Suppression of precipitation by dust particles originated in the Tibetan Plateau

Dust aerosols play an important role in modulating the hydrologic cycle. The Tibetan Plateau (TP) is little polluted by human activities as an ideal site to study the effect of dust aerosol on precipitation. In this study, observational data of dust storms and precipitation in the TP and its vicinities as well as CALIPSO satellite data were used to analyze the distributions and vertical structure of dust storms on the plateau. The results showed that dust storms occur with high frequency and raise dust particles into the troposphere from ground level to a height of 5–9 km to modulate the hydrologic cycle in the TP. There are significant negative correlations between dust aerosol and precipitation in the dust source regions during the period of both 40 and 200 years. It is found that the role of precipitation in suppressing dust storms could be unimportant, while dust aerosol may play an important role in suppressing precipitation in the hinterland of the TP. Our study provides a potential approach to better understand the climate changes in the TP.     

Dry atmospheric inputs of trace metals at the Mediterranean coast of Israel (SE Mediterranean): sources and fluxes

This study presents the first detailed data on aerosol concentrations of trace metals (Cd, Pb, Cu, Zn, Cr, Mn, Fe and Al) at the SE Mediterranean coast of Israel, and assesses their sources and fluxes. Aerosol samples were collected at two sampling stations (Tel-Shikmona and Maagan Michael) along the coast between 1994 and 1997. Two broad categories of aerosol trace metal sources were defined; anthropogenic (Cd, Cu, Pb and Zn) and naturally derived elements (Al, Fe, Mn and Cr). The extent of the anthropogenic contribution was estimated by the degree of enrichment of these elements compared to the average crustal composition (EF_crust). High values (median >100) were calculated for Cd, Pb and Zn, minor values for Cu and relatively low values (<10) for Fe, Mn and Cr. The crustal-derived elements exhibited a statistically significant seasonal pattern of higher concentrations during spring and autumn (e.g. Al concentrations in some cases during these periods were observed to be in excess of 1500 ng m⁻³). In the eastern Mediterranean basin crustal-dominated elements are enriched by 2–3 times while others (Cd and Pb) are comparable to the northwestern Mediterranean. The Pb : Cd ratios of ∼150 are higher than in coastal European sites (60–116) or emission materials (∼50). It is speculated that these differences are attributed mainly to the mixing of crustal material with local and European emissions. At present, it is impossible to quantify the latter two fractions. Back trajectory analysis and the subsequent categorization of two main aerosol populations, ‘European’ and ‘North Africa–Arabian’, exhibited a significantly different geochemical imprint on the aerosol chemical composition. ‘European’-derived air masses indicated significantly higher EF_crust values for Cd and Pb due to the greater anthropogenic character of the aerosol population, with a dilution by crustal material of this population leading to comparatively lower EF_crust values associated with the North African–Arabian air masses.     

Atmospheric phosphorus deposition at a montane site: Size distribution,effects of wildfire,and ecological implications

The dry deposition of atmospheric particulate matter can be a significant source of phosphorus (P) to oligotrophic aquatic ecosystems, including high-elevation lakes. In this study, measurements of the mass concentration and size distribution of aerosol particles and associated particulate P are reported for the southern Sierra Nevada, California, for the period July–October, 2008. Coarse and fine particle samples were collected with Stacked Filter Units and analyzed for Total P (TP) and inorganic P (IP) using a digestion-extraction procedure, with organic P (OP) calculated by difference. Particle size-resolved mass and TP distributions were determined concurrently using a MOUDI cascade impactor. Aerosol mass concentrations were significantly elevated at the study site, primarily due to transport from offsite and emissions from local and regional wildfires. Atmospheric TP concentrations ranged from 11 to 75 ng m^?3 (mean = 37 ± 16 ng m^?3), and were typically dominated by IP. Phosphorus was concentrated in the coarse (>1 μm diameter) particle fraction and was particularly enriched in the 1.0–3.2 μm size range, which accounted for 30–60% of the atmospheric TP load. Wildfire emissions varied widely in P content, and may be related to fire intensity. The estimated dry depositional flux of TP for each daily sampling period ranged between 7 and 118 μg m^?2 d^?1, with a mean value of 40 ± 27 μg m^?2 d^?1. Relative rates of dry deposition of N and P in the Sierra Nevada are consistent with increasing incidence of N limitation of phytoplankton growth and previously observed long-term eutrophication of lakes.     

Variability of atmospheric dust loading over the central Tibetan Plateau based on ice core glaciochemistry

A Mt. Geladaindong (GL) ice core was recovered from the central Tibetan Plateau (TP) spanning the period 1940–2005 AD. High-resolution major ion (Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl^?, SO₄^2?, NO₃^?) time-series are used to investigate variations in atmospheric dust loading through time. The crustal source ions vary seasonally with peaks in dust concentrations occurring during the winter and spring which are consistent with atmospheric dust observations at local meteorological stations. However, both similarities and dissimilarities are displayed between the decadal variation of atmospheric dust in the GL core and dust observation records from meteorological stations, which can be attributed to local environmental effects at the stations. This paper compares the 1980s and 1970s as case periods for low and high atmospheric dust loading, respectively, two periods reflecting shifts in spring atmospheric circulation (a weakening of zonal and meridional winds) from the 1970s (a period of enhanced dust aerosol transportation to central TP) to the 1980s (a period of diminished dust aerosol transportation to central TP), especially a significant decrease of meridional wind speeds in the 1980s. GL ice core dust proxies (Ca²⁺ and K⁺) are correlated with Total Ozone Mapping Spectrometer (TOMS) Aerosol Index (AI) data in spring over the TP and in the northwestern China (especially for K⁺). Thus variability of crustal ions in central TP ice core provides a proxy for reconstructing a history of atmospheric dust loading not only on the TP, but also in northwestern China.     

Coarse and fine aerosol source apportionment in Rio de Janeiro,Brazil

The metropolitan area of Rio de Janeiro is one of the twenty biggest urban agglomerations in the world, with 11 million inhabitants in the metropolitan area, and has a high population density, with 1700 hab. km^?2. For this aerosol source apportionment study, the atmospheric aerosol sampling was performed at ten sites distributed in different locations of the metropolitan area from September/2003 to December/2005, with sampling during 24 h on a weekly basis. Stacked filter units (SFU) were used to collect fine and coarse aerosol particles with a flow rate of 17 L min^?1. In both size fractions trace elements were analyzed by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) as well as water-soluble species by Ion-Chromatography (IC). Also gravimetric analysis and reflectance measurements provided aerosol mass and black carbon concentrations. Very good detection limits for up to 42 species were obtained. Mean annual PM₁₀ mass concentration ranged from 20 to 37 μg m^?3, values that are within the Brazilian air quality standards. Receptor models such as principal factor analysis, cluster analysis and absolute principal factor analysis were applied in order to identify and quantify the aerosol sources. For fine and coarse modes, circa of 100% of the measured mass was quantitatively apportioned to relatively few identified aerosol sources. A very similar and consistent source apportionment was obtained for both fine and coarse modes for all 10 sampling sites. Soil dust is an important component, accounting for 22–72% and for 25–48% of the coarse and fine mass respectively. On the other hand, anthropogenic sources as vehicle traffic and oil combustion represent a relatively high contribution (52–75%) of the fine aerosol mass. The joint use of ICP-MS and IC analysis of species in aerosols has proven to be reliable and feasible for the analysis of large amount of samples, and the coupling with receptor models provided an excellent method for quantitative aerosol source apportionment in large urban areas.     

Chemical composition and complex refractive index of Saharan Mineral Dust at Izaña,Tenerife (Spain) derived by electron microscopy

Samples from two strong homogeneous dust plumes from the Saharan desert reaching Izaña (Tenerife, Spain) in July and August 2005 were taken with a miniature impactor system and filter samplers. Size, aspect ratio and chemical composition of more than 22,000 individual particles were studied by scanning electron microscopy. The mineralogical phase composition of about 200 particles was investigated by transmission electron microscopy. In addition, the aerosol size distribution was measured with an optical particle spectrometer. In all samples, the aerosol was dominated by mineral dust with an average composition (by volume) of 64% silicates, 6% quartz, 5% calcium-rich particles, 14% sulfates, 1% hematite, 1% soot and 9% other carbonaceous material. Sulfate was found predominantly as coating on other particles with an average thickness of approximately 60 nm. The aerosol calcium content is correlated with the calcite concentrations of soils in the source region, highest values were observed for northern and central Algeria and Morocco. The average aspect ratio of the particles was 1.64. The distributions of the aspect ratios are parameterized by log-normal functions for modeling purpose. Single-scattering albedo (0.95) and asymmetry factor (0.74–0.81) was measured by polar aerosol photometry on filter samples using a light source resembling the solar spectrum. The apparent soot content of the sample (1 vol%) was determined by the same technique. From the mineralogical data, an average complex refractive index of 1.59–9×10⁻³i for visible light was derived. The imaginary part of the complex refractive index decreases with increasing particle size from −2.5×10⁻²i to <−10⁻³i, reflecting the decreasing hematite and soot contents. The imaginary part derived from optical measurements was −7×10⁻³i.     

Seasonal Variations in Aerosol Composition and Acidity at Shenandoah and Great Smoky Mountains National Parks

The concentration of elements Na through Pb, select ions, and organic carbon from fine (<2.5 µm) particles has been monitored at Shenandoah and Great Smoky Mountains National Parks from 1988 through 1995. The data obtained from 1988 through 1994 show that significant changes in the concentrations of many aerosol constituents occur on a seasonal basis. Particulate sulfate and organic carbon are shown to exhibit substantially higher concentrations during the summer, while sulfur dioxide and nitrate concentrations are highest during the winter.

A method for estimating the degree of neutralization of particulate sulfate is given. This method uses routinely measured aerosol elemental compositions because ammonium ion, the primary neutralizing species for sulfate, is not measured on a routine basis. Application of this method to the selected data set shows that sulfate aerosol is most acidic during summer with an average molar H_s (moles of hydrogen associated with sulfur) to S (moles of sulfur) ratio of approximately 4. This suggests the average sulfate particle during the summer has a molar coon slightly more acidic than ammonium bisulfate (NH₄HSO₄) which has a molar hydrogen to sulfur ratio of 5. Winter H_s to S ratios, however, are approximately 8, suggesting the aerosol is on average fully neutralized ammonium sulfate [(NH₄)₂SO₄].     

Aerosol composition and sources in Urban areas in India

The elemental composition of aerosols over four cities in India was determined by EDXRF over a 1-year period and the results are presented. The crustal element levels in air in all the cities are found to be similar to those reported for urban areas elsewhere in the world while that of anthropogenic elements are lower. The aerosol compositions show a seasonal variation. The levels of crustal elements are higher during summer and decrease with rainfall. The anthropogenic elements are generally higher during winter. The lead levels are essentially from non-auto exhaust sources such as refuse burning, smelter etc., and in three of the cities they are strongly correlated to zinc. The crustal elements are from local soils and no significant crust-air fractionation is seen. Factor analysis of the data suggests between four and six aerosol source types for the four cities. Soil dust accounts for the major fraction of the measured mass. About 68–80 % of the aerosol mass comprising the residuals seems to consist of C, O₂ and N, in particular, which were not measured.     

Evaluation of secondary organic aerosol formation in winter

Three different methods are used to predict secondary organic aerosol (SOA) concentrations in the San Joaquin Valley of California during the winter of 1995–1996 [Integrated Monitoring Study, (IMS95)]. The first of these methods estimates SOA by using elemental carbon as a tracer of primary organic carbon. The second method relies on a Lagrangian trajectory model that simulates the formation, transport, and deposition of secondary organic aerosol. The model includes a recently developed gas–particle partitioning mechanism. Results from both methods are in good agreement with the chemical speciation of organic aerosol during IMS95 and suggest that most of the OC measured during IMS95 is of primary origin. Under suitable conditions (clear skies, low winds, low mixing heights) as much as 15–20 μg C m⁻³ of SOA can be produced, mainly due to oxidation of aromatics. The low mixing heights observed during the winter in the area allow accumulation of SOA precursors and the acceleration of SOA formation. Clouds and fog slow down the production of secondary compounds, reducing their concentrations by a factor of two or three from the above maximum levels. In addition, it appears that there is significant diurnal variation of SOA concentration. A strong dependence of SOA concentrations on temperature is observed, along with the existence of an optimal temperature for SOA formation.     

Accumulation of Mn and Pb in linden (Tilia platyphyllos Scop.) bark and wood

As an indicator of environmental pollution, we collected tree rings and bark of linden (Tilia platyphyllos Scop.) from four sampling locations in Serbia. Mn and Pb were determined with a spectrochemical method that has an argon-stabilized U-shaped DC arc with aerosol supply as excitation source. Increased concentrations of Mn in linden tree rings and bark were found at the Debeli Lug location, where the Mn transfer factors were largest. The availability of Mn in soil and tree rings was greatly influenced by pH. Since 1950, Mn level decreased more noticeably on acidic soils. Higher concentrations of Pb were found in linden tree rings and bark at the locations Fru?ka Gora and Zemun. Proximity of the road to Novi Sad at both sites may be a possible reason for this. The Pb transfer factor was highest at Fru?ka Gora. The ratio of bioavailable elements in soil for Mn and Pb were also calculated. Close correlations between Mn and Pb concentrations in linden tree rings and the ratio of bioavailable elements in soil were seen at all four locations.     

Distribution,origin, and transformation of metal and metalloid pollution in vegetable fields,irrigation water,and aerosols near a Pb-Zn mine

Pollution of arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), lead (Pb), and zinc (Zn) in vegetable fields was investigated near a Pb-Zn mine that has been exploited for over 50 years without a tailing reservoir. A total of 205 water, soil, and aerosol samples were taken and quantified by combined chemical, spectrometric, and mineral analytical methods. The pollution origins were identified by Pb isotopes and the pathways of transformation and transport of the elements and minerals was studied. The data showed that the vegetable fields were seriously polluted by As, Cd, and Pb. Some concentrations in the samples were beyond the regulatory levels and not suitable for agricultural activities. This study revealed that: (1) particulate matter is a major pollution source and an important carrier of mineral particles and pollutants; (2) the elements from the polluted water and soils were strongly correlated with each other; (3) Pb isotope ratios from the samples show that Pb minerals were the major pollution sources in the nearby vegetable fields, and the aerosols were the main carrier of mining pollution; (4) the alkaline, rich-carbonate, and wet conditions in this area promoted the weathering and transformation of galena into the secondary minerals, anglesite and cerussite, which are significant evidence of such processes; (5) the soil and the aerosols are a recycled secondary pollution source for each other when being re-suspended with wind. Highlights ? Mining activities generated heavy metal pollution in fields around a Pb-Zn mine ? The elements from water and soils are strongly correlated ? Anglesite and cerussite are evidence of galena transformation into secondary minerals ? Particulate matter is an important transport carrier of pollution     

Distribution and seasonal variability of trace elements in atmospheric particulate in the Venice Lagoon

Size distribution and selected element concentrations of atmospheric particulate matter (PM) were investigated in the Venice Lagoon, at three sites characterised by different anthropogenic influence. The PM₁₀ samples were collected in six size fractions (10-7.2, 7.2-3.0, 3.0-1.5, 1.5-0.95; 0.95-0.49 and <0.49 μm) with high volume cascade impactors, and the concentration of 17 elements (Al, As, Ca, Cd, Co, Cu, Fe, K, Li, Mg, Mn, Na, Ni, Pb, Sr, V, Zn) was determined by inductively coupled plasma quadrupole mass spectroscopy. More than 1 year of sampling activities allowed the examination of seasonal variability in size distribution of atmospheric particulates and element contents for each site.At all the stations, particles with an aerodynamic diameter <3 μm were predominant, thus accounting for more than 78% of the total aerosol mass concentration. The highest PM₁₀ concentrations for almost all elements were found at the site which is more influenced by industrial and urban emissions. Similarity in size distribution of elements at all sites allowed the identification of three main behavioural types: (a) elements found mainly within coarse particles (Ca, Mg, Na, Sr); (b) elements found mainly within fine particles (As, Cd, Ni, Pb, V) and (c) elements with several modes spread throughout the entire size range (Co, Cu, Fe, K, Zn, Mn).Factor Analysis was performed on aerosol data separately identified as fine and coarse types in order to examine the relationships between the inorganic elements and to identify their origin. Multivariate statistical analysis and assessment of similarity in the size distribution led to similar conclusions on the sources.     

Size distribution and anthropogenic sources apportionment of airborne trace metals in Kanazawa,Japan

Aerosol samples were collected from Kanazawa, Japan to examine the size distribution of 12 elements and to identify the major sources of anthropogenic elements. Key emission sources were identified and, concentrations contributed from individual sources were estimated as well. Concentrations of elements V, Ca, Cd, Fe, Ba, Mg, Mn, Pb, Sr, Zn, Co and Cu in aerosols were determined with ICP-MS. The results showed that Ca, Mg, Sr, Mn, Co and Fe were mainly associated with coarse particles (>2.1 μm), primarily from natural sources. In contrast, the elements Zn, Ba, Cd, V, Pb and Cu dominated in fine aerosol particles (<2.1 μm), implying that the anthropogenic origin is the dominant source. Results of the factor analysis on elements with high EF_Crust values (>10) showed that emissions from waste combustion in incinerators, oil combustion (involving waste oil burning and oil combustion in both incinerators and electricity generation plants), as well as coal combustion in electricity generation plants were major contributors of anthropogenic metals in the ambient atmosphere in Kanazawa. Quantitatively estimated sum of mean concentrations of anthropogenic elements from the key sources were in good agreement with the observed values. Results of this study elucidate the need for making pollution control strategy in this area.     

Characterization of soluble and insoluble components in PM2.5 and PM10 fractions of airborne particulate matter in Kofu city,Japan

A systematic method combining water and diluted-acid extractions has been developed for the manifold evaluation of soluble and insoluble fractions in ambient aerosol. The pre-washed regenerated cellulose membrane filter was used as a collection medium of a low-volume air sampler. The collection time of 7–14 days was required to obtain the sample amounts enough for the systematic analysis. Simple and efficient extraction procedures using the filtration of water and 0.1 M hydrochloric acid were recommended in order to obtain the information about the dissolution behaviors of various elements in the aerosol. Soluble components in both the extracts were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and ion chromatography (IC). These extraction procedures were also preferred to prepare thin-layer specimens suitable to the succeeding X-ray fluorescence spectrometry (XRF) for insoluble components. Elemental compositions of the extraction residues were conveniently determined by the XRF calibrated with thin-layer standard specimens prepared with activated carbon. The determination of the 17 representative elements (Na, Mg, Al, Si, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Cu, Zn, Br, Pb) in these three fractions from an aerosol sample was performed rapidly within 4 h. The proposed systematic method was applied to PM_2.5 and PM₁₀ aerosol samples collected in Kofu City, Central Japan, and the enrichment behaviors of various elements and their source apportionment such as soil, anthropogenic substances and vehicle exhaust particulates could be demonstrated by the present method.     

Validation of Three New Methods for Determination of Metal Emissions Using a Modified Environmental Protection Agency Method 301

Abstract

Three new methods applicable to the determination of hazardous metal concentrations in stationary source emissions were developed and evaluated for use in U.S. Environmental Protection Agency (EPA) compliance applications. Two of the three independent methods, a continuous emissions monitor-based method (Xact) and an X-ray-based filter method (XFM), are used to measure metal emissions. The third method involves a quantitative aerosol generator (QAG), which produces a reference aerosol used to evaluate the measurement methods. A modification of EPA Method 301 was used to validate the three methods for As, Cd, Cr, Pb, and Hg, representing three hazardous waste combustor Maximum Achievable Control Technology (MACT) metal categories (low volatile, semivolatile, and volatile). The modified procedure tested the methods using more stringent criteria than EPA Method 301; these criteria included accuracy, precision, and linearity. The aerosol generation method was evaluated in the laboratory by comparing actual with theoretical aerosol concentrations. The measurement methods were evaluated at a hazardous waste combustor (HWC) by comparing measured with reference aerosol concentrations. The QAG, Xact, and XFM met the modified Method 301 validation criteria. All three of the methods demonstrated precisions and accuracies on the order of 5%. In addition, correlation coefficients for each method were on the order of 0.99, confirming the methods’ linear response and high precision over a wide range of concentrations. The measurement methods should be applicable to emissions from a wide range of sources, and the reference aerosol generator should be applicable to additional analytes. EPA recently approved an alternative monitoring petition for an HWC at Eli Lilly’s Tippecanoe site in Lafayette, IN, in which the Xact is used for demonstrating compliance with the HWC MACT metal emissions (low volatile, semivolatile, and volatile). The QAG reference aerosol generator was approved as a method for providing a quantitative reference aerosol, which is required for certification and continuing quality assurance of the Xact.     

Inorganic element concentrations in near surface aerosols sampled on the northwest slopes of Mount Kenya

Eight trace elements, Si, Cl, K, Ca, Ti, Mn, Fe and Zn in the near-ground atmospheric aerosols were evaluated in the northwestern part of Mount Kenya using a dichotomous sampler and an EDXRF spectrometer. The samples were taken at 2 sites situated in Nanyuki area, which is roughly on the Equator. The sampler segregated the aerosol into two aerodynamic diameter (ad) size fractions, fine (<3.5 μm ad) and coarse (>3.5 and <18 μm ad). The elemental concentrations in the two size fractions were quantified and the elements assigned to known sources. Local wind blown dust related to agricultural activities and fire burning was found to dominate the lower tropospheric aerosols. There was inconclusive evidence of long range-transported aerosols being moved by night transport from the middle to the lower parts of the troposphere. Influence of the Indian Ocean marine aerosol was suggested but conclusive evidence was lacking.     

Polycyclic aromatic hydrocarbons in Costa Rican air and soil: A tropical/temperate comparison

Surface soil and passive air samples from a network of 23 sampling sites across Costa Rica were analyzed for polycyclic aromatic hydrocarbons (PAHs), allowing for an evaluation of absolute levels, spatial distribution patterns, air/soil concentration (A/S) ratios and relative composition. Annual mean concentrations of four-ring PAHs in air were low (median of approximately 40 pg m⁻³), except in Costa Rica's densely populated central valley (approximately 650 pg m⁻³). PAH concentrations in soil were also low (median of 5 ng g⁻¹ dry weight) and comparable to those reported for other tropical regions. These low soil concentrations result in A/S ratios of four-ring PAHs in Costa Rica that are higher than the equilibrium air–soil partitioning coefficients and also higher than A/S ratios reported for temperate locations. A series of model calculations of increasing complexity were used to seek an explanation for variable A/S ratios of PAHs under tropical and temperate conditions. Temperature-driven changes in air–soil partitioning and differences in PAH degradability under temperate and tropical conditions are insufficient to explain the higher soil concentrations and lower A/S ratios in temperate regions. However, these can be explained by atmospheric deposition of PAHs during historical periods of much higher emissions and air concentrations and by persistence of PAHs in soils on the order of decades. Low PAH concentrations in tropical soils were found to be consistent with constant or increasing emissions, and in particular, do not require that degradation rates in soil are much faster than in temperate areas. In comparison to temperate soils, soils from Costa Rica and other tropical regions have a higher relative abundance of the lighter PAHs. This likely reflects a higher source contribution from biomass burning in the tropics, as well as the preferential loss of lighter PAHs from temperate soils that experienced high PAH deposition in the past.     

Soil type affects migration pattern of airborne Pb and Cd under a spruce-beech forest of the UN-ECE integrated monitoring site Zöbelboden, Austria

Anthropogenic trace element emissions have declined. However, top soils all over the world remain enriched in trace elements. We investigated Pb and Cd migration in forest soils of a remote monitoring site in the Austrian limestone Alps between 1992 and 2004. Large spatial variability masked temporal changes in the mineral soil of Lithic Leptosols (Skeltic), whereas a significant reduction of Pb concentrations in their forest floors occurred. Reductions of concentrations in the less heterogeneous Cambisols (Chromic) were significant. In contrast, virtually no migration of Pb and Cd were found in Stagnosols due to their impeded drainage. Very low element concentrations (<1 μg l⁻¹) in field-collected soil solutions using tension lysimeters (0.2 μm nylon filters) imply that migration largely occurred by preferential flow as particulate-bound species during intensive rainfall events. Our results indicate that the extent of Pb and Cd migration in soils is largely influenced by soil type.     

Validation of three new methods for determination of metal emissions using a modified Environmental Protection Agency Method 301

Three new methods applicable to the determination of hazardous metal concentrations in stationary source emissions were developed and evaluated for use in U.S. Environmental Protection Agency (EPA) compliance applications. Two of the three independent methods, a continuous emissions monitor-based method (Xact) and an X-ray-based filter method (XFM), are used to measure metal emissions. The third method involves a quantitative aerosol generator (QAG), which produces a reference aerosol used to evaluate the measurement methods. A modification of EPA Method 301 was used to validate the three methods for As, Cd, Cr, Pb, and Hg, representing three hazardous waste combustor Maximum Achievable Control Technology (MACT) metal categories (low volatile, semivolatile, and volatile). The modified procedure tested the methods using more stringent criteria than EPA Method 301; these criteria included accuracy, precision, and linearity. The aerosol generation method was evaluated in the laboratory by comparing actual with theoretical aerosol concentrations. The measurement methods were evaluated at a hazardous waste combustor (HWC) by comparing measured with reference aerosol concentrations. The QAG, Xact, and XFM met the modified Method 301 validation criteria. All three of the methods demonstrated precisions and accuracies on the order of 5%. In addition, correlation coefficients for each method were on the order of 0.99, confirming the methods' linear response and high precision over a wide range of concentrations. The measurement methods should be applicable to emissions from a wide range of sources, and the reference aerosol generator should be applicable to additional analytes. EPA recently approved an alternative monitoring petition for an HWC at Eli Lilly's Tippecanoe site in Lafayette, IN, in which the Xact is used for demonstrating compliance with the HWC MACT metal emissions (low volatile, semivolatile, and volatile). The QAG reference aerosol generator was approved as a method for providing a quantitative reference aerosol, which is required for certification and continuing quality assurance of the Xact.     

An examination of oxidant amounts on secondary organic aerosol formation and aging

The effect of HO_x radicals (OH and HO₂) and ozone (O₃) on aerosol formation and aging has been studied. Experiments were performed in presence as well as in absence of oxygen in a flow-through chamber at 299 K for three organic precursor gases, isoprene, α-pinene and m-xylene. The HO_x source was the UV photolysis of humidified air or nitrogen and was measured with a GTHOS (Ground-based Tropospheric Hydrogen Oxides Sensor). The precursor gases concentration was monitored with an online GC-FID. The aerosol mass was then quantified by a Tapered Element Oscillating Microbalance (TEOM). Typical oxidant mixing ratios were (0–4.5) ppm for O₃, 200 pptv for OH and 3 ppbv for HO₂. A simple kinetics model is used to infer the aerosol production mechanism. In the present of O₃ (or O₂), the SOA yields were 0.46, 0.036 and 0.12 for α-pinene with an initial concentration of 100 ppbv (RH = 37%), isoprene with an initial concentration of 177 ppbv (RH = 50%) and m-xylene with an initial concentration of 100 ppbv (RH = 37%), respectively. When the chosen precursor gases reacted with HO_x in the absence of O₃, the maximum SOA yields were significantly increased by factors of 1.6 for isoprene 1.1 for α-pinene, and 3 for m-xylene respectively. The comparison of the calculated and measured potential aerosol mass concentrations as function of time shows that presence of ozone or oxygen can influence the aerosol yield and the absence of ozone or oxygen in the system resulted in high concentrations of its organic aerosol products.