James J. Schwab

Measurement of Ambient Aerosol Composition during the PMTACS-NY 2001 using an Aerosol Mass Spectrometer. Part I: Mass Concentrations

Semicontinuous ambient aerosol composition measurements performed during the PMTACS-NY Summer 2001 field campaign in Queens/New York with an aerosol mass spectrometer (AMS, developed by Aerodyne Research Inc.) are described. The measurements include 10 min averages of the nonrefractory sulfate, nitrate, ammonium, chloride, and organic mass concentrations in the particle size range of 50 to approximately 1000 nm. Particle-bound water concentrations (i.e., aerosol liquid water content) were estimated from the mass spectral information and local meteorological data. Aggregate semicontinuous AMS mass measurements were compared with those from a TEOM mass monitor that was also deployed at the PMTACS-NY 2001 site. On average, the AMS observed 64% of the total particulate matter mass measured by the TEOM Monitor. Filter and additional semicontinuous particulate sulfate measurements performed simultaneously at the site suggest that the observed discrepancy in mass balance between the two instruments is attributable to a combination of large particles (≥1 μm) lost in the AMS inlet system and the refractory aerosol components not measured by the AMS. Measured diurnal patterns of sulfate, nitrate, organics, and total nonrefractory mass concentrations indicate that elevated PM levels measured during this campaign were due to regional transport as well as local production of particulate matter.

Pollution Gradients and Chemical Characterization of Particulate Matter from Vehicular Traffic near Major Roadways: Results from the 2009 Queens College Air Quality Study in NYC

We present measurements of traffic-related pollutants made near the Long Island Expressway (LIE, I-495), in Queens, New York. The Aerodyne Research Inc. (ARI) mobile laboratory (AML) was deployed to map spatial and temporal gradients of gas-phase species and particulate matter (PM) associated with vehicular exhaust in the residential areas near the LIE. We observe that pollutant levels build up during the early morning hours under stable boundary layer conditions yet fall off quickly within 150 m downwind of the highway. An ARI soot particle aerosol mass spectrometer (SP-AMS) provided measurements of the size-resolved chemical composition of refractory black carbon (rBC) and the associated coating species. The average size distribution of the traffic related PM is characterized by a rBC mode centered at ∼100 nm in vacuum aerodynamic diameter, D va (rBC mass fraction ∼50%). A second rBC mode (rBC mass fraction ∼5%) more heavily coated with organic material is also observed at D va ∼500 nm. Positive matrix factorization (PMF) analyses of the traffic-related PM indicates that rBC is mostly associated with hydrocarbon-like organic (HOA) PM. These results are discussed in the context of chemically resolved size distributions and PMF analysis results performed on the SP-AMS stationary data collected at the Queens College site. Finally, we report emission indices (EI) for both fleet-average conditions and single vehicles, including several New York City Metropolitan Transit Authority (MTA) buses, sampled by the AML in “chase” mode during the study. Copyright 2012 American Association for Aerosol Research

New York State urban and rural measurements of continuous PM2.5 mass by FDMS, TEOM, and BAM.

Abstract Field evaluations and comparisons of continuous fine particulate matter (PM2.5) mass measurement technologies at an urban and a rural site in New York state are performed. The continuous measurement technologies include the filter dynamics measurement system (FDMS) tapered element oscillating microbalance (TEOM) monitor, the stand-alone TEOM monitor (without the FDMS), and the beta attenuation monitor (BAM). These continuous measurement methods are also compared with 24-hr integrated filters collected and analyzed under the Federal Reference Method (FRM) protocol. The measurement sites are New York City (the borough of Queens) and Addison, a rural area of southwestern New York state. New York City data comparisons between the FDMS TEOM, BAM, and FRM are examined for bias and seasonality during a 2-yr period. Data comparisons for the FDMS TEOM and FRM from the Addison location are examined for the same 2-yr period. The BAM and FDMS measurements at Queens are highly correlated with each other and the FRM. The BAM and FDMS are very similar to each other in magnitude, and both are ∼25% higher than the FRM filter measurements at this site. The FDMS at Addison measures ∼9% more mass than the FRM. Mass reconstructions using the speciation trends network filter data are examined to provide insight as to the contribution of volatile species of PM2.5 in the FDMS mass measurement and the fraction that is likely lost in the FRM mass measurement. The reconstructed mass at Queens is systematically lower than the FDMS by ∼10%.

Semicontinuous PM2.5 sulfate and nitrate measurements at an urban and a rural location in New York: PMTACS-NY summer 2001 and 2002 campaigns.

Abstract Several collocated semicontinuous instruments measuring particulate matter with particle sizes ≤2.5 μm (PM2.5) sulfate (SO4 22−) and nitrate (NO3 −) were intercompared during two intensive field campaigns as part of the PM2.5 Technology Assessment and Characterization Study. The summer 2001 urban campaign in Queens, NY, and the summer 2002 rural campaign in upstate New York (Whiteface Mountain) hosted an operation of an Aerosol Mass Spectrometer, Ambient Particulate Sulfate and Nitrate Monitors, a Continuous Ambient Sulfate Monitor, and a Particle-Into-Liquid Sampler with Ion Chromato-graphs (PILS-IC). These instruments provided near realtime particulate SO4 2− and NO3 − mass concentration data, allowing the study of particulate SO4 2−/NO3 − diurnal patterns and detection of short-term events. Typical particulate SO4 2− concentrations were comparable at both sites (ranging from 0 to 20 μg/m3), while ambient urban particulate NO3 − concentrations ranged from 0 to 11 μg/m3 and rural NO3 − concentration was typically less than 1 μg/m3. Results of the intercomparisons of the semicontinu-ous measurements are presented, as are results of the comparisons between the semicontinuous and time-integrated filter-based measurements. The comparisons at both sites, in most cases, indicated similar performance characteristics. In addition, charge balance calculations, based on major soluble ionic components of atmospheric aerosol from the PILS-IC and the filter measurements, indicated slightly acidic aerosol at both locations.

An Intercomparison of Measurement Methods for Carbonaceous Aerosol in the Ambient Air in New York City

Measurement methods for fine carbonaceous aerosol were compared under field sampling conditions in Flushing, New York during the period of January and early February 2004. In-situ 5- to 60-minute average PM 2.5 organic carbon (OC), elemental carbon (EC), and black carbon (BC) concentrations were obtained by the following methods: Sunset Laboratory field OC/EC analyzer, Rupprecht and Patashnick (R&P) series 5400 ambient carbon particulate monitor, Aerodyne aerosol mass spectrometer (AMS) for total organic matter (OM), and a two-wavelength AE-20 Aethalometer. Twenty-four hour averaged PM 2.5 filter measurements for OC and EC were also made with a Speciation Trends Network (STN) sampler. The diurnal variations in OC/EC/BC concentrations peaked during the morning and afternoon rush hours indicating the dominant influence of vehicle emissions. BC/EC slopes are found to range between 0.86 and 1.23 with reasonably high correlations (r > 0.75). Low mixing heights and absence of significant transported carbonaceous aerosol are indicated by the measurements. Strong correlations are observed between BC and thermal EC as measured by the Sunset instrument and between Sunset BC and Aethalometer BC. Reasonable correlations are observed among collocated OC/EC measurements by the various instruments.

Development, Operation and Applications of an Aerosol Generation, Calibration and Research Facility

An aerosol generation, calibration, and research facility has been developed with the major purpose of evaluating aerosol instrumentation, including quality assurance testing, intercomparison, performance evaluation, and calibration of aerosol sizing, bulk, and speciated mass-measuring instruments. The aerosol facility also provides excellent opportunities for basic aerosol research. Polydisperse test aerosols are generated most often through spray atomization of solutions. Monodisperse test aerosols can be produced by mobility classification of polydisperse aerosols, by a vibrating orifice aerosol generator, by an electrospray aerosol generator, or by nebulization of polystyrene latex (PSL) particle suspensions. Generated inorganic, organic, and mixed aerosol particles range in size from 0.005 to greater than 1 micrometer. Physical characterization of the test aerosols is done using scanning mobility particle sizers, condensation particle counters, and an aerodynamic particle sizer. The facility includes a 450 l cylindrical glass slow-flow chamber that is used mainly for the dilution, equilibration, and controlled humidification of generated primary aerosol particles larger than 50 nm as well as for the generation of secondary aerosols through the choice of appropriate precursor reactants. Test aerosols can also be subjected to controlled concentrations of pollutant gases (O3, NOx, SO2, and VOCs). Smaller particles can also be generated and sampled either from a fast-flow chamber or a static chamber. The well-characterized aerosol environment produced in the slow-flow chamber is used to evaluate the performance of various instruments designed to measure aerosol mass, composition, and size over a range of ambient conditions. Instruments evaluated to date include an R&P standard TEOM mass monitor; a SES TEOM mass monitor; a Differential TEOM mass monitor with an electrostatic precipitator (ESP); R&P Ambient Particulate Sulfate, Nitrate, and Carbon monitors; a Particle-Into-Liquid Sampler with IC (PILS-IC); an Aerodyne Aerosol Mass Spectrometer (AMS); TSI scanning mobility particle sizers (SMPSs); and condensation particle counters (CPCs). Several examples of applications of the aerosol facility involving the TEOM mass monitors and the AMS are also discussed in this article.

Ozone, Trace Gas, and Particulate Matter Measurements at a Rural Site in Southwestern New York State: 1995–2005

Abstract A research site for atmospheric chemistry and air pollution measurements was established at Pinnacle State Park in Addison, NY, in 1995. This paper presents an overview of the site characteristics and measurement program, as well as monthly average concentrations for many of the trace gas and aerosol pollutants over the full measurement period. Monthly averaged ozone concentrations range from values as low as 15 parts per billion (ppb) during cold-season months, to values approaching 50 ppb during some spring and summer months. Sulfur dioxide (SO2), oxides of nitrogen (NOx), and reactive odd nitrogen (NOy) all show distinct seasonal variation, with summertime monthly averages as low as 1–3 ppb, and wintertime monthly averages from 6–12 ppb. The variation in carbon monoxide (CO) is much smaller, with minimums of approximately 150 ppb and maximums only rarely exceeding 250 ppb. Data for three hydrocarbon species propane, benzene, and isoprene—are presented. Propane and benzene show higher monthly averaged concentrations in the winter and lower values in the summer, with values ranging over a factor of 4–5. Isoprene, on the other hand has much higher values during the summer season, sometimes a factor of 10 or more greater than concentrations measured in the winter. Monthly averaged plots for fine particulate matter (PM2.5) beginning in 1999 show a robust summer maximum and winter minimum, and roughly a factor of two difference between the two. An empirical measure of ozone production using the correlation of hour-averaged ozone and NOy data illustrates relatively robust ozone production during some, but not all, summertime months over the time period. Also, an analysis of the frequency distribution of the hours of maximum ozone concentration shows a strong mid-afternoon peak, as expected, but also a prominent secondary maximum centered around midnight. The secondary peak is interpreted as ozone transported from ozone-producing areas to the west, including Buffalo, Cleveland, Pittsburgh, and the Ohio Valley. Finally, SO2 concentrations as a function of wind direction clearly indicate maximum impacts when the winds are out of the south (Pittsburgh and Philadelphia), with a secondary peak when the winds are from the north-northeast, consistent with the locations of major SO2 emission sources in the region.

Field and Laboratory Evaluation of the Thermo Electron 5020 Sulfate Particulate Analyzer

The Thermo Electron Model 5020 Sulfate Particulate Analyzer is a recently commercialized instrument that provides continuous measurements of the sulfate component of ambient particulate matter. The technique uses a stainless steel rod placed inside a quartz oven to reduce the particle sulfate to sulfur dioxide; followed by pulsed fluorescence detection of the sulfur dioxide. Field and laboratory evaluations of a pre-production version of the analyzer are described as well as laboratory evaluations of the pre-production version and two production units. Laboratory tests concentrated on challenging the instruments with ammonium sulfate aerosol, but tests with sodium, potassium, and calcium sulfate are reported as well. The instrument performed very well in field and laboratory settings, reporting values that were highly correlated with continuous mass measurements in the lab, and 24-hour filters in the field. Conversion/detection efficiencies for ammonium sulfate in the laboratory, and for ambient sulfate aerosol at our rural site in Addison, New York, were both very close to 80%. Laboratory conversion efficiencies for calcium, sodium, and potassium sulfate salts ranged from 4% to 63%. These lower efficiencies for mineral-type sulfates will be an important consideration in areas with significant concentrations of sea salt or mineral dust sulfate, and less important for the high sulfate Eastern US which is dominated by ammonium sulfate.

Long-term field characterization of tapered element oscillating microbalance and modified tapered element oscillating microbalance samplers in urban and rural New York State locations.

Abstract Long-term field comparisons of continuous and integrated filter measurements of mass concentrations of par-ticulate matter (PM) with an aerodynamic diameter less than or equal to 2.5 μm (PM2.5) were performed at rural and urban sites in New York State. Two versions of the continuous tapered element oscillating microbalance (TEOM) mass monitor are deployed at each site, in addition to Federal Reference Method filter samplers. Data are grouped into monthly averages to retain and demonstrate seasonal differences. Strong seasonal dependence is observed—the TEOM monitors with the heated sensors are biased systematically low with respect to the Federal Reference Method measurements during the cold season. For the rural site, the average bias for the sample equilibration system (SES)-equipped and standard TEOM monitors is 14 and 24%, respectively. At this location, the TEOM monitor measurements were biased low for all 34 months. For the urban site, the average bias for the SES and standard TEOM monitors is 8 and 18%, respectively. At this location, the TEOM monitor measurements are as likely to be biased high as low during the warm-season months. The hour averaged data from the two versions of the TEOM monitor are also compared, and also indicate that the SES-equipped version of the TEOM monitor captures 7-11% more PM2.5 mass at these locations.

Field Evaluation of a TSI Model 3034 Scanning Mobility Particle Sizer in New York City: Winter 2004 Intensive Campaign

A new “single box” Scanning Mobility Particle Sizer (TSI SMPS Model 3034) was deployed and operated during a period of four weeks as a part of the PMTACS-NY Winter 2004 intensive study in Queens College, New York City. The SMPS 3034 is an alternative to a conventional multi-component TSI SMPS and houses a Differential Mobility Analyzer and butanol-based Condensation Particle Counter in one cabinet. The SMPS 3034 operates at a fixed 1 l/min sample flow rate (4 l/min sheath flow rate) and measures size distributions within a 10–487 nm size range. One size scan is produced every 3 minutes. Four other measurement systems (a conventional TSI SMPS with a Nano Differential Mobility Analyzer, an Aerodynamic Particle Sizer, a stand-alone Condensation Particle Counter, and an R&P Inc. Filter Dynamic Measurement System (FDMS) TEOM mass monitor) were operated side-by-side with the SMPS 3034. It is shown that total particle number concentrations measured by the SMPS 3034 are highly correlated with those from the conventional Nano SMPS, the Condensation Particle Counter and the FDMS TEOM monitor, and that the number median diameters measured by the SMPS 3034 and the Nano SMPS agree within 3 nm.