The Sensitivity of PM25 Source-Receptor Relationships to Atmospheric Chemistry and Transport in a Three-Dimensional Air Quality Model

ABSTRACT

Air quality model simulations constitute an effective approach to developing source-receptor relationships (so-called transfer coefficients in the risk analysis framework) because a significant fraction of particulate matter (particularly PM_2.5) is secondary (i.e., formed in the atmosphere) and, therefore, depends on the atmospheric chemistry of the airshed. In this study, we have used a comprehensive three-dimensional air quality model for PM_{2 5} (SAQM-AERO) to compare three approaches to generating episodic transfer coefficients for several source regions in the Los Angeles Basin. First, transfer coefficients were developed by conducting PM_2.5 SAQM-AERO simulations with reduced emissions of one of four precursors (i.e., primary PM, sulfur dioxide (SO₂), oxides of nitrogen (NO_x), and volatile organic compounds) from each source region. Next, we calculated transfer coefficients using two other methods: (1) a simplified chemistry for PM_2.5 formation, and (2) simplifying assumptions on transport using information limited to basin-wide emission reductions. Transfer coefficients obtained with the simplified chemistry were similar to those obtained with the comprehensive model for VOC emission changes but differed for NO and SO emission changes. The differences were due to the parameterization of the rates of secondary PM formation in the simplified chemistry. In 90% of the cases, transfer coefficients estimated using only basin-wide information were within a factor of two of those obtained with the explicit source-receptor simulations conducted with the comprehensive model. The best agreement was obtained for VOC emission changes; poor agreement was obtained for primary PM_2.5.     

Quantification of Monosaccharide Anhydrides by Liquid Chromatography Combined with Mass Spectrometry: Application to Aerosol Samples from an Urban and a Suburban Site Influenced by Small-Scale Wood Burning

Abstract

Levels of the monosaccharide anhydride (MA) levoglucosan and its isomeric compounds galactosan and mannosan were quantified in the PM₁₀ fraction (particulate matter ≤10 µm in aerodynamic diameter) of ambient aerosols from an urban (Oslo) and a suburban (Elverum) site in Norway, both influenced by small-scale wood burning. MAs are degradation products of cellulose and hemicellulose, and levoglucosan is especially emitted in high concentrations during pyrolysis and combustion of wood, making it a potential tracer of primary particles emitted from biomass burning. MAs were quantified using a novel high-performance liquid chromatography/ high-resolution mass spectrometry-time of flight method. This approach distinguishes between the isomeric compounds of MAs and benefits from the limited sample preparation required before analysis, and no extensive derivatization step is needed. The highest concentrations of levogucosan, galactosan, and mannosan (∑MA) were recorded in winter because of wood burning for residential heating (∑MA_MAX = 1,240 ng m^-3). This finding was substantiated by a relatively high correlation (R² = 0.64) between the levoglucosan concentration and decreasing ambient temperature. At the suburban site, ∑MA accounted for 3.1% of PM₁₀, whereas the corresponding level at the urban site was 0.6%. The mass size distribution of MAs associated with atmospheric aerosols was measured using a Berner cascade impactor. The size distribution was characterized with a single mode at 561 nm. Ninety-five percent of the mass concentration of the MAs was found to be associated with particles <2 µm. A preliminary attempt to estimate the contribution of wood burning to the mass concentration of PM₁₀ in Oslo using levoglucosan as a tracer indicates that 24% comes from wood burning. This is approximately a factor of 2 lower than estimated by the AirQUIS dispersion model.     

Mercury pollution trends in subarctic lakes in the northern Swedish mountains

Despite many years of research about mercury pollution, data concerning high-latitude regions of Europe are limited, particularly studies of long-term temporal trends. It is not clear whether the mercury load at high latitudes follows the recent decreasing trends in European mercury emissions or whether the load is still high because of continuing global emissions. In this study we use sediments from 12 lakes, located above the Arctic Circle in the Swedish mountains, to assess the past and recent mercury pollution situation, especially for the last 200 y. The mercury load increased clearly in sediment deposited from the late 19th or early 20th century to a peak between 1960 and 1990. This peak represents an enrichment of 1.4 to 4.2 times over background concentrations. This enrichment is comparable with enrichments in sediments from lower latitudes as well as other Arctic regions. Since the 1990s mercury concentration has declined in 8 of the 12 lakes, i.e., similar to emission trends in Europe.     

A synthesis of progress and uncertainties in attributing the sources of mercury in deposition

A panel of international experts was convened in Madison, Wisconsin, in 2005, as part of the 8th International Conference on Mercury as a Global Pollutant. Our charge was to address the state of science pertinent to source attribution, specifically our key question was: "For a given location, can we ascertain with confidence the relative contributions of local, regional, and global sources, and of natural versus anthropogenic emissions to mercury deposition?" The panel synthesized new research pertinent to this question published over the past decade, with emphasis on four major research topics: long-term anthropogenic change, current emission and deposition trends, chemical transformations and cycling, and modeling and uncertainty. Within each topic, the panel drew a series of conclusions, which are presented in this paper. These conclusions led us to concur that the answer to our question is a "qualified yes," with the qualification being dependent upon the level of uncertainty one is willing to accept. We agreed that the uncertainty is strongly dependent upon scale and that our question as stated is answerable with greater confidence both very near and very far from major point sources, assuming that the "global pool" is a recognizable "source." Many regions of interest from an ecosystem-exposure standpoint lie in between, where source attribution carries the greatest degree of uncertainty.     

Assessment of the natural attenuation of chlorinated ethenes in an anaerobic contaminated aquifer in the Bitterfeld/Wolfen area using stable isotope techniques, microcosm studies and molecular biomarkers

The in situ degradation of chlorinated ethenes was assessed in an anaerobic aquifer using stable isotope fractionation approaches, microcosm studies and taxon specific detection of specific dehalogenating groups of bacteria. The aquifer in the Bitterfeld/Wolfen region in Germany contained all chlorinated ethenes, benzene and toluene as contaminants. The concentrations and isotope composition of the chlorinated ethenes indicated biodegradation of the contaminants. Microcosm studies confirmed the presence of in situ microbial communities capable of the complete dechlorination of tetrachloroethene. Taxon specific investigation of the microbial communities indicated the presence of various potential dechlorinating organisms including Dehalococcoides, Desulfuromonas, Desulfitobacterium and Dehalobacter. The integrated approach, using metabolite spectra, molecular marker analysis and isotope studies, provided several lines of evidence for natural attenuation of the chlorinated ethenes.     

Applicability of the bioluminescence inhibition test in the 96-well microplate format for PAH-solutions and elutriates of PAH-contaminated soils

The use of conventional plastic microplates for a miniaturised luminescent bacteria test may result in an underestimation of the toxicity for poorly water soluble highly adsorbing toxicants such as PAHs. In this study, the suitability of microplates for testing elutriates of PAH-contaminated soils was investigated. The LUMIStox test was performed as the standard test in the miniaturised format using contaminated soil elutriates and aqueous solutions of four selected PAHs (viz. naphthalene (NAP), acenaphthene (ACE), fluorene (FLU), and phenanthrene (PHE)). For the aqueous PAH-solutions, we observed reduced light inhibition values for the miniaturised bioassay when using black microplates made of polypropylene (PP) and polystyrene (PS) compared to the standard LUMIStox test. This phenomenon was most likely due to adsorption of toxicants to the microplate surfaces with PAHs of lower water solubility being significantly more affected; however, after minimizing the exposure of samples to plastic surfaces, polystyrene microplates revealed equivalent performance (>80% 'relative' light inhibition) to the standard glass cuvette test system. For soil elutriates, black microplates again exhibited slightly lower light inhibition values while white plates made of PS and Barex resulted in a pronounced overestimation of toxicity for a coloured soil elutriate. In general, microplates were applicable for testing elutriates of PAH-contaminated soils. In cases where samples are coloured or turbid, the application of black microplates is recommended.     

Concentrations of polychlorinated dibenzo-p-dioxins in processed ball clay from the United States

Processed ball clays commonly used by the ceramic art industry in the United States were collected from retail suppliers and analyzed for the presence and concentration of the 2,3,7,8-Cl substituted polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs). The average PCDD toxic equivalent (TEQ) concentrations of these processed ball clays was approximately 800 pg/g (TEQ-WHO) with characteristic congener profiles and isomer distributions similar to patterns of previously analyzed raw and processed ball clays. The PCDF concentrations were below the average limit of detection (LOD) of 0.5 pg/g. Correlation analyses reveal no significant relationship between total organic carbon (TOC) and either individual, homologues, and total tetra-through octa-chlorinated PCDD congeners, or TEQ concentrations of the processed ball clays. The results are consistent with earlier studies on levels of PCDDs in ball clays. Data from earlier studies indicated that dioxins may be released to the environment during the processing of raw clay or the firing process used in commercial ceramic facilities. The presence of dioxin in the clays also raises concerns about potential occupational exposure for individuals involved in the mining/processing of ball clay, ceramics manufacturing and ceramic artwork.     

Solid-state conformations and absolute configurations of (+) and (-) alpha-, beta-, and gamma-hexabromocyclododecanes (HBCDs)

Hexabromocyclododecanes (HBCDs) are high production volume chemicals used as flame retardants for plastics and textiles. They are currently produced in quantities exceeding 20,000 t/y. Despite this fact, the correct stereochemistry of most HBCDs is still not known. Six stereocenters are formed during bromination of cyclododecatrienes, resulting in mixtures of different stereoisomers. Considering all elements of symmetry, 16 different stereoisomers including six pairs of enantiomers as well as 4 meso forms are possible theoretically. Recently, we isolated 8 of the 16 possible stereoisomers from a technical HBCD mixture and assigned their relative configurations. Herein, we report on the isolation of 6 enantiomerically pure alpha-, beta-, and gamma-HBCDs, obtained from preparative chiral-phase liquid chromatography, and we present their absolute configurations, which were determined from X-ray diffraction analysis. The absolute configuration of (-) alpha-HBCD was found to be (1R,2R,5S,6R,9R,10S), while the one of (+) beta-HBCD is assigned to (1S,2S,5S,6R,9S,10R), whereas the one of (-) gamma-HBCD corresponds to (1S,2S,5S,6R,9R,10S). The given structural information allows the unambiguous identification of the six most important HBCD stereoisomers, which typically account for more than 95% of technical HBCDs. In addition, we compared the solid-state conformations of racemic and enantiomerically pure alpha-, beta-, and gamma-HBCDs. In all cases, vicinal dibromides adopted a synclinal (sc) conformation with torsion angles of 69+/-6 degrees. A unique structural motive was common to all examined HBCD solid-state conformations. This conserved structure was described as an extended triple turn consisting of an arrangement of three pairs of synclinal and two antiperiplanar torsion angles.     

In situ transformations of fine lead oxide particles in different soils

We present a field application of a new in situ technique to analyze phase transformations of fine lead oxide particles (50-100mum) in different soils directly in the field over 18 months. After the first month of exposure to a calcareous sand we found newly precipitated secondary mineral phases on the lead oxide. The samples exposed to two loamy soils (Dystric Cambisol and Luvisol) showed only very few traces of new phases. We identified the new phases as mainly lead-hydroxy carbonates (hydrocerussite). Whereas the results confirm the transformation of lead phases to lead carbonates in calcareous soil, they also show that an easily soluble phase such as PbO may persist in soils virtually unweathered for more than one year. The formation of a weathering crust is therefore not necessarily needed for preservation of easily soluble phases. The use of experimental in situ methods is thus giving new information on contaminant mineral behavior under field conditions.