichment process.