Organic nitrogen in PM2.5 aerosol at a forest site in the Southeast US

There is growing evidence that organo-nitrogen compounds may constitute a significant fraction of the aerosol nitrogen (N) budget. However, very little is known about the abundance and origin of this aerosol fraction. In this study, the concentration of organic nitrogen (ON) and major inorganic ions in PM2.5 aerosol were measured at the Duke Forest Research Facility near Chapel Hill, NC, during January and June of 2007. A novel on-line instrument was used, which is based on the Steam Jet Aerosol Collector (SJAC) coupled to an on-line total carbon/total nitrogen analyzer and two on-line ion chromatographs. The concentration of ON was determined by tracking the difference in concentrations of total nitrogen and of inorganic nitrogen (determined as the sum of N-ammonium and N-nitrate). The time resolution of the instrument was 30 min with a detection limit for major aerosol components of ∼0.1 mu;gm-3. Nitrogen in organic compounds contributed ∼33% on average to the total nitrogen concentration in PM2.5, illustrating the importance of this aerosol component. Absolute concentrations of ON, however, were relatively low (lt;1.0 mu;gm-3) with an average of 0.16 mu;gm-3. The absolute and relative contribution of ON to the total aerosol nitrogen budget was practically the same in January and June. In January, the concentration of ON tended to be higher during the night and early morning, while in June it tended to be higher during the late afternoon and evening. Back-trajectories and correlation with wind direction indicate that higher concentrations of ON occur in air masses originating over the continental US, while marine air masses are characterized by lower ON concentrations. The data presented in this study suggests that ON has a variety of sources, which are very difficult to quantify without information on chemical composition of this important aerosol fraction.

In situ concentration of semi-volatile aerosol using water-condensation technology

The effect of concentrating semi-volatile aerosols using a water-condensation technology was investigated using the Versatile Aerosol Concentration Enrichment System (VACES) and the Aerodyne Aerosol Mass Spectrometer (AMS) during measurements of ambient aerosol in Pittsburgh, PA. It was found that the shape of the sulfate mass-weighed size distribution was approximately preserved during passage through the concentrator for all the experiments performed, with a mass enhancement factor of about 10-20 depending on the experiment. The size distributions of organics, ammonium and nitrate were preserved on a relatively clean day (sulfate concentration around 7μg/m3), while during more polluted conditions the concentration of these compounds, especially nitrate, was increased at small sizes after passage through the concentrator. The amount of the extra material, however, is rather small in these experiments: between 2.4% and 7.5% of the final concentrated PM mass is due to "artifact" condensation. An analysis of thermodynamic processes in the concentrator indicates that the extra particle material detected can be explained by redistribution of gas-phase material to the aerosol phase in the concentrator. The analysis shows that the condensation of extra material is expected to be larger for water-soluble semi-volatile material, such as nitrate, which agrees with the observations. The analysis also shows that artifact formation of nitrate will be more pronounced in ammonia-limited conditions and virtually undetectable in ammonia-rich conditions. © 2004 Elsevier Ltd. All rights reserved.

Ambient aerosol size distributions and number concentrations measured during the Pittsburgh Air Quality Study (PAQS)

Twelve months of aerosol size distributions from 3 to 560nm, measured using scanning mobility particle sizers are presented with an emphasis on average number, surface, and volume distributions, and seasonal and diurnal variation. The measurements were made at the main sampling site of the Pittsburgh Air Quality Study from July 2001 to June 2002. These are supplemented with 5 months of size distribution data from 0.5 to 2.5μm measured with a TSI aerosol particle sizer and 2 months of size distributions measured at an upwind rural sampling site. Measurements at the main site were made continuously under both low and ambient relative humidity. The average Pittsburgh number concentration (3-500nm) is 22,000cm-3 with an average mode size of 40nm. Strong diurnal patterns in number concentrations are evident as a direct effect of the sources of particles (atmospheric nucleation, traffic, and other combustion sources). New particle formation from homogeneous nucleation is significant on 30-50% of study days and over a wide area (at least a hundred kilometers). Rural number concentrations are a factor of 2-3 lower (on average) than the urban values. Average measured distributions are different from model literature urban and rural size distributions. © 2004 Elsevier Ltd. All rights reserved.

THE STEAM-JET AEROSOL COLLECTOR

A new principle of sampling aerosol particles by means of steam injection with the consequent collection of grown droplets has been established. An air stream free of water-soluble gases is rapidly mixed with steam. The resulting supersaturation causes aerosol particles to grow into droplets. The droplets containing dissolved aerosol species are then collected by two cyclones in series. The solution collected in the cyclones is constantly pumped out and can be on- or off-line analysed by means of ion chromatography or flow injection analysis. On the basis of the new sampling principle a prototype of an aerosol sampler was designed which is capable of sampling particles quantitatively down to several nanometres in diameter. The mass sampling efficiency of the instrument was found to be 99\%. The detection limit of the sampler for ammonium, sulphate, nitrate and chloride ions is below 0.7 mu g m(-3). By reduction of an already identified source of contamination, much lower detection limits can be achieved. During measurements the sampler proved to be stable, working without any assistance for extended periods of time. Comparison of the sampler with filter packs during measurements of ambient air aerosols showed that the sampler gives good results.

An approach to monitor the fraction of elemental carbon in the ultrafine aerosol

Attempts were made to measure the fraction of elemental carbon (EC) in ultrafine aerosol by modifying an Ambient Carbonaceous Particulate Monitor (ACPM, R&P 5400). The main modification consisted in placing a quartz filter in one of the sampling lines of this dual-channel instrument. With the filter all aerosol and EC contained in it is collected, while in the other line of the instrument the standard impactor samples only particles larger than 0.14 μm. The fraction of EC in particles smaller than 0.14 μm is derived from the difference in concentration as measured via the two sampling lines. Measurements with the modified instrument were made at a suburban site in Amsterdam, The Netherlands. An apparent adsorption artefact, which could not be eliminated by the use of denuders, precluded meaningful evaluation of the data for total carbon. Blanks in the measurements of EC were negligible and the EC data were hence further evaluated. We found that the concentration of EC obtained via the channel with the impactor was systematically lower than that in the filter-line. The average ratio of the concentrations was close to 0.6, which indicates that approximately 40% of the EC was in particles smaller than 0.14 μm. Alternative explanations for the difference in the concentration in the two sampling lines could be excluded, such as a difference in the extent of oxidation. This should be a function of loading, which is not the case. Another reason for the difference could be that less material is collected by the impactor due to rebound, but such bounce of aerosol is very unlikely in The Netherlands due to co-deposition of abundant deliquesced and thus viscous ammonium compounds. The conclusion is that a further modification to assess the true fraction of ultrafine EC, by installing an impactor with cut-off diameter at 0.1 μm, would be worth pursuing. © 2005 Elsevier Ltd. All rights reserved.

Assessing variability and long-term trends in burned area by merging multiple satellite fire products

Long term, high quality estimates of burned area are needed for improving both prognostic and diagnostic fire emissions models and for assessing feedbacks between fire and the climate system. We developed global, monthly burned area estimates aggregated to 0.5° spatial resolution for the time period July 1996 through mid-2009 using four satellite data sets. From 2001ĝ€ "2009, our primary data source was 500-m burned area maps produced using Moderate Resolution Imaging Spectroradiometer (MODIS) surface reflectance imagery; more than 90% of the global area burned during this time period was mapped in this fashion. During times when the 500-m MODIS data were not available, we used a combination of local regression and regional regression trees developed over periods when burned area and Terra MODIS active fire data were available to indirectly estimate burned area. Cross-calibration with fire observations from the Tropical Rainfall Measuring Mission (TRMM) Visible and Infrared Scanner (VIRS) and the Along-Track Scanning Radiometer (ATSR) allowed the data set to be extended prior to the MODIS era. With our data set we estimated that the global annual area burned for the years 1997ĝ€ "2008 varied between 330 and 431 Mha, with the maximum occurring in 1998. We compared our data set to the recent GFED2, L3JRC, GLOBCARBON, and MODIS MCD45A1 global burned area products and found substantial differences in many regions. Lastly, we assessed the interannual variability and long-term trends in global burned area over the past 13 years. This burned area time series serves as the basis for the third version of the Global Fire Emissions Database (GFED3) estimates of trace gas and aerosol emissions.

A method of assessing air toxics concentrations in urban areas using mobile platform measurements.

The objective of this paper is to demonstrate an approach to characterize the spatial variability in ambient air concentrations using mobile platform measurements. This approach may be useful for air toxics assessments in Environmental Justice applications, epidemiological studies, and environmental health risk assessments. In this study, we developed and applied a method to characterize air toxics concentrations in urban areas using results of the recently conducted field study in Wilmington, DE. Mobile measurements were collected over a 4- x 4-km area of downtown Wilmington for three components: formaldehyde (representative of volatile organic compounds and also photochemically reactive pollutants), aerosol size distribution (representing fine particulate matter), and water-soluble hexavalent chromium (representative of toxic metals). These measurements were,used to construct spatial and temporal distributions of air toxics in the area that show a very strong temporal variability, both diurnally and seasonally. An analysis of spatial variability indicates that all pollutants varied significantly by location, which suggests potential impact of local sources. From the comparison with measurements at the central monitoring site, we conclude that formaldehyde and fine particulates show a positive correlation with temperature, which could also be the reason that photochemically generated formaldehyde and fine particulates over the study area correlate well with the fine particulate matter measured at the central site.

Fate of products of degradation processes: consequences for climatic change.

The end products of atmospheric degradation are not only CO2 and H2O but also sulfate and nitrate depending on the chemical composition of the substances which are subject to degradation processes. Atmospheric degradation has thus a direct influence on the radiative balance of the earth not only due to formation of greenhouse gases but also of aerosols. Aerosols of a diameter of 0.1 to 2 micrometer, reflect short wave sunlight very efficiently leading to a radiative forcing which is estimated to be about -0.8 watt per m2 by IPCC. Aerosols also influence the radiative balance by way of cloud formation. If more aerosols are present, clouds are formed with more and smaller droplets and these clouds have a higher albedo and are more stable compared to clouds with larger droplets. Not only sulfate, but also nitrate and polar organic compounds, formed as intermediates in degradation processes, contribute to this direct and indirect aerosol effect. Estimates for the Netherlands indicate a direct effect of -4 watt m-2 and an indirect effect of as large as -5 watt m-2. About one third is caused by sulfates, one third by nitrates and last third by polar organic compounds. This large radiative forcing is obviously non-uniform and depends on local conditions.

Pittsburgh air quality study overview

Ambient sampling for the Pittsburgh Air Quality Study (PAQS) was conducted from July 2001 to September 2002. The study was designed (1) to characterize particulate matter (PM) by examination of size, surface area, and volume distribution, chemical composition as a function of size and on a single particle basis, morphology, and temporal and spatial variability in the Pittsburgh region; (2) to quantify the impact of the various sources (transportation, power plants, biogenic sources, etc.) on the aerosol concentrations in the area; and (3) to develop and evaluate the next generation of atmospheric aerosol monitoring and modeling techniques. The PAQS objectives, study design, site descriptions and routine and intensive measurements are presented. Special study days are highlighted, including those associated with elevated concentrations of daily average PM2.5 mass. Monthly average and diurnal patterns in aerosol number concentration, and aerosol nitrate, sulfate, elemental carbon, and organic carbon concentrations, light scattering as well as gas-phase ozone, nitrogen oxides, and carbon monoxide are discussed with emphasis on the processes affecting them. Preliminary findings reveal day-to-day variability in aerosol mass and composition, but consistencies in seasonal average diurnal profiles and concentrations. For example, the seasonal average variations in the diurnal PM2.5 mass were predominately driven by the sulfate component. © 2004 Elsevier Ltd. All rights reserved.

Effect of peak inert-mode temperature on elemental carbon measured using thermal-optical analysis

Thermal-optical analysis is a conventional method for classifying carbonaceous aerosols as organic carbon (OC) and elemental carbon (EC). This article examines the effects of three different temperature protocols on the measured EC. For analyses of parallel punches from the same ambient sample, the protocol with the highest peak helium-mode temperature (870°C) gives the smallest amount of EC, while the protocol with the lowest peak helium-mode temperature (550°C) gives the largest amount of EC. These differences are observed when either sample transmission or reflectance is used to define the OC/EC split. An important issue is the effect of the peak helium-mode temperature on the relative rate at which different types of carbon with different optical properties evolve from the filter. Analyses of solvent-extracted samples are used to demonstrate that high temperatures (870°C) lead to premature EC evolution in the helium-mode. For samples collected in Pittsburgh, this causes the measured EC to be biased low because the attenuation coefficient of pyrolyzed carbon is consistently higher than that of EC. While this problem can be avoided by lowering the peak helium-mode temperature, analyses of wood smoke dominated ambient samples and levoglucosan-spiked filters indicate that too low helium-mode peak temperatures (550°C) allow non-light absorbing carbon to slip into the oxidizing mode of the analysis. If this carbon evolves after the OC/EC split, it biases the EC measurements high. Given the complexity of ambient aerosols, there is unlikely to be a single peak helium-mode temperature at which both of these biases can be avoided. Copyright © American Association for Aerosol Research.

Variability of particulate matter concentrations along roads and motorways determined by a moving measurement unit

The spatial variability of aerosol number and mass along roads was determined in different regions (urban, rural and coastal-marine) of the Netherlands. A condensation particle counter (CPC) and an optical aerosol spectrometer (LAS-X) were installed in a van along with a global positioning system (GPS). Concentrations were measured with high-time resolutions while driving allowing investigations not possible with stationary equipment. In particular, this approach proves to be useful to identify those locations where numbers and mass attain high levels ('hot spots'). In general, concentrations of number and mass of particulate matter increase along with the degree of urbanisation, with number concentration being the more sensitive indicator. The lowest particle numbers and PM1-concentrations are encountered in a coastal and rural area: <5000cm-3 and 6μgm-3, respectively. The presence of sea-salt material along the North-Sea coast enhances PM>1-concentrations compared to inland levels. High-particle numbers are encountered on motorways correlating with traffic intensity; the largest average number concentration is measured on the ring motorway around Amsterdam: about 160000cm-3 (traffic intensity 100000vehday-1). Peak values occur in tunnels where numbers exceed 106cm-3. Enhanced PM1 levels (i.e. larger than 9μgm-3) exist on motorways, major traffic roads and in tunnels. The concentrations of PM>1 appear rather uniformly distributed (below 6μgm-3 for most observations). On the urban scale, (large) spatial variations in concentration can be explained by varying intensities of traffic and driving patterns. The highest particle numbers are measured while being in traffic congestions or when behind a heavy diesel-driven vehicle (up to 600×103cm-3). Relatively high numbers are observed during the passages of crossings and, at a decreasing rate, on main roads with much traffic, quiet streets and residential areas with limited traffic. The number concentration exhibits a larger variability than mass: the mass concentration on city roads with much traffic is 12% higher than in a residential area at the edge of the same city while the number of particles changes by a factor of two (due to the presence of the ultrafine particles (aerodynamic diameter <100nm). It is further indicated that people residing at some 100m downwind a major traffic source are exposed to (still) 40% more particles than those living in the urban background areas. © 2004 Elsevier Ltd. All rights reserved.