Charles O. Stanier

Nucleation events during the Pittsburgh air quality study: Description and relation to key meteorological, gas phase, and aerosol parameters

During the Pittsburgh Air Quality Study (PAQS) aerosol size distributions between 3 nm and 680 nm were measured between July 2001 and June 2002. These distributions have been analyzed to assess the importance of nucleation as a source of ultrafine particles in Pittsburgh and the surrounding areas. The analysis shows nucleation on 50% of the study days and regional-scale formation of ultrafine particles on 30% of the days. Nucleation occurred during all seasons, but it was most frequent in fall and spring and least frequent in winter. Regional nucleation was most common on sunny days with below average PM2.5 concentrations. Local nucleation events were usually associated with elevated SO2 concentrations. The observed nucleation events ranged from weak events with only a slight increase in the particle number to relatively intense events with increases of total particle counts between 50,000 cm−3 up to 150,000 cm−3. Averaging all days of the study, days with nucleation events had number concentrations peaking at around noon at about 45,000 cm−3. This is compared to work days without nucleation, when the daily maximum was 8 am at 23,000 cm−3, and to weekends without nucleation, when the daily maximum was at noon at 16,000 cm−3. Twenty-four-hour average number concentrations were approximately 40% higher on days with nucleation compared to those without. Nucleation was typically observed starting around 9 am EST, although the start of nucleation events was later in winter and earlier in summer. The nucleation events are fairly well correlated with the product of [UV intensity * SO2 concentration] and also depend on the effective area available for condensation. This indicates that H2SO4 is a component of the new particles. Published correlations for nucleation by binary H2SO4—H2O cannot explain the observed nucleation frequency and intensity, suggesting that an additional component (perhaps ammonia) is participating in the particle formation.

An algorithm for combining electrical mobility and aerodynamic size distributions data when measuring ambient aerosol

Ambient aerosol particles vary in size from a few nanometers to several micrometers. No instrument is currently available to cover such a wide size range, and so a combination of several instruments is usually used. One such combination is that of electrical mobility classifiers and an aerodynamic sizer. Because of the differences in measurement principles between the instruments, difficulties arise in the combination of the measurements into a single size distribution. Here we report a simple algorithm that was developed to combine aerosol size distributions measured with commercially available scanning mobility particle sizers (SMPS; TSI Inc.) and an aerodynamic particle sizer (APS; TSI Inc.). This algorithm was tested during July 2001 in the Pittsburgh Air Quality Study. The aerosol during the study had both urban and regional origin and is characteristic of urban atmosphere in the Northeastern U.S. The integrated volume concentrations from the SMPS–APS showed a good correlation with PM2.5 mass concentration measurements using a TEOM. The relation of the aerosol mass to its volume is an “effective” density, a ratio of the bulk aerosol density to the shape factor. As a result of the comparison with the TEOM the ambient aerosol in the Pittsburgh area was found to have an effective density of 1.5 ± 0.3 g cm−3. Given that the aerosol during the study was found to always contain water, the particles are expected to be spherical and thus the shape factor may be assumed to be 1. This assumption has been supported by a comparison with the MOUDI, using the aerosol density of 1.5 g/cm3. It should be noted that the estimated aerosol density and the shape factor are applicable to this study only and may be different in other locations.

Photosynthetic control of atmospheric carbonyl sulfide during the growing season.

Climate models incorporate photosynthesis-climate feedbacks, yet we lack robust tools for large-scale assessments of these processes. Recent work suggests that carbonyl sulfide (COS), a trace gas consumed by plants, could provide a valuable constraint on photosynthesis. Here we analyze airborne observations of COS and carbon dioxide concentrations during the growing season over North America with a three-dimensional atmospheric transport model. We successfully modeled the persistent vertical drawdown of atmospheric COS using the quantitative relation between COS and photosynthesis that has been measured in plant chamber experiments. Furthermore, this drawdown is driven by plant uptake rather than other continental and oceanic fluxes in the model. These results provide quantitative evidence that COS gradients in the continental growing season may have broad use as a measurement-based photosynthesis tracer.

Health impacts and economic losses assessment of the 2013 severe haze event in Beijing area.

Haze is a serious air pollution problem in China, especially in Beijing and surrounding areas, affecting visibility, public health and regional climate. In this study, the Weather Research and Forecasting-Chemistry (WRF-Chem) model was used to simulate PM2.5 (particulate matters with aerodynamic diameter≤2.5 μm) concentrations during the 2013 severe haze event in Beijing, and health impacts and health-related economic losses were calculated based on model results. Compared with surface monitoring data, the model results reflected pollution concentrations accurately (correlation coefficients between simulated and measured PM2.5 were 0.7, 0.4, 0.5 and 0.6 in Beijing, Tianjin, Xianghe and Xinglong stations, respectively). Health impacts assessments show that the PM2.5 concentrations in January might cause 690 (95% confidence interval (CI): (490, 890)) premature deaths, 45,350 (95% CI: (21,640, 57,860)) acute bronchitis and 23,720 (95% CI: (17,090, 29,710)) asthma cases in Beijing area. Results of the economic losses assessments suggest that the haze in January 2013 might lead to 253.8 (95% CI: (170.2, 331.2)) million US

Advanced Factor Analysis on Pittsburgh Particle Size-Distribution Data Special Issue of Aerosol Science and Technology on Findings from the Fine Particulate Matter Supersites Program

losses, accounting for 0.08% (95% CI: (0.05%, 0.1%)) of the total 2013 annual gross domestic product (GDP) of Beijing.

Water content of ambient aerosol during the Pittsburgh Air Quality Study

Positive matrix factorization (PMF) method was applied to particle size-distribution data acquired during the Pittsburgh Air Quality Study (PAQS) from July 2001 to August 2001. After removing those days with nucleation events, a total of 1632 samples, each with 165 evenly-sized intervals from 0.003 to 2.5 μm, were obtained from scanning mobility particle spectrometer (SMPS) and aerodynamic particle sampler (APS). The temporal resolution was 15 min. The values for each set of five consecutive-size bins were averaged to produce 33 new size channels. The size distributions of particle number as well as volume were analyzed with a bilinear model. Three kinds of information were used to identify the sources: the number and volume size distributions associated with the factors, the time frequency properties of the contribution of each source (Fourier analysis of source contribution values) and the correlations of the contribution values with the gas-phase data and some composition data. Through these analyses, the sources were assigned as sparse nucleation, local traffic, stationary combustion, grown particles and remote traffic, and secondary aerosol in a sequence of decreasing number concentration contributions. Conditional probability function (CPF) analysis was performed for each source so as to ascertain the likely directions in which the sources were located.

Investigation of the relationship between chemical composition and size distribution of airborne particles by partial least squares and positive matrix factorization

The aerosol water content and volumetric growth factors of fine particulate matter were measured during July-August 2001 and January-June 2002 in an urban park about 6 km from downtown Pittsburgh, Pennsylvania. Most of the aerosol during the study was transported to the region from other areas, and its composition and concentration were characteristic of the regional particulate matter in the northeastern United States. During the summer months the ambient aerosol practically always contained water even when the relative humidity ( RH) was as low as 30%. In contrast, during the winter the aerosol was dry below 60% RH. The spring months were characterized by a transitional behavior between these two states. The observed seasonal behavior can be explained by the aerosol acidity. The summer aerosol was acidic and retained water at low RH. The winter aerosol was neutral and became wet when the relative humidity reached the deliquescence point of ammonium nitrate. The observations during July 2001 were compared with the predictions of the thermodynamic Gibbs Free Energy Minimization (GFEMN) model and the aerosol inorganics model ( AIM), neglecting the organic aerosol contribution to water absorption. The models under-predicted water concentrations by about 35%, but no clear correlation between organic mass and the excess water was observed. On average, the contribution of the organics to water absorption appeared to be higher during the afternoon hours and when the aerosol was presumably more oxidized.

Cyclic siloxanes in air, including identification of high levels in Chicago and distinct diurnal variation.

[1] Two multivariate data analysis methods, partial least square (PLS) and positive matrix factorization (PMF), were used to analyze aerosol size distribution data and composition data. The relationships between the size distribution data and composition data were investigated by PLS. Three latent variables summarized chemical composition data and most variations in size distribution data especially for large particles and proved the existence of the linearity between the two data sets. The three latent variables were associated with traffic and local combustion sources, secondary aerosol, and coal-fired power plants. The size distribution, particle composition, and gas composition data were combined and analyzed by PMF. Source information was obtained for each source using size distribution and chemical composition simultaneously. Eleven sources were identified: secondary nitrate 1 and 2, remote traffic, secondary sulfate, lead, diesel traffic, coal-fired power plant, steel mill, nucleation, local traffic, and coke plant.

A method for the in situ measurement of fine aerosol water content of ambient aerosols: The dry-ambient aerosol size spectrometer (DAASS)

The organosilicon compounds octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) are high production volume chemicals that are widely used in household goods and personal care products. Due to their prevalence and chemical characteristics, cyclic siloxanes are being assessed as possible persistent organic pollutants. D4, D5, and D6 were measured in indoor and outdoor air to quantify and compare siloxane concentrations and compound ratios depending on location type. Indoor air samples had a median concentration of 2200 ng m(-3) for the sum of D4, D5, and D6. Outdoor sampling locations included downtown Chicago, Cedar Rapids, IA, and West Branch, IA, and had median sum siloxane levels of 280, 73, and 29 ng m(-3) respectively. A diurnal trend is apparent in the samples taken in downtown Chicago. Nighttime samples had a median 2.7 times higher on average than daytime samples, which is due, in part, to the fluctuations of the planetary boundary layer. D5 was the dominant siloxane in both indoor and outdoor air. Ratios of D5 to D4 averaged 91 and 3.2 for indoor and outdoor air respectively.

Abiotic mechanism for the formation of atmospheric nitrous oxide from ammonium nitrate.

Hygroscopic growth of atmospheric particles affects a number of environmentally important aerosol properties. Due to the hysteresis exhibited by the aerosol hygroscopic growth, the physical state of particles and the amount of aerosol water are uncertain within a wide range of relative humidities (RHs) found in the troposphere, leading to uncertainties in optical and chemical properties of the aerosol. Here we report the design and tests of an automated system that was built to assess the amount of aerosol water at atmospheric conditions. The system consists of two scanning mobility particle sizers (SMPS) and an aerodynamic particle sizer (APS) that measure the aerosol size distribution between 3 nm and 10 μm in diameter. The inlets of the instruments and their sheath air lines are equipped with computer-controlled valves that direct air through Nafion dryers or bypass them. The Nafion dryers dehydrate the air streams to below 30% RH at which point ambient particles are expected to lose most or all water. The switch between the dried and the ambient conditions occurs every 7 min and is synchronized with the scan times of the aerosol spectrometers. In this way the system measures alternatively dried (below 30% RH) and ambient aerosol size distributions. A comparison of the ambient RH and the dried RH size distributions and the corresponding integrated volume concentrations provides a measure of the physical state of particles and the amount of aerosol water. The aerosol water content can be treated as a growth factor or as an absolute quantity and can be calculated as a time series or as a function of RH (humidigram). When combined with aerosol composition measurements, the DAASS can be used to compare hygroscopic growth models and measurements.