Design and Laboratory Evaluation of a Sequential Spot Sampler for Time-Resolved Measurement of Airborne Particle Composition

A new sampling approach has been developed to enable affordable, time-resolved monitoring of particulate chemical composition, and more generally to provide concentrated samples of airborne particles. Using a newly developed, moderated water-based condensational growth technology, individual particle samples are deposited in a 1-mm diameter dry “spot.” The moderated condensation technology enables this collection with minimal temperature rise, providing robust collection for volatile constituents. Measured collection efficiencies are above 95% for particles in the size range from 0.010 μm to 2.5 μm. A set of 20 or more time-resolved samples, plus blanks, may be collected onto a multiwell collection plate. For chemical analysis the plate is returned to the laboratory, and placed directly into a modified autosampler, without extraction or preparation. The autosampler handles the addition of eluent, extraction, and sample injection without user manipulation. This article presents the design and laboratory evaluation of a 1.5 L/min sampling rate version of this system.

Copyright 2014 American Association for Aerosol Research     

Seasonal Influence on Vapor-and Particle-Phase Polycyclic Aromatic Hydrocarbon Concentrations in School Communities Located in Southern California

Ambient concentrations of 15 vapor-and particle-phase (PM _2.5 ) polycyclic aromatic hydrocarbons (PAHs), listed by the US EPA as priority pollutants, were measured between July 2002 and November 2003 in six Southern California communities participating in a multi-year chronic respiratory health study of schoolchildren. The communities were geographically distributed over two hundred kilometers, extending from Long Beach in coastal Los Angeles, to high mountain areas to the north and west of the Los Angeles basin, and south into Eastern San Diego County. Seasonal and spatial variation in the atmospheric concentrations of PAHs is of interest because this class of compounds includes potent mutagens, carcinogens, and species capable of generating reactive oxygen species (ROS) that may lead to oxidative stress. Naphthalene accounted for 95% of the total PAH mass; annual averages ranged from 89 to 142 ng m ^{? 3} . Benzo[ghi]perylene (BGP) and the pro-carcinogen benzo[a]pyrene (BAP), present almost exclusively in the particle-phase, ranged respectively from 38 to 231 pg m ^?3 and 75 and 111 pg m ^{? 3} , with the highest values observed in Long Beach, a community with a high volume of seaport-related activities, and Lancaster, a commuter dormitory community. A considerable increase in the particle-phase PAH concentration, relative to the vapor-phase, was observed as ambient temperature decreased. Cold/hot season ratios for PAHs in PM _2.5 averaged 5.7, reaching 54 at Long Beach. The presented data underscore the importance of seasonal variations on atmospheric PAH concentrations. These observations are relevant to future interpretation and analysis of community-scale human health effects research.     

Observations of Twelve USEPA Priority Polycyclic Aromatic Hydrocarbons in the Aitken Size Range (10–32 nm D p )

Particle size distribution measurements of twelve USEPA priority pollutant polycyclic aromatic hydrocarbons (PAHs)—collected in Riverside, California, down to 10 nm aerodynamic diameter (D_p)—observed on integrated nocturnal samples (7:00 p.m.-6:30 a.m.) revealed that between 46 and 100% of the mass of particles in the Aitken size range was found in the 10–18 nm size bin. Particles in this size range have high alveolar deposition efficiency.     

Water condensation-based nanoparticle charging system: Physical and chemical characterization

Abstract

A water condensation-based ion charging system has been developed to enhance both the charging efficiency and the concentration of sub-20?nm particles. This NanoCharger consists of a bipolar ion source followed by a parallel plate water-based condensation system, an embedded ion scavenger, and an aerodynamic focusing stage. Sufficient numbers of ions are transported through the system to attach to the formed droplets. An ion scavenger removes the ions immediately after the droplet formation to minimize multiple charging. A subsequent cold-walled condensation stage removes most of the water vapor, lowering the dew point to below 16?°C, while a set of focusing nozzles concentrates the droplets into ～10% of the flow. The flow is then slightly heated to evaporate the droplets. The physical enhancement of electrical charging was evaluated in the laboratory using mobility-selected particles, and found to provide ～40-fold enhancement over bipolar charging for 6–15?nm particles. Chemical artifacts were evaluated through thermal desorption chemical ionization mass spectrometry. Data comparing ion spectra for flow that passed through the NanoCharger to that obtained without it showed nearly equivalent ion spectra, indicating that no significant artifacts were introduced from the condensation–evaporation process.

Copyright © 2018 American Association for Aerosol Research     

Detection near 1-nm with a laminar-flow,water-based condensation particle counter

Presented is a laminar-flow, water-based condensation particle counter capable of particle detection near 1 nm. This instrument employs a three-stage, laminar-flow growth tube with a “moderator” stage that reduces the temperature and water content of the output flow without reducing the peak supersaturation, and makes feasible operation at the large temperature differences necessary for achieving high supersaturations. The instrument has an aerosol flow of 0.3 L/min, and does not use a filtered sheath flow. It is referred to as a “versatile” water condensation particle counter, or vWCPC, as operating temperatures can be adjusted in accordance with the cut-point desired. When operated with wall temperatures of ～2°C, >90°C, and ～22°C for the three stages, respectively, the vWCPC detects particles generated from a heated nichrome wire with a 50% efficiency cut-point near 1.6 nm mobility diameter. At these operating temperatures, it also detects 10–20% of large molecular ions formed from passing filtered ambient air through a bipolar ion source. Decreasing the temperature difference between the first two stages, with the first and second stages operated at 10 and 90°C, respectively, essentially eliminates the response to charger ions, and raises the 50% efficiency cut-point for the nichrome wire particles to 1.9 nm mobility diameter. The time response, as measured by rapid removal of an inlet filter, yields a characteristic time constant of 195 ms.

Copyright © 2017 American Association for Aerosol Research     

Size-resolved polycyclic aromatic hydrocarbon emission factors from on-road gasoline and diesel vehicles: temperature effect on the nuclei-mode

Motor vehicles are a major source of polycyclic aromatic hydrocarbon (PAH) emissions in urban areas. Motor vehicle emission control strategies have included improvements in engine design, exhaust emission control, and fuel reformulation. Therefore, an updated assessment of the effects of the shifts in fuels and vehicle technologies on PAH vehicular emission factors (EFs) is needed. We have evaluated the effects of ambient temperature on the size-resolved EFs of nine US EPA Priority Pollutant PAH, down to 10 nm diameter, from on-road California gasoline light-duty vehicles with spark ignition (SI) and heavy-duty diesels with compression ignition (CI) in summer 2004 and winter 2005. During the winter, for the target PAH with the lowest subcooled equilibrium vapor pressure --benzo[a]pyrene, benzo[ghi]perylene, and indeno[1,2,3-cd]pyrene-- the mass in the nucleation mode, defined here as particles with dp <32 nm, ranged between 14 and 38% for SI vehicles and 29 and 64% for CI vehicles. Our observations of the effect of temperature on the mass of PAH in the nucleation mode are similar to the observed effect of temperature on the number concentration of diesel exhaust particles in the nucleation mode in a previous report.     

Determination of Semivolatile and Particulate Polycyclic Aromatic Hydrocarbons in SRM 1649a and PM 2.5 Samples by HPLC-Fluorescence

The concentrations of 15 "priority pollutant" semivolatile and particulate polycyclic aromatic hydrocarbons (PAHs) were determined in three sets of samples supplied by the National Institute for Standards and Technology (NIST) as part of an interlaboratory analytical exercise. The purpose of the exercise, organized by NIST and the U.S. Environmental Protection Agency, was to determine the comparability of measurements for various organic analytes among the participating laboratories, and to establish consensus values for SRM 1649a and interim materials. The commercially available SRM 1649a Atmospheric Urban Dust and two subsamples of this popular reference material were analyzed: an extract designated as Air Particulate Extract, and a resieved portion labeled Air Particulate I. The method used in our laboratory for the exercise consists of the extraction of the PAHs from the solid samples by ultrasonication, followed by separation and quantification using high-performance liquid chromatographyfluorescence detection. The accuracy and precision of the results obtained by our analytical protocol and by 14 other participating laboratories were evaluated using the International Union of Pure and Applied Chemistry guidelines of z-scores ( = 25% of the exercise assigned value) and p -scores. Using these guidelines the accuracy of our method provided results that are satisfactory for all 15 target PAHs (|z| h 2) determined in the Air Particulate Extract and, except for fluorene, in the Air Particulate I sample. Finally, application of the methodology is demonstrated for the quantification of PAHs present at the pg m m 3 range in PM 2.5 samples collected from 163 m 3 of air in the Los Angeles basin.     

Evaluation of a Denuder-MOUDI-PUF Sampling System to Measure the Size Distribution of Semi-Volatile Polycyclic Aromatic Hydrocarbons in the Atmosphere

This study describes a field comparison conducted between 2 methods employing different MOUDI impactor configurations to evaluate their performance in sampling and measurement of the size distribution of 15 priority pollutant polycyclic aromatic hydrocarbons (PAHs). Samples were collected during 24 h periods approximately every 7th day, beginning at 8:00 AM, in 2 different sites of the Los Angeles Basin. One site was near Central Los Angeles in an area impacted by high vehicular traffic, whereas the other site was located about 60 km downwind of central Los Angeles (receptor site). Particle samples from about 43 m 3 of air were collected using collocated MOUDI impactors and classified in 3 aerodynamic diameter size intervals: 0-0.18 w m (ultrafine mode I), 0.18-2.5 w m (accumulation mode II), and 2.5-10 w m (coarse mode III). One MOUDI operated in the conventional mode, the other with a vapor trapping system that included an XAD-4 coated annular denuder placed upstream of the impactor and a polyurethane foam plug (PUF) placed in series behind the impactor. PAHs were separated and quantified by HPLC with fluorescence detection optimized for the highest sensitivity. The results showed that for both sites, using either sampling system, the size distributions obtained are similar for the less volatile PAHs (log [ p ° L ] h m 3.2), but different for the more volatile PAHs (log [ p ° L ] S m 2.06). In the central Los Angeles site, the largest PAH fraction was found in the 0-0.18 w m (mode I) size range, typical of primary emissions. At the downwind location, the largest fraction was in the 0.18-2.5 w m (mode II) size range, consistent with an "aged" aerosol. At both sites, albeit not statistically significant, the mean regular to denuded MOUDI mass ratios were 33-36% and 11-19% higher, respectively, for the more volatile and the less volatile PAH groups. Sampling with the regular MOUDI configuration is simpler and thus recommended for measurement of the size distribution of PAHs in either group.     

Seasonal and Spatial Variation of Polycyclic Aromatic Hydrocarbons in Vapor-Phase and PM2.5 in Southern California Urban and Rural Communities

Fifteen priority polycyclic aromatic hydrocarbons (PAHs) were measured in two rural communities (Atascadero and Lompoc) located several hundred km northwest of Los Angeles and in four urban communities 40–100 km downwind of Los Angeles (San Dimas, Upland, Mira Loma, and Riverside), during all seasons, from May 2001 to July 2002. PM_2.5 and vapor-phase PAHs were collected, on prebaked quartz fiber filters and PUF-XAD-4 resin, respectively, at 113 LPM, during 24 h periods, every eighth day, and quantified by HPLC-Fluorescence. At all sites vapor-phase PAHs contained > 99.9% of the total PAH mass and were dominated by naphthalene (NAP), which varied from about 60 ng m ^{? 3} in Lompoc, a community with light traffic, to ～580 ng m ^{? 3} in Riverside, a community traversed by ～200,000 vehicles day^{? 1}. During summer pollution episodes in urban sites, NAP concentrations reached 7–30 times annual averages. Except for summer episodes, concentrations of low MW PAHs showed small seasonal variations (～2 times higher in winter). Similar concentrations of particle-phase PAHs were observed at all sites except for Lompoc. Benzo[ghi]perylene (BGP), a marker of gasoline exhaust emissions, showed the highest concentration among particle-phase PAHs, varying from 23.3 pg m^?3 in Lompoc to 193 pg m^?3 in Mira Loma. Benzo[a]pyrene and indeno[1,2,3-cd]pyrene, found exclusively in the particle phase, were much higher in urban sites (～40–100 pg m^?3), than in Lompoc (～12 pg m^?3). Winter particle-phase PAHs were 2 to 14 times higher than summer levels. Particle-phase PAHs were negatively correlated with mean air temperature in urban sites (r = ?0.50 to ?0.75), probably resulting from surface inversions occurring during winter. The data suggest that in Southern California vehicular exhaust emissions are a major contributor to particle-phase PAHs.