Mixture Of Particulate Matter Research Articles

Effects of Exposure to Urban Atmospheric Particulate Matter Suspended in Seawater on the Mussel Mytilus galloprovincialis

Atmospheric particulate matter (PM) contains numerous constituents, including organic molecules, inorganic ions, and metals, with some of them possessing hazardous properties. Although mainly associated with air pollution, PM can rapidly be transferred from air and land to aquatic ecosystems, and consequently poses a risk to marine biota. The aim of this work was to evaluate how urban atmospheric PM (a standard reference mixture of urban PM, known to contain various organic and inorganic contaminants), suspended in seawater, may cause toxicity in marine organisms. To this purpose, mussels (Mytilus galloprovincialis) were exposed to two concentrations of suspended PM: 5.7 and 11.4 mg/L. After 7, 14, and 21 days, the animals were collected and the gills and digestive gland were analysed for stress biomarkers (CAT, SOD, GPX, GST, MDA, and Ubi). In general, the results show that exposure to different concentrations of PM caused an increase in GST, UBI, and GPx activities compared to their respective controls. The average activities of GST (87.65 ± 30.23 nmol/min/mg of total protein) in the gills of the animals exposed to 11.4 mg/L of PM increased after 21 days of exposure, and the activity of GPx (8.04 ± 3.09 nmol/min/mg of total protein) in the gills increased after 14 days in the animals exposed to 5.7 mg/L of PM. MDA results also provided information on cellular damage, with the most pronounced effects being found in the gills of exposed mussels. This study confirms that mussels are useful as “early warning” indicators of environmental contamination and provides important information on the effects of PM on marine biota.

Particulate matter composition drives differential molecular and morphological responses in lung epithelial cells.

Particulate matter (PM) is a ubiquitous component of air pollution that is epidemiologically linked to human pulmonary diseases. PM chemical composition varies widely, and the development of high-throughput experimental techniques enables direct profiling of cellular effects using compositionally unique PM mixtures. Here, we show that in a human bronchial epithelial cell model, exposure to three chemically distinct PM mixtures drive unique cell viability patterns, transcriptional remodeling, and the emergence of distinct morphological subtypes. Specifically, PM mixtures modulate cell viability, DNA damage responses, and induce the remodeling of gene expression associated with cell morphology, extracellular matrix organization, and cellular motility. Profiling cellular responses showed that cell morphologies change in a PM composition-dependent manner. Finally, we observed that PM mixtures with higher cadmium content induced increased DNA damage and drove redistribution among morphological subtypes. Our results demonstrate that quantitative measurement of individual cellular morphologies provides a robust, high-throughput approach to gauge the effects of environmental stressors on biological systems and score cellular susceptibilities to pollution.

Origin of non-exhaust PM in cities by individual analysis of particles collected by honey bees (Apis mellifera)

Urban areas present multiple challenges to scientists interested in unraveling the source, transport, and fate of airborne particulate matter (PM). Airborne PM consists of a heterogeneous mixture of particles with different sizes, morphologies, and chemical compositions. However, standard air quality stations only detect the mass concentration of PM mixtures with aerodynamic diameters ≤10 μm (PM10) and/or ≤ 2.5 μm (PM2.5). During honey bee foraging flights, airborne PM up to 10 μm in size attaches to their bodies, making them suitable for collecting spatiotemporal data on airborne PM. The individual particulate chemistry of this PM can be assessed using scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy on a sub-micrometer scale, allowing accurate identification and classification of the particles.Herein, we analyzed the PM fractions of 10–2.5 μm, 2.5–1 μm, and below 1 μm in average geometric diameter collected by bees from hives located in the city of Milan, Italy. Bees showed contamination by natural dust, originating from soil erosion and rock outcropping in the foraging area, and particles with recurrent heavy metal content, most likely attributed to vehicular braking systems and possibly tires (non-exhaust PM). Notably, approximately 80% of non-exhaust PM was ≤1 μm in size. This study provides a possible alternative strategy to apportion the finer fraction of PM in urban areas and determine citizens’ exposure. Our findings may also prompt decision-makers to issue policy addressal for non-exhaust pollution, especially for the ongoing restructuring of European regulations on mobility and the shift toward electric vehicles whose contribution to PM pollution is debated.

Investigating the Performance of the Compact Particulate Matter Collector for Use in Domestic Water Systems

The concept of the new water treatment system was developed. The system is based on the previously invented technology – Compact Particulate Matter Collector (CPMC). A primary area was defined in which such technology is intended to be used: water treatment in compact flue-gas condensation systems for a low-power wood-fuelled biomass boiler. Such a system is intended for use in domestic conditions. Such a process involves contamination of technical water with a mixture of particulate matter, resulting in suspension. The CPMC aims to divide the suspension into the relevant fractions effectively. A prototype operating based on CPMC technology was built. An experimental plan was developed, and an experimental stand was constructed to determine the prototype’s efficiency. The experimental plan envisaged five different prototype operating modes and two research steps, depending on the degree of prototype modification. Based on the research results, it was concluded that the prototype could operate effectively in the laboratory environment: achievable efficiency is equal on average between 57.84 % and 88.09 % depending on the operating mode (see the diagram below). The result is assessed as positive. TRL 3 has been reached. The next phases of the study would be the integration of the prototype into the relevant compact flue-gas condensation system and the exploration of commercialisation capabilities, which will stimulate TRL increase.

Joint effect of indoor size-fractioned particulate matters and black carbon on cardiopulmonary function and relevant metabolic mechanism: A panel study among school children

Indoor particulate matter (PM) and black carbon (BC) are associated with adverse cardiopulmonary effect. However, the cumulative and interactive effects of the mixture of size-fractioned PMs and BC on cardiopulmonary function are not well understood, and the underlying biological mechanisms remain unclear. This repeated-measure study was conducted to assess the joint cardiopulmonary effect and metabolic mechanisms of multiple-size particles and BC among 46 children. PM0.5, PM1, PM2.5, PM5, PM10 and BC were monitored for 5 weekdays. Cardiorespiratory function measurements and urine samples collection were conducted three times. Untargeted-metabolomics and meet-in-metabolite approach were applied to mechanism investigation. Bayesian machine kernel regression was adopted to analyze associations among PMs, cardiopulmonary function and metabolites. Lung function and heart rate variability significantly decreased with the increased PMs and BC co-exposure (p < 0.05). The effective particles were BC, PM1-2.5 and PM0.5 in turn. No interaction effects of different particles on cardiopulmonary function were observed at different lag days. BC-related glucose and fatty acid increase, and PM1-2.5-related branched-chain amino acid degradation were primarily observed. Other metabolisms were successively disturbed. The greatest joint effects of PMs and BC on metabolism were mainly at lag0 and lag01 day. They occurred earlier than the strongest effects on cardiopulmonary function, which were at lag01 and lag02 day. BC, PM1-2.5 and PM0.5 were mainly associated with cardiorespiratory indices by disturbing amino acids, glucose, lipid, isoflavone and purine metabolism. Mitochondrial productivity and antioxidation reduction are pivotal to the relevant metabolic alterations. More attention should be paid to BC and smaller-size PMs to control indoor PM pollution and its adverse effect on children.

Iron Speciation in Respirable Particulate Matter and Implications for Human Health.

Particulate matter (PM) air pollution poses a major global health risk, but the role of iron (Fe) is not clearly defined because chemistry at the particle-cell interface is often not considered. Detailed spectromicroscopy characterizations of PM2.5 samples from the San Joaquin Valley, CA identified major Fe-bearing components and estimated their relative proportions. Iron in ambient PM2.5 was present in spatially and temporally variable mixtures, mostly as Fe(III) oxides and phyllosilicates, but with significant fractions of metallic iron (Fe(0)), Fe(II,III) oxide, and Fe(III) bonded to organic carbon. Fe(0) was present as aggregated, nm-sized particles that comprised up to ∼30% of the Fe spectral fraction. Mixtures reflect anthropogenic and geogenic particles subjected to environmental weathering, but reduced Fe in PM originates from anthropogenic sources, likely as abrasion products. Possible mechanistic pathways involving Fe(0) particles and mixtures of Fe(II) and Fe(III) surface species may generate hydrogen peroxide and oxygen-centered radical species (hydroxyl, hydroperoxyl, or superoxide) in Fenton-type reactions. From a health perspective, PM mixtures with reduced and oxidized Fe will have a disproportionate effect in cellular response after inhalation because of their tendency to shuttle electrons and produce oxidants and electrophiles that induce inflammation and oxidative stress.

Invited Perspective: Air Pollution and Breast Cancer Risk: Current State of the Evidence and Next Steps.

Invited Perspective: Air Pollution and Breast Cancer Risk: Current State of the Evidence and Next Steps.

Toxic effects of gunshot fumes from different ammunitions for small arms on lung cells exposed at the air liquid interface

Concerns have been raised as to whether gunshot fumes induce prolonged reduced lung capacity or even cancer due to inhalation. Gunshot fumes from three different types of ammunition calibre 5.56 mm × 45 NATO were investigated. SS109 has a soft lead (Pb) core, while NM255 and NM229 have a harder steel core. Emissions from ammunitions were characterized with respect to particle number- and mass-size, and mass distribution, heavy metal content, and different gases. Lung epithelial cells were exposed to the fumes at the air liquid interface to elucidate cytotoxicity and genotoxicity. Irrespectively of ammunition type, the largest mass fraction of generated particulate matter (PM) had a size between 1 and 3 μm. The highest number of particles generated was in the size range of 30 nm. Fumes from NM255 and NM229 induced cytotoxic effects of which the emission from NM229 induced the highest effect. Fumes from NM229 induced a dose-related increase in DNA-damage. Significant effects were only achieved at the highest exposure level, which led to approximately 40% reduced cell viability after 24 h. The effect probably relates to the mass of emitted particles where the size may be of importance, in addition to emission of Cu and Zn. A complex mixture of chemical substances and PM may increase the toxicity of the fumes and should encourage measures to reduce exposure.

Atmospheric particulate matter characterization by Fourier transform infrared spectroscopy: a review of statistical calibration strategies for carbonaceous aerosol quantification in US measurement networks

Abstract. Atmospheric particulate matter (PM) is a complex mixture of many different substances and requires a suite of instruments for chemical characterization. Fourier transform infrared (FT-IR) spectroscopy is a technique that can provide quantification of multiple species provided that accurate calibration models can be constructed to interpret the acquired spectra. In this capacity, FT-IR spectroscopy has enjoyed a long history in monitoring gas-phase constituents in the atmosphere and in stack emissions. However, application to PM poses a different set of challenges as the condensed-phase spectrum has broad, overlapping absorption peaks and contributions of scattering to the mid-infrared spectrum. Past approaches have used laboratory standards to build calibration models for prediction of inorganic substances or organic functional groups and predict their concentration in atmospheric PM mixtures by extrapolation. In this work, we review recent studies pursuing an alternate strategy, which is to build statistical calibration models for mid-IR spectra of PM using collocated ambient measurements. Focusing on calibrations with organic carbon (OC) and elemental carbon (EC) reported from thermal–optical reflectance (TOR), this synthesis serves to consolidate our knowledge for extending FT-IR spectroscopy to provide TOR-equivalent OC and EC measurements to new PM samples when TOR measurements are not available. We summarize methods for model specification, calibration sample selection, and model evaluation for these substances at several sites in two US national monitoring networks: seven sites in the Interagency Monitoring of Protected Visual Environments (IMPROVE) network for the year 2011 and 10 sites in the Chemical Speciation Network (CSN) for the year 2013. We then describe application of the model in an operational context for the IMPROVE network for samples collected in 2013 at six of the same sites as in 2011 and 11 additional sites. In addition to extending the evaluation to samples from a different year and different sites, we describe strategies for error anticipation due to precision and biases from the calibration model to assess model applicability for new spectra a priori. We conclude with a discussion regarding past work and future strategies for recalibration. In addition to targeting numerical accuracy, we encourage model interpretation to facilitate understanding of the underlying structural composition related to operationally defined quantities of TOR OC and EC from the vibrational modes in mid-IR deemed most informative for calibration. The paper is structured such that the life cycle of a statistical calibration model for FT-IR spectroscopy can be envisioned for any substance with IR-active vibrational modes, and more generally for instruments requiring ambient calibrations.

A chronology of ratios between black smoke and PM10 and PM2.5 in the context of comparison of air pollution epidemiology concentration-response functions

BackgroundFor many air pollution epidemiological studies in Europe, ‘black smoke’ (BS) was the only measurement available to quantify ambient particulate matter (PM), particularly for exposures prior to the mid-1990s when quantification via the PM10 and/or PM2.5 metrics was introduced. The aim of this work was to review historic BS and PM measurements to allow comparison of health concentration-response functions (CRF) derived using BS as the measure of exposure with CRFs derived using PM10 or PM2.5.MethodsThe literature was searched for quantitative information on measured ratios of BS:PM10, BS:PM2.5, and chemical composition of PM; with specific focus on the United Kingdom (UK) between 1970 and the early 2000s when BS measurements were discontinued.ResultsThe average BS:PM10 ratio in urban background air was just below unity at the start of the 1970s, decreased rapidly to ≈ 0.7 in the mid-1970s and to ≈ 0.5 at the end of the 1970s, with continued smaller declines in the 1980s, and was within the range 0.2–0.4 by the end of the 1990s. The limited data for the BS:PM2.5 ratio suggest it equalled or exceeded unity at the start of the 1970s, declined to ≈ 0.7 by the end of the 1970s, with slower decline thereafter to a range 0.4–0.65 by the end of the 1990s. For an epidemiological study that presents a CRFBS value, the corresponding CRFPM10 value can be estimated as RBS:PM10 × CRFBS where RBS:PM10 is the BS:PM10 concentration ratio, if the toxicity of PM10 is assumed due only to the component quantified by a BS measurement. In the general case of some (but unknown) contribution of toxicity from non-BS components of PM10 then CRFPM10 > RBS:PM10 × CRFBS, with CRFPM10 exceeding CRFBS if the toxicity of the other components in PM10 is greater than the toxicity of the component to which the BS metric is sensitive. Similar analyses were applied to relationships between CRFPM2.5 and CRFBS.ConclusionsApplication of this analysis to example published CRFBS values for short and long-term health effects of PM suggest health effects from other components in the PM mixture in addition to the fine black particles characterised by BS.

Anthropogenic influences on the physical state of submicron particulate matter over a tropical forest

Abstract. The occurrence of nonliquid and liquid physical states of submicron atmospheric particulate matter (PM) downwind of an urban region in central Amazonia was investigated. Measurements were conducted during two intensive operating periods (IOP1 and IOP2) that took place during the wet and dry seasons of the GoAmazon2014/5 campaign. Air masses representing variable influences of background conditions, urban pollution, and regional- and continental-scale biomass burning passed over the research site. As the air masses varied, particle rebound fraction, an indicator of physical state, was measured in real time at ground level using an impactor apparatus. Micrographs collected by transmission electron microscopy confirmed that liquid particles adhered, while nonliquid particles rebounded. Relative humidity (RH) was scanned to collect rebound curves. When the apparatus RH matched ambient RH, 95 % of the particles adhered as a campaign average. Secondary organic material, produced for the most part by the oxidation of volatile organic compounds emitted from the forest, produces liquid PM over this tropical forest. During periods of anthropogenic influence, by comparison, the rebound fraction dropped to as low as 60 % at 95 % RH. Analyses of the mass spectra of the atmospheric PM by positive-matrix factorization (PMF) and of concentrations of carbon monoxide, total particle number, and oxides of nitrogen were used to identify time periods affected by anthropogenic influences, including both urban pollution and biomass burning. The occurrence of nonliquid PM at high RH correlated with these indicators of anthropogenic influence. A linear model having as output the rebound fraction and as input the PMF factor loadings explained up to 70 % of the variance in the observed rebound fractions. Anthropogenic influences can contribute to the presence of nonliquid PM in the atmospheric particle population through the combined effects of molecular species that increase viscosity when internally mixed with background PM and increased concentrations of nonliquid anthropogenic particles in external mixtures of anthropogenic and biogenic PM.

Atmospheric corrosion of copper and silver influenced by particulate matter

The atmospheric corrosion of copper and silver influenced by graphite and alumina as particulate matter (PM) in an environment containing 200 μg m−3 SO2 + 150 μg m−3 NO2 at 85% RH and 25 °C was analyzed. Different proportions of PM mixture conditions were used, and the corrosion rate was followed using gravimetric analysis. Results of linear sweep voltammetry (LSV) and coulometric reduction (CR) indicated that larger corrosion rates were obtained in the presence of deposited PM. Under present exposure conditions, copper corrosion rate was larger than silver corrosion rate. X-ray diffraction (XRD) shows the presence of cuprite (Cu2O) and brochantite (Cu4SO4(OH)6) in the case of copper and achantite (Ag2S) in the case of silver.

Airborne particulate matter pollution in urban China: a chemical mixture perspective from sources to impacts

AbstractRapid urban and industrial development has resulted in severe air-pollution problems in developing countries such as China, especially in highly industrialized and populous urban clusters. Dissecting the complex mixtures of airborne particulate matter (PM) has been a key scientific focus in the last two decades, leading to significant advances in understanding physicochemical compositions for comprehensive source apportionment. However, identifying causative components with an attributable link to population-based health outcomes remains a huge challenge. The microbiome, an integral dimension of the PM mixture, is an unexplored frontier in terms of identities and functions in atmospheric processes and human health. In this review, we identify the major gaps in addressing these issues, and recommend a holistic framework for evaluating the sources, processes and impacts of atmospheric PM pollution. Such an approach and the knowledge generated will facilitate the formulation of regulatory measures to control PM pollution in China and elsewhere.

Incomplete lung recovery following sub-acute inhalation of combustion-derived ultrafine particles in mice.

BackgroundParticulate matter (PM) is one of the six criteria pollutant classes for which National Ambient Air Quality Standards have been set by the United States Environmental Protection Agency. Exposures to PM have been correlated with increased cardio-pulmonary morbidity and mortality. Butadiene soot (BDS), generated from the incomplete combustion of 1,3-butadiene (BD), is both a model PM mixture and a real-life example of a petrochemical product of incomplete combustion. There are numerous events, including wildfires, accidents at refineries and tank car explosions that result in sub-acute exposure to high levels of airborne particles, with the people exposed facing serious health problems. These real-life events highlight the need to investigate the health effects induced by short-term exposure to elevated levels of PM, as well as to assess whether, and if so, how well these adverse effects are resolved over time. In the present study, we investigated the extent of recovery of mouse lungs 10 days after inhalation exposures to environmentally-relevant levels of BDS aerosols had ended.MethodsFemale BALB/c mice exposed to either HEPA-filtered air or to BDS (5 mg/m3 in HEPA filtered air, 4 h/day, 21 consecutive days) were sacrificed immediately, or 10 days after the final BDS exposure. Bronchoalveolar lavage fluid (BALF) was collected for cytology and cytokine analysis. Lung proteins and RNA were extracted for protein and gene expression analysis. Lung histopathology evaluation also was performed.ResultsSub-acute exposures of mice to hydrocarbon-rich ultrafine particles induced: (1) BALF neutrophil elevation; (2) lung mucosal inflammation, and (3) increased BALF IL-1β concentration; with all three outcomes returning to baseline levels 10 days post-exposure. In contrast, (4) lung connective tissue inflammation persisted 10 days post-exposure; (5) we detected time-dependent up-regulation of biotransformation and oxidative stress genes, with incomplete return to baseline levels; and (6) we observed persistent particle alveolar load following 10 days of recovery.ConclusionThese data show that 10 days after a 21-day exposure to 5 mg/m3 of BDS has ended, incomplete lung recovery promotes a pro-biotransformation, pro-oxidant, and pro-inflammatory milieu, which may be a starting point for potential long-term cardio-pulmonary effects.

Particulate matter components, sources, and health: Systematic approaches to testing effects

Exposure to particulate matter (PM) is associated with adverse health outcomes. There has long been a question as to whether some components of the PM mixture are of greater public health concern than others so that the sources that emit the more toxic components could be controlled. In this paper, we describe the National Particle Component Toxicity (NPACT) initiative, a comprehensive research program that combined epidemiologic and toxicologic approaches to evaluate this critical question, partly relying on information from a national network of air quality monitors that provided data on speciated PM2.5 (PM with an aerodynamic diameter <2.5 μm) starting in 2000. We also consider the results of the NPACT program in the context of selected research on PM components and health in order to assess the current state of the field. Overall, the ambitious NPACT research program found associations of secondary sulfate and, to a somewhat lesser extent, traffic sources with health effects. Although this and other research has linked a variety of health effects to multiple groups of PM components and sources of PM, the collective evidence has not yet isolated factors or sources that would be closely and unequivocally more strongly related to specific health outcomes. If greater success is to be achieved in isolating the effects of pollutants from mobile and other major sources, either as individual components or as a mixture, more advanced approaches and additional measurements will be needed so that exposure at the individual or population level can be assessed more accurately. Enhanced understanding of exposure and health effects is needed before it can be concluded that regulations targeting specific sources or components of PM2.5 will protect public health more effectively than continuing to follow the current practices of targeting PM2.5 mass as a whole.Implications: This paper describes a comprehensive epidemiologic and toxicologic research program to evaluate whether some components and sources of PM may be more toxic than others. This question is important for regulatory agencies in setting air quality standards to protect people’s health. The results show that PM from coal and oil combustion and from traffic sources was associated with adverse health outcomes, but other components and sources could not definitively be ruled out. Thus, given current knowledge, the current practice of setting air quality standards for PM mass as a whole likely remains an effective approach to protecting public health.

Compositional variance in extracted particulate matter using different filter extraction techniques

Collection and subsequent extraction of particulate matter (PM) from filter substrates is a common requirement for in vivo and in vitro toxicological studies, as well as chemical analyses such as ion chromatography and inductively coupled plasma mass spectrometry. Several filter extraction protocols exist and different laboratories employ different methods, potentially biasing inter-study comparisons. Previous studies have shown significant differences in extraction efficiency between techniques and identified the relevant extraction artifacts. However, a comprehensive inter-comparison of different methods based on the chemical composition of the extracted PM has never been conducted. In the current study, an exhaustive suite of chemical analyses is performed on PM extracted from glass micro-fiber filters using techniques commonly employed in different laboratories: Multi-solvent extraction (MSE) and spin-down extraction (SDE). PM samples were collected simultaneously during field studies conducted in an urban and rural setting using a high-volume PM2.5 sampler. Results show remarkable compositional variance between the PM extracts for all chemical components analyzed, including metals, water soluble ions, polycyclic aromatic hydrocarbons, non-aromatic organics, elemental carbon and organic carbon. Mass closure was greater than 90% for MSE but deviated substantially for SDE. Detailed retrospective gravimetric analysis of archived SDE samples revealed that a process-based loss of PM mass is the root cause of the differences. These losses are shown to be compositionally biased, both externally between different PM mixtures and internally within a given PM mixture. In combination, the results of this study are the first to demonstrate (i) an exhaustive chemical characterization of a single PM extract, (ii) the significance of directly characterizing the extracted PM used in toxicological studies, (iii) the existence of substantial compositional biases between different filter extraction techniques and (iv) the importance of standardizing filter extraction objectives and procedures to avoid introducing study bias into toxicological studies.

Engine exhaust particulate and gas phase contributions to vascular toxicity

Cardiovascular health effects of near-roadway pollution appear more substantial than other sources of air pollution. The underlying cause of this phenomenon may simply be concentration-related, but the possibility remains that gases and particulate matter (PM) may physically interact and further enhance systemic vascular toxicity. To test this, we utilized a common hypercholesterolemic mouse model (Apolipoprotein E-null) exposed to mixed vehicle emission (MVE; combined gasoline and diesel exhausts) for 6 h/d × 50 d, with additional permutations of removing PM by filtration and also removing gaseous species from PM by denudation. Several vascular bioassays, including matrix metalloproteinase-9 protein, 3-nitrotyrosine and plasma-induced vasodilatory impairments, highlighted that the whole emissions, containing both particulate and gaseous components, was collectively more potent than MVE-derived PM or gas mixtures, alone. Thus, we conclude that inhalation of fresh whole emissions induce greater systemic vascular toxicity than either the particulate or gas phase alone. These findings lend credence to the hypothesis that the near-roadway environment may have a more focused public health impact due to gas–particle interactions.

Effects of particulate matter (PM) sources on mortality in Mediterranean cities: the MED-Particles project

Background: Acute exposure to particulate matter (PM) has been linked to increases in mortality in several studies. Recently, some studies have examined which species and sources in the PM mixture are responsible for these associations, but this is not well documented in Southern Europe. The Mediterranean area has specific characteristics that influence air pollution levels and composition, such as highly urbanized areas with intense traffic, elevated sea traffic, intense solar radiation, and high frequency of wildfires and Saharan dust episodes. Aims: Examine the association between several PM sources and mortality in three Mediterranean cities. Methods: PM10 and PM2.5 concentrations were collected once or twice a week in three Spanish cities, Barcelona (2003-2010), Madrid (2007-2008) and Huelva (2003-2009). Source apportionment using positive matrix factorization was developed for both PM2.5 and PM10. A case-crossover regression analysis will be used to determine the effects of daily exposure to each source and non-accidental, cardiovascular and respiratory mortality for each city. Single-city estimates will be combined using meta-analysis. Results: Source apportionment resulted in three sources that were common in the three cities: traffic, mineral and industrial. Traffic accounted for 47%, 39% and 22% of PM2.5 concentrations in Barcelona, Madrid and Huelva, respectively. The city percentages were 9%, 18% and 13% for the mineral source. The industrial source was only detected in Barcelona and Huelva, where it accounted for 5% and 13% of PM2.5 concentrations. Similar percentages were found for PM10. Taken together, they common sources accounted for an average of between 56% and 71% of PM concentrations. Conclusions: Traffic is one of the main contributors to PM concentrations in the three cities. These sources will be linked to mortality in the subsequent analysis, including more cities, to provide the first multi-city study on health and PM sources in Europe. Acknowledgements: MED-PARTICLES EU LIFE10 ENV/IT/327

Gaseous VOCs rapidly modify particulate matter and its biological effects – Part 2: Complex urban VOCs and model PM

Abstract. This is the second study in a three-part study designed to demonstrate dynamic entanglements among gaseous organic compounds (VOCs), particulate matter (PM), and their subsequent potential biological effects. We study these entanglements in increasingly complex VOC and PM mixtures in urban-like conditions in a large outdoor chamber, both in the dark and in sunlight. To the traditional chemical and physical characterizations of gas and PM, we added new measurements of gas-only- and PM-only-biological effects, using cultured human lung cells as model living receptors. These biological effects are assessed here as increases in cellular damage or expressed irritation (i.e., cellular toxic effects) from cells exposed to chamber air relative to cells exposed to clean air. Our exposure systems permit side-by-side, gas-only- and PM-only-exposures from the same air stream containing both gases and PM in equilibria, i.e., there are no extractive operations prior to cell exposure for either gases or PM. In Part 1 (Ebersviller et al., 2012a), we demonstrated the existence of PM "effect modification" (NAS, 2004) for the case of a single gas-phase toxicant and an inherently non-toxic PM (mineral oil aerosol, MOA). That is, in the presence of the single gas-phase toxicant in the dark, the initially non-toxic PM became toxic to lung cells in the PM-only-biological exposure system. In this Part 2 study, we used sunlit-reactive systems to create a large variety of gas-phase toxicants from a complex mixture of oxides of nitrogen and 54 VOCs representative of those measured in US city air. In these mostly day-long experiments, we have designated the period in the dark just after injection (but before sunrise) as the "Fresh" condition and the period in the dark after sunset as the "Aged" condition. These two conditions were used to expose cells and to collect chemical characterization samples. We used the same inherently non-toxic PM from the Part 1 study as the target PM for "effect modification". Fortunately, in the absence of "seed particles", the complex highly-reactive VOC system used does not create any secondary aerosol in situ. All PM present in these tests were, therefore, introduced by injection of MOA to serve as PM-to-be-modified by the gaseous environment. PM addition was only done during dark periods, either before or after the daylight period. The purpose of this design is to test if a non-toxic PM becomes toxic in initially unreacted ("Fresh"), or in reacted ("Aged") complex VOC conditions. To have a complete design, we also tested the effects of clean air and the same VOC conditions, but without introducing any PM. Thus, there were six exposure treatment conditions that were evaluated with the side-by-side, gas-only- and PM-only-effects exposure systems; five separate chamber experiments were performed: two with clean air and three with the complex VOC/NOx mixture. For all of these experiments and exposures, chemical composition data and matching biological effects results for two end-points were compared. Chemical measurements demonstrate the temporal evolution of oxidized species, with a corresponding increase in toxicity observed from exposed cells. The largest increase in gas-phase toxicity was observed in the two "Aged" VOC exposures. The largest increase in particle-phase toxicity was observed in the "Aged" VOC exposure with the addition of PM after sunset. These results are a clear demonstration that the findings from Part 1 can be extended to the complex urban oxidized environment. This further demonstrates that the atmosphere itself cannot be ignored as a source of toxic species when establishing the risks associated with exposure to PM. Because gases and PM are transported and deposited differently within the atmosphere and lungs, these results have significant consequences. In the next (and final) part of the study, testing is further applied to systems with real diesel exhaust, including primary PM from a vehicle operated with different types of diesel fuel.

Gaseous VOCs rapidly modify particulate matter and its biological effects – Part 1: Simple VOCs and model PM

Abstract. This is the first of a three-part study designed to demonstrate dynamic entanglements among gaseous organic compounds (VOC), particulate matter (PM), and their subsequent potential biological effects. We study these entanglements in increasingly complex VOC and PM mixtures in urban-like conditions in a large outdoor chamber. To the traditional chemical and physical characterizations of gas and PM, we added new measurements of biological effects, using cultured human lung cells as model indicators. These biological effects are assessed here as increases in cellular damage or expressed irritation (i.e., cellular toxic effects) from cells exposed to chamber air relative to cells exposed to clean air. The exposure systems permit virtually gas-only- or PM-only-exposures from the same air stream containing both gases and PM in equilibria, i.e., there are no extractive operations prior to cell exposure. Our simple experiments in this part of the study were designed to eliminate many competing atmospheric processes to reduce ambiguity in our results. Simple volatile and semi-volatile organic gases that have inherent cellular toxic properties were tested individually for biological effect in the dark (at constant humidity). Airborne mixtures were then created with each compound to which we added PM that has no inherent cellular toxic properties for another cellular exposure. Acrolein and p-tolualdehyde were used as model VOCs and mineral oil aerosol (MOA) was selected as a surrogate for organic-containing PM. MOA is appropriately complex in composition to represent ambient PM, and exhibits no inherent cellular toxic effects and thus did not contribute any biological detrimental effects on its own. Chemical measurements, combined with the responses of our biological exposures, clearly demonstrate that gas-phase pollutants can modify the composition of PM (and its resulting detrimental effects on lung cells). We observed that, even if the gas-phase pollutants are not considered likely to partition to the condensed phase, the VOC-modified-PM showed significantly more damage and inflammation to lung cells than did the original PM. Because gases and PM are transported and deposited differently within the atmosphere and the lungs, these results have significant consequences for a wide range of people. For example, current US policies for research and regulation of PM do not recognize this "effect modification" phenomena (NAS, 2004). These results present an unambiguous demonstration that – even in these simple mixtures – physical and thermal interactions alone can cause a modification of the distribution of species among the phases of airborne pollution mixtures that can result in a non-toxic phase becoming toxic due to atmospheric thermal processes only. Subsequent work (described in companion papers) extends the simple results reported here to systems with photochemical transformations of complex urban mixtures and to systems with diesel exhaust produced by different fuels.