Hygroscopic Organic Aerosols during BRAVO?

Abstract

The hygroscopic properties of the organic fraction of aerosols are poorly understood. The ability of organic aerosols to absorb water as a function of relative humidity (RH) was examined using data collected during the 1999 Big Bend Regional Aerosol and Visibility Observational Study (BRAVO). (On average, organics accounted for 22% of fine particulate matter with an aerodynamic diameter less than 2.5 µm (PM_2.5) mass). Hourly RH exceeded 80% only 3.5% of the time and averaged 44%. BRAVO aerosol chemical composition and dry particle size distributions were used to estimate PM_2.5 light scattering (Bsp) at low and high ambient RH. Liquid water growth associated with inorganic species was sufficient to account for measured Bsp for RH between 70 and 95%.     

Predicting black smoke levels from deposit gauge and SO2 data to estimate long-term exposure in the United Kingdom, 1956–1961

BackgroundIn the UK air quality has been monitored systematically since 1914, providing valuable data for studies of the long-term trends in air pollution and potentially for studies of health effects of air pollutants. There are, however, challenges in interpreting these data due to changes over time in the number and location of monitored sites, and in monitoring techniques. Particulate matter was measured as deposited matter (DM) using deposit gauge monitors until the 1950s when black smoke (BS) filters were introduced. Estimating long-term exposure to particulates using data from both deposit gauge and BS monitors requires an understanding of the relationships between DM, SO₂ and BS.AimsTo explore whether DM and/or SO₂, along with seasonal and location specific variables can be used to predict BS levels.MethodsAir quality data were abstracted from hard copies of the monthly Atmospheric Pollution Bulletins for the period April 1956–March 1961 for any sites with co-located DM, SO₂ and BS data for three or more consecutive years. The relationships between DM, SO₂, and BS were assessed using mixed models.ResultsThere were 34 eligible sites giving 1521 triplets of data. There was a consistent correlation between SO₂ and BS at all sites, but the association between DM and BS was less clear and varied by location. Mixed modelling allowing for repeat measurements at each site revealed that SO₂, year, rainfall and season of measurement explained 72% of the variability in BS levels.ConclusionsSO₂ can be used as a surrogate measure for BS in all monitoring locations. This surrogate can be improved upon by consideration of site specific characteristics, seasonal effects, rainfall and year of measurement. These findings will help in estimating historic, long-term exposure to particulates where BS or other measures are not available.     

Source Apportionment of Ambient Total Suspended Particulates and Coarse Particulate Matter in Urban Areas of Jiaozuo,China

Abstract

Approximately 750 total suspended particulates (TSPs) and coarse particulate matter (PM₁₀) filter samples from six urban sites and a background site and >210 source samples were collected in Jiaozuo City during January 2002 to April 2003. They were analyzed for mass and abundances of 25 chemical components. Seven contributive sources were identified, and their contributions to ambient TSP/PM₁₀ levels at the seven sites in three seasons (spring, summer, and winter days) and a “whole” year were estimated by a chemical mass balance (CMB) receptor model. The spatial TSP average was high in spring and winter days at a level of approximately 530 ～g/m³ and low in summer days at 456 ～g/m³; however, the spatial PM₁₀ average exhibited little variation at a level of approximately 325 ～g/m³, and PM_10-to-TSP ratios ranged from 0.58 to 0.81, which suggested heavy particulate matter pollution existing in the urban areas. Apportionment results indicated that geological material was the largest contributor to ambient TSP/PM₁₀ concentrations, followed by dust emissions from construction activities, coal combustion, secondary aerosols, vehicle movement, and other industrial sources. In addition, paved road dust and re-entrained dust were also apportioned to the seven source types and found soil, coal combustion, and construction dust to be the major contributors.     

Source Profiles of Particulate Matter Emissions from a Pilot-Scale Boiler Burning North American Coal Blends

ABSTRACT

Recent awareness of suspected adverse health effects from ambient particulate matter (PM) emission has prompted publication of new standards for fine PM with aerodynamic diameter less than 2.5 μm (PM_2.5). However, scientific data on fine PM emissions from various point sources and their characteristics are very limited. Source apportionment methods are applied to identify contributions of individual regional sources to tropospheric particulate concentrations. The existing industrial database developed using traditional source measurement techniques provides total emission rates only, with no details on chemical nature or size characteristics of particulates. This database is inadequate, in current form, to address source-receptor relationships.

A source dilution system was developed for sampling and characterization of total PM, PM_2.5, and PM₁₀ (i.e., PM with aerodynamic diameter less than 10 μm) from residual oil and coal combustion. This new system has automatic control capabilities for key parameters, such as relative humidity (RH), temperature, and sample dilution. During optimization of the prototype equipment, three North American coal blends were burned using a 0.7-megawatt thermal (MW_t) pulverized coal-fired, pilot-scale boiler. Characteristic emission profiles, including PM_2.5 and total PM soluble acids, and elemental and carbon concentrations for three coal blends are presented.     

Dissipation of DDT in natural water under field conditions

Abstract

¹⁴C‐DDT dissipated gradually from natural water under outdoor conditions and declined to 40% of the applied radioactivity after 5 months. The losses are due to adsorption to particulates and volatilization from the water surface. In natural water DDT undergoes gradual conversion to DDE as the major degradation product and to a lesser extent to DDD. It may be concluded that DDT dissipates and degrades fairly rapidly in subtropical natural waters. Adsorption to particulate matter contributes to partial “removal” of DDT.     

Characterization of particulate emissions from Australian open-cut coal mines: Toward improved emission estimates

Given the significance of mining as a source of particulates, accurate characterization of emissions is important for the development of appropriate emission estimation techniques for use in modeling predictions and to inform regulatory decisions. The currently available emission estimation methods for Australian open-cut coal mines relate primarily to total suspended particulates and PM₁₀ (particulate matter with an aerodynamic diameter <10 μm), and limited data are available relating to the PM_2.5 (<2.5 μm) size fraction. To provide an initial analysis of the appropriateness of the currently available emission estimation techniques, this paper presents results of sampling completed at three open-cut coal mines in Australia. The monitoring data demonstrate that the particulate size fraction varies for different mining activities, and that the region in which the mine is located influences the characteristics of the particulates emitted to the atmosphere. The proportion of fine particulates in the sample increased with distance from the source, with the coarse fraction being a more significant proportion of total suspended particulates close to the source of emissions. In terms of particulate composition, the results demonstrate that the particulate emissions are predominantly sourced from naturally occurring geological material, and coal comprises less than 13% of the overall emissions. The size fractionation exhibited by the sampling data sets is similar to that adopted in current Australian emission estimation methods but differs from the size fractionation presented in the U.S. Environmental Protection Agency methodology. Development of region-specific emission estimation techniques for PM₁₀ and PM_2.5 from open-cut coal mines is necessary to allow accurate prediction of particulate emissions to inform regulatory decisions and for use in modeling predictions.

Implications: Development of region-specific emission estimation techniques for PM₁₀ and PM_2.5 from open-cut coal mines is necessary to allow accurate prediction of particulate emissions to inform regulatory decisions and for use in modeling predictions. Comprehensive air quality monitoring was undertaken, and corresponding recommendations were provided.     

Organic Content of Particulate Matter In Turbine Engine Exhaust

Solid particulate matter, mainly carbon, emitted into the air from the combustion of fossil fuels contains a variety of organic species adsorbed on it. In our examination of these particulates from the combustion of kerosene type fuels in a gas turbine engine, attention was focused on polynuclear aromatic compounds, phenols, nitrosamines, and total organics. Polynuclears were determined by HPLC, GC/MS, and NMR examination. Phenols and nitrosamines were isolated and then measured by gas chromatography using a flame ionization detector and nitrogen detector. Total organics were determined by a backflush chromatographic procedure. The particulates were collected using a high capacity pumping system and 293 mm diameter teflon filters through which was passed up to 43 m³ of exhaust gas. Extraction of the organic matter was done in a Soxhlet extractor using hexane usually. The engine was operated at idle, approach, climb, and takeoff power settings with low sulfur and high sulfur (0.25%) fuels. Most of the PAH were small 3 and 4 fused ring compounds with very few, at low concentrations, of 5 and 6 fused ring species. No nitrosamines were found and except in a few cases, at low levels, no phenols. PNA and total organic levels decreased with increase in a power setting and were higher in the exhaust from low sulfur fuels. Less than 1% of the organic matter emitted by the engine was absorbed on the particulate matter. The body of information presented in the paper is directed to individuals concerned with the nature of emissions from gas turbine engines. The work was supported by a contract with the Environmental Protection Agency.     

Development and Preliminary Evaluation of a Particulate Matter Emission Factor Model for European Motor Vehicles

ABSTRACT

Although modeling of gaseous emissions from motor vehicles is now quite advanced, prediction of particulate emissions is still at an unsophisticated stage. Emission factors for gasoline vehicles are not reliably available, since gasoline vehicles are not included in the European Union (EU) emission test procedure. Regarding diesel vehicles, emission factors are available for different driving cycles but give little information about change of emissions with speed or engine load. We have developed size-specific speed-dependent emission factors for gasoline and diesel vehicles. Other vehicle-generated emission factors are also considered and the empirical equation for re-entrained road dust is modified to include humidity effects. A methodology is proposed to calculate modal (accelerating, cruising, or idling) emission factors. The emission factors cover particle size ranges up to 10 um, either from published data or from user-defined size distributions.

A particulate matter emission factor model (PMFAC), which incorporates virtually all the available information on particulate emissions for European motor vehicles, has been developed. PMFAC calculates the emission factors for five particle size ranges [i.e., total suspended particulates (TSP), PM₁₀, PM₅, PM₂₅, and PM₁] from both vehicle exhaust and nonexhaust emissions, such as tire wear, brake wear, and re-entrained road dust. The model can be used for an unlimited number of roads and lanes, and to calculate emission factors near an intersection in user-defined elements of the lane. PMFAC can be used for a variety of fleet structures. Hot emission factors at the user-defined speed can be calculated for individual vehicles, along with relative cold-to-hot emission factors. The model accounts for the proportions of distance driven with cold engines as a function of ambient temperature and road type (i.e., urban, rural, or motorway).

A preliminary evaluation of PMFAC with an available dispersion model to predict the airborne concentration in the urban environment is presented. The trial was on the A6 trunk road where it passes through Loughborough, a medium-size town in the English East Midlands. This evaluation for TSP and PM₁₀ was carried out for a range of traffic fleet compositions, speeds, and meteorological conditions. Given the limited basis of the evaluation, encouraging agreement was shown between predicted and measured concentrations.     

Size Distribution and Sources of Aerosol in Launceston,Australia, during Winter 1997

ABSTRACT

As part of a pilot study into the chemical and physical properties of Australian fine particles, a suite of aerosol samples was collected at Ti Tree Bend in Launceston, Tasmania, during June and July 1997. This period represents midwinter in the Southern Hemisphere, a period when aerosol sources in Launceston are dominated by smoke from domestic wood burning. This paper describes the results from this measurement campaign, with the aim of assessing the effect of wood smoke on the chemical and physical characteristics of ambient aerosol. A micro orifice uniform deposit impactor (MOUDI) was used to measure the size distributions of the aerosol from 0.05 to 20 n m aerodynamic diameter. Continuous measurements of fine particle mass were made using a PM_2.5 tapered element oscillating microbalance (TEOM) and light scattering coefficients at 530 nm were measured with nephelometers.

Mass size distributions tended to be bimodal, with the diameter of the dominant mode tending to smaller sizes with increases in total mass. Non-sea salt potassium and polycyclic aromatic hydrocarbons (PAHs) were used as chemical tracers for wood smoke. Wood smoke was found to increase absolute particle mass (enough to regularly exceed air quality standards), and to concentrate mass in a single mode below 1 μm aerodynamic diameter. The acid-base equilibrium of the aerosol was altered by the wood smoke source, with free acidity hydrogen ion, non-sea salt sulfate, and ammonium concentrations being higher and the concentration of all species, including nitrate (to differing extents), focused in the fine particle size ranges. The wood smoke source also heavily influenced the aerosol scattering efficiency, adding to a strong diurnal cycle in both mass concentration and light scattering.     

The Formation of Reactive Oxygen Species Catalyzed by Neutral,Aqueous Extracts of NIST Ambient Particulate Matter and Diesel Engine Particles

ABSTRACT

It is important to characterize the chemical properties of particulate matter in order to understand how low doses, inhaled by a susceptible population, might cause human health effects. The formation of reactive oxygen species catalyzed by neutral, aqueous extracts of two ambient par-ticulate samples, National Institute of Standards & Technology (NIST) Standard Reference Materials (SRM) 1648 and 1649, and two diesel particulate samples, NIST SRM 1650 and SRM 2975, were measured. The formation of reactive oxygen species was estimated by measuring the formation of malondialdehyde from 2-deoxyribose in the presence of ascorbic acid; H₂O₂ was not added to this assay. SRM 1649, ambient particulate matter collected from Washington, DC, generated the most malondialdehyde, while SRM 2975, diesel particulate matter collected from a forklift, yielded the least amount. Desferrioxamine inhibited the formation of malondialdehyde from the par-ticulate samples providing additional data to support the observation that transition metals were involved in the generation of reactive oxygen species. Six transition metal sulfates (iron sulfate, copper sulfate, vanadyl sulfate, cobalt sulfate, nickel sulfate, and zinc sulfate) were assayed     

The sorption of Zectran on bottom sediments and peat moss

Abstract

A modified analytical method employed to determine the insecticide Zectran in natural waters frequently has resulted in erroneous data. The errors have been attributed to interferences from particulate matter in these waters. In order to evaluate analytical interferences due to sorption of Zectran on particu‐lates, a series of experiments was performed using bottom sediments and a peat moss in contact with aqueous solutions of Zectran at a pH value of 6.0 and 20°C.

Isotherm studies confirmed that Zectran sorption occurs in a direct relation to the amount of chemically oxidizable carbon present in the bottom sediments or peat moss. However, the extent of sorption was limited, which suggested that particulates may not be the primary interference in the modified analytical method.     

Characterization of Particulates from Power Plants

The emphasis on participate control from industrial processes has been shifted recently towards fine particulates, having diameters less than 3 microns. There exists an urgent need for more scientific information of fine particle characterization.^1,2 Coal and oil fired power plants are among the largest anthropogenic point sources of particulate matter.³ Limited knowledge is available on particle size distribution and trace metal composition in power plant emissions.^4-7 The morphological properties of particle emissions have been largely neglected. In this report we present some information on particle characteristics for an oil-fired and coal-fired power plant.     

Effects of wastewater from olive processing on seed germination and early plant growth of different vegetable species

Abstract

The effects of wastewater from olive processing on seed germination and early plant growth of different vegetable species were examined. Three types of wastewater at different concentrations were tested: raw wastewater, wastewater with organic matter removed and deionized wastewater.

Results generally indicate an inhibitory effect on seed germination and early plant growth by all treatments containing any kind of wastewater. Of the three types of effluent, raw wastewater had the greatest depressive effect, followed by deionized wastewater and finally effluent with organic matter removed. Barley showed the least sensitivity to phytotoxic effects while tomato was the plant most affected. The remaining vegetable species showed an intermediate sensitivity.     

Diagnostics for Determining Influential Species in the Chemical Mass Balance Receptor Model

ABSTRACT

The chemical mass balance (CMB) model can be applied to estimate the amount of airborne particulate matter (PM) coming from various sources given the ambient chemical composition of the particles measured at the receptor and the chemical composition of the source emissions. Of considerable practical importance is the identification of those chemical species that have a large effect on either the source contributions or errors estimated by the CMB model. This paper details a study of a number of influential diagnostics for application of the CMB software. Some of the diagnostics studied are standard regression diagnostics based on single-row deletion diagnostics. A number of new diagnostics were developed specifically for the CMB application, based on the pseudo-inverse of the source composition matrix and called nondeletion diagnostics to distinguish them from the standard deletion diagnostics. Simulated data sets were generated to compare the diagnostics and their response to controlled amounts of random error.

A particular diagnostic called a modified pseudoinverse matrix (MPIN), developed for this study, was found to be the best choice for CMB model application. The MPIN diagnostic contains virtually all the information present in both deletion and nondeletion diagnostics. Since the MPIN diagnostic requires only the source profiles, it can be used to identify influential species in advance without sampling the ambient data and to improve CMB results through possible remedial actions for the influential species. Specific recommendations are given for interpretation and use of the MPIN diagnostic with the CMB model software. Elements with normalized MPIN absolute values of 1 to 0.5 are associated with influential elements. Noninfluential elements have normalized MPIN absolute values of 0.3 or less. Elements with absolute values between 0.3 and 0.5 are ambiguous but should generally be considered noninfluential.     

What Have We Learned from Highly Time-Resolved Measurements during EPA’s Supersites Program and Related Studies?

Abstract

A wide range of new and exciting highly time-resolved instruments were deployed during the U.S. Environmental Protection Agency (EPA) Supersite program and related studies that occurred during the same time period. These measurements elucidated the temporal variation of a suite of gas-phase species, particle physical properties, and size-resolved particulate chemical composition. Because the temporal resolution was so high, concentration and size distribution changes as short as 1 min or less were discerned. Often data from multiple instruments were correlated with each other and with meteorological measurements, and these correlations enabled conclusions to be drawn about the photochemical activity of the atmosphere, the location of point sources, and even the emissions characteristics of these sources. For instance, rapid changes in particulate matter (PM) concentration were due to meteorological conditions, emissions, and plume excursions that led to increases in nitrate, sulfate, and organic carbon concentrations. This paper summarizes the conclusions that have been reached, to date, using these new, highly time-resolved instruments, and demonstrates their promise for future studies.     

Feasibility of Soil Dust Source Apportionment by the Pyrolysis-Gas Chromatography/Mass Spectrometry Method

Abstract

This study tested the feasibility of using pyrolysis (Py)-gas chromatography (GC)/mass spectrometry (MS) to obtain organic chemical species data suitable for source apportionment modeling of soil-derived coarse particulate matter (PM₁₀) dust on ambient filters. A laboratory resuspension apparatus was used with known soils to generate simulated receptor filter samples loaded with ～0.4 mg of PM₁₀ dust, which is within the range of mass loading on ambient filters. Py-GC/MS at 740 °C generated five times more resolvable compounds than were obtained with thermal desorption GC/MS at 315 °C. The identified compounds were consistent with literature from Py experiments using larger samples of bulk soils. A subset of 91 organic species out of the 178 identified Py products was used as input to CMB8 software in a demonstration of source apportionment using laboratory-generated mixtures simulating ambient filter samples. The 178 quantified organic species obtained by Py of soil samples is an improvement compared with the 38 organic species obtained by thermal desorption of soils and the four functionally defined organic fractions reported by thermal/optical reflectance. Significant differences in the concentration of specific species were seen between samples from different sites, both geographically distant and close, using analysis of variance and cluster analysis. This feasibility study showed that Py-GC/MS can generate useful source profile data for receptor modeling and justifies continued method development.     

Global scale emission and distribution of sea-spray aerosol: Sea-salt and organic enrichment

The chemical composition of marine aerosols as a function of their size is an important parameter for the evaluation of their impact on the global climate system. In this work we model fine particle organic matter emitted by sea spray processes and its influence on the aerosol chemical properties at the global scale using the off-line global Chemistry-Transport Model TM5. TM5 is coupled to a microphysical aerosol dynamics model providing size resolved information on particle masses and numbers. The mass of the emitted sea spray particles is partitioned between water insoluble organic matter (WIOM) and sea salt components in the accumulation mode using a function that relates the emitted organic fraction to the surface ocean chlorophyll-a concentrations. The global emission in the sub-micron size range of organic matter by sea spray process is 8.2 Tg yr^?1, compared to 24 Tg fine yr^?1 sea-salt emissions. When the marine sources are included, the concentrations of modelled primary particulate organic matter (POM) increase mainly over the oceans. The model predictions of WIOM and sea salt are evaluated against measurements carried out at Mace Head (Northern Hemisphere) and Amsterdam Island (Southern Hemisphere), showing that in clean marine conditions WIOM marine emissions contribute significantly to POM values.     

Metallic Element Composition of Particulate Matter During Day and Night Sampling at a Traffic Site

Day and night period sampling programs were carried out using a versatile air pollutant system to collect fine particulate matter (PM_2.5) and coarse particulate matter (PM_2.5–10) simultaneously at a traffic junction that is only 60 m from HungKuang University located in Central Taiwan. Therefore, HungKuang University is regarded as the traffic sampling site in this study. Similar measurements were carried out in a previous 2013 study by Fang and colleagues during October 2012 to November 2012. Determination of metallic element composition of fine and coarse particulates collected during the day and the night was accomplished with inductively coupled plasma atomic emission spectrometry (ICP-AES). The results indicated that there were no significant differences in composition of metallic elements Zn, Cu, Cr, Mn, Fe, Pb, and Cd in either coarse or fine particles for both day and night sampling periods. The statistical results indicated no significant differences for metallic elements in the PM_2.5–10 particulates for day and night sampling periods. Also, no significant differences were noted for metallic elements in the PM_2.5 particulates for day and night sampling periods at this traffic sampling site. The proposed reason is the limited sampling period employed in this study. Another potential reason is the presence of traffic that runs heavily both day and night being a major contributor to the ambient air metallic pollutants in this region.     

A Technique for Respirable Sampling

The purpose of this paper is to describe instrumentation to aerodynamically size suspended particulates found in ambient air and to summarize results of field testing utilizing the new technique.

A four-stage, multiorifice high-volume fractionating impactor with backup filter, which can be operated as a component of the standard high-volume sampler, collects particulate matter in five separate aerodynamic size ranges: 7 micrometer (μm) or larger, 3.3 to 7 μm, 2.0 to 3.3 μm, 1.1 to 2.0 μm, and 0.01 to 1.1 μm.

Comparative field tests utilizing duplicate sampling techniques were conducted to determine the feasibility of using the size fractionator on a routine basis in field operations. Verification of the actual particle size separation was not undertaken; however, earlier tests utilizing laboratory-generated aerosols have been performed with satisfactory results.

The results of field tests indicate that the fractionator can be used to determine the aerodynamic size distribution of particulate matter. A glass fiber surface with a pH of 11.0 was found to adsorb atmospheric acid gases during sampling and thus gave erroneous mass concentration results when compared to the standard high-volume sampler. Glass fiber filters with a pH of 6.5 eliminated the acid gas adsorption.     

Indoor-outdoor relationship of suspended particulate matter and its chemical composition at different sizes

The indoor-outdoor concentration relationship of particulate matter PM_9.0 (aerodynamic diameter 9 μm or smaller) and its chemical composition (sulfate, nitrate, chloride and ammonium) has been studied. Samples were collected using four identical Anderson impactors, each one collecting nine size ranges by eight impactor stages (9, 5.8, 4.7, 3.3, 2.1, 1.1, 0.65 and 0.43 μm) plus a back-up filter representing particles finer than 0.45 μm. Concentrations of sulfate, nitrate and chloride were determined by ion chromatography, and an ammonium-selective ion electrode plus a Corning pH ion meter were used to determine ammonium ion. The results revealed that sulfate was the predominant component and chloride the least abundant. The size distribution of sulfate, nitrate and ammonium very strongly peaked near 0.65 μm and with very little at the larger sizes. The chloride concentration was depleted in the fine particles and enhanced in the relatively coarser particles, with the peak at 3.3 μm. All these concentrations had a significant linear relationship with mass concentrations in outdoor samples. In indoor samples, the same relation was observed only for sulfate and ammonium, which were also significantly correlated with each other. Furthermore, indoor sulfate, chloride and ammonium concentrations were higher towards the finest particle sizes, indicating a higher potential inhalation health hazard. The study also confirmed that indoor air quality depends on outdoor atmospheric pollution level, indoor activities and virtually on the particle size. Finally, the study would assist in selecting the type of collector required to reduce the level of particulates to an acceptable level for indoor ambient air.