Urban Particulate Matter Samples Research Articles

Determination of trace concentrations of simple phenols in ambient PM samples.

Phenols are hazardous, but yet ubiquitous in the environment, including in atmospheric aerosols due to combustion emissions. There, phenols are subjected to secondary transformations, producing even more toxic nitrophenolic air pollutants. However, primary simple phenols, i.e. those containing only hydroxyl, methyl and methoxy substituents are not easy to detect. Trace concentrations, semi-volatile character and poorly ionizable functional groups prevent us from their determination by the most common analytical techniques, such as gas and liquid chromatography with mass spectrometric detection (GC/LC-MS). Here, we present a new derivatization method for MS/MS detection with positive ion electrospray ionization (+ESI-MS/MS) of simple phenols in atmospheric particulate matter (PM) extracts. The method is sensitive, selective, and robust, and requires no sample concentration step, which is critical due to the volatile character of the target analytes. After derivatization with dansyl chloride, phenol, catechol, cresols and guaiacol were detected in urban PM samples from Ljubljana, Slovenia. This method finally enables to study the abundance of primary phenols in atmospheric PM from different sources, which will improve understanding of secondary aerosol (trans)formation pathways and allow for more targeted mitigation strategies in respect to airborne phenolic pollutants.

Precipitation of aqueous transition metals in particulate matter during the dithiothreitol (DTT) oxidative potential assay.

Transition metals in particulate matter (PM) are hypothesized to have enhanced toxicity based on their oxidative potential (OP). The acellular dithiothreitol (DTT) assay is widely used to measure the OP of PM and its chemical components. In our prior study, we showed that the DTT assay (pH 7.4, 0.1 M phosphate buffer, 37 °C) provides favorable thermodynamic conditions for precipitation of multiple metals present in PM. This study utilizes multiple techniques to characterize the precipitation of aqueous metals present at low concentrations in the DTT assay. Metal precipitation was identified using laser particle light scattering analysis, direct chemical measurement of aqueous metal removal, and microscopic imaging. Experiments were run with aqueous metals from individual metal salts and a well-characterized urban PM standard (NIST SRM-1648a, Urban Particulate Matter). Our results demonstrated rapid precipitation of metals in the DTT assay. Metal precipitation was independent of DTT but dependent on metal concentration. Metal removal in the chemically complex urban PM samples exceeded the thermodynamic predictions and removal seen in single metal salt experiments, suggesting co-precipitation and/or adsorption may have occurred. These results have broad implications for other acellular assays that study PM metals using phosphate buffer, and subsequently, the PM toxicity inferred from these assays.

The Influence of Redox‐Active Transition Metal Containing Micro‐ and Nanoparticles on the Properties of Representative Bioinorganic Reaction Systems

The use of nanomaterials in biological applications requires a better understanding of the effect of nanoparticles on the activity of proteins and related molecules. We have examined the influence of environmental particulate matter (PM) on the interaction of myoglobin and microperoxidase‐11 as model systems with the small molecules O2 and NO, respectively. The influence of PM on the reaction of dioxygen with deoxymyoglobin to form oxymyoglobin, and subsequently metmyoglobin, was studied for its essential role in living organisms. Samples of urban PM (SRM 1648a) were used as standard reference material. Also the influence of Fe2O3 nanoparticles on the stability of the investigated protein was studied. The obtained results show that binding and release of dioxygen by deoxymyoglobin may be affected by the presence of PM especially over longer periods of time. Similar studies were performed on the nitrosylation of microperoxidase‐11 as a model for the catalytic center of enzymes, for which the influence of the standard reference material, its water‐soluble extract, as well as metal oxide nanoparticles (Fe2O3 and ZnO), were studied. The reported results show that the presence of PM had no influence on the kinetics of the nitrosylation of the model microperoxidase under the selected experimental conditions.

Particle size distribution and gas-particle partitioning of polychlorinated biphenyls in the atmosphere in Beijing, China.

Size-fractionated samples of urban particulate matter (PM; ≤1.0, 1.0-2.5, 2.5-10, and >10μm) and gaseous samples were simultaneously obtained to study the distribution of polychlorinated biphenyls (PCBs) in the atmosphere in Beijing, China. Most recent investigations focused on the analysis of gaseous PCBs, and much less attention has been paid to the occurrence of PCBs among different PM fractions. In the present study, the gas-particle partitioning and size-specific distribution of PCBs in atmosphere were investigated. The total concentrations (gas + particle phase fractions) of Σ12 dioxin-like PCBs, Σ7 indicator PCBs, and ΣPCBs were 1.68, 42.1, and 345pg/m3, respectively. PCBs were predominantly in the gas phase (86.8-99.0% of the total concentrations). The gas-particle partition coefficients (K p ) of PCBs were found to be a significant linear correlated with the subcooled liquid vapor pressures (P L0) (R 2=0.83, P<0.01). The slope (m r ) implied that the gas-particle partitioning of PCBs was affected both by the mechanisms of adsorption and absorption. In addition, the concentrations of PCBs increased as the particle size decreased (>10, 2.5-10, 1.0-2.5, and ≤1.0μm), with most of the PCBs contained in the fraction of ≤1.0μm (53.4% of the total particulate concentrations). Tetra-CBs were the main homolog in the air samples in the gas phase and PM fractions, followed by tri-CBs. This work will contribute to the knowledge of PCBs among different PM fractions and fill the gap of the size distribution of particle-bound dioxin-like PCBs in the air.

PAH Accessibility in Particulate Matter from Road-Impacted Environments.

Snowmelt, surface runoff, or stormwater releases in urban environments can result in significant discharges of particulate matter-bound polycyclic aromatic hydrocarbons (PAHs) into aquatic environments. Recently, more-specific activities such as road-tunnel washing have been identified as contributing to contaminant load to surface waters. However, knowledge of PAH accessibility in particulate matter (PM) of urban origin that may ultimately be released into urban surface waters is limited. In the present study, we evaluated the accessibility of PAHs associated with seven distinct (suspended) particulate matter samples collected from different urban sources. Laboratory-based infinite sink extractions with silicone rubber (SR) as the extractor phase demonstrated a similar pattern of PAH accessibility for most PM samples. Substantially higher accessible fractions were observed for the less-hydrophobic PAHs (between 40 and 80% of total concentrations) compared with those measured for the most-hydrophobic PAHs (<5% of total concentrations). When we focused on PAHs bound to PM from tunnel-wash waters, first-order desorption rates for PAHs with log Kow > 5.5 were found in line with those commonly found for slowly or very slowly desorbing sediment-associated contaminants. PAHs with log Kow < 5.5 were found at higher desorbing rates. The addition of detergents did not influence the extractability of lighter PAHs but increased desorption rates for the heavier PAHs, potentially contributing to increases in the toxicity of tunnel-wash waters when surfactants are used. The implications of total and accessible PAH concentrations measured in our urban PM samples are discussed in a context of management of PAH and PM emission to the surrounding aquatic environment. Although we only fully assessed PAHs in this work, further study should consider other contaminants such as OPAHs, which were also detected in all PM samples.

Concentration Distribution and Bioaccessibility of Trace Elements in Nano and Fine Urban Airborne Particulate Matter: Influence of Particle Size

Trace elements, especially those associated with fine particles in airborne particulate matter (PM), may play an important role in PM adverse health effect. The aim of this paper is to characterize elements in a wide particle size range from nano (57–100 nm) to fine (100–1,000 nm) and to coarse (1,000–10,000 nm) fractions of two urban PM samples collected in Ottawa. Size-selective particle sampling was performed using a micro-orifice uniform deposit impactor, and element concentrations were determined in each different size fraction by inductively coupled plasma-mass spectroscopy. A general trend of increasing element concentration with decreasing aerodynamic diameter was observed for elements V, Mn, Ni, Cu, Zn, Se, and Cd, indicating they were predominately concentrated in the nanoparticle size range. Other elements including Fe, Sr, Mo, Sn, Sb, Ba, and Pb were predominately concentrated in the fine-size range. Increased concentration of elements in the nano and fine particle size range is significant due to their ability to penetrate into the deepest alveolar area of the lungs. This was confirmed by the calculation of median concentration diameters, which were less than 800 nm for most of the investigated elements. Particle size distribution and element correlation analysis suggest that the elements concentrated in the nano- and fine-size fractions originated mainly from vehicular combustion and emission. Long-range airborne transport and soil or road dust resuspension may also contribute. Particle size had an important effect on element bioaccessibility for the studied urban PM samples showing a general trend of increasing element bioaccessibility with decreasing particle size. These results emphasize the importance of acquiring information on nano and/or fine PM-bound elements and their bioaccessibilities for accurate element and PM exposure assessment.

Seasonal variation of the size distribution of urban particulate matter and associated organic pollutants in the ambient air

Size-segregated samples of urban particulate matter (<0.95, 0.95–1.5, 1.5–3.0, 3.0–7.5, >7.5 μm) were collected in Thessaloniki, northern Greece, during winter and summer of 2007–2008, in order to study the size distribution of organic compounds such as polycyclic aromatic hydrocarbons (PAHs), aliphatic hydrocarbons (AHs) including n-alkanes and the isoprenoids pristane and phytane, organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). All organic compounds were accumulated in the particle size fraction <0.95 μm particularly in the cold season. Particulate matter displayed a bimodal normalized distribution in both seasons with a stable coarse mode located at 3.0–7.5 μm and a fine mode shifting from 0.95–1.5 μm in winter to <0.95 μm in summer. Unimodal normalized distributions, predominant at 0.95–1.5 μm size range, were found for most organic compounds in both seasons, suggesting gas-to-particle transformation after emission. A second minor mode at larger particles (3.0–7.5 μm) was observed for C 19 and certain OCPs suggesting redistribution due to volatilization and condensation.

Genotoxicity of size-fractionated samples of urban particulate matter

Urban particulate matter (UPM) includes particles of size smaller than 10 microm (PM10), which may impact on human respiratory and cardiovascular health. It has been reported previously that PM10 can induce DNA damage. We have collected size-fractionated PM10 at the roadside and measured the induction of DNA damage by different-sized UPM using the alkaline Comet assay and the plasmid strand-break assay. We found that foil disks were more suitable for collecting UPM than quartz fiber filters, as the UPM could be easily extracted from the foil disks and accurately weighed. Using the Comet assay, all size fractions induced DNA damage in A549 lung epithelial cells, with the finer fractions (D50% = 0.65 microm and lower) inducing the most damage. In the plasmid strand-break assay, in which DNA damage is induced by free-radical species generated in solution, the most damage was also induced by the finer fractions, although the finest fraction (D50% < 0.43 microm) did not induce as much damage as D50% = 0.65 and 0.43 microm. When an organic extract of a standard UPM sample was compared to the whole particles and the washed particles in the Comet assay, it was found that around 75% of the damage induced by the whole UPM could be induced by the organic extract. These results show that finer particulates have the greatest ability to induce DNA damage in lung epithelial cells and naked DNA, and that both organic and inorganic components of the UPM contribute to its genotoxic effects.

Genotoxicity and physicochemical characteristics of traffic‐related ambient particulate matter

Exposure to ambient particulate matter (PM) has been linked to several adverse health effects. Since vehicular traffic is a PM source of growing importance, we sampled total suspended particulate (TSP), PM(10), and PM(2.5) at six urban locations with pronounced differences in traffic intensity. The mutagenicity, DNA-adduct formation, and induction of oxidative DNA damage by the samples were studied as genotoxicological parameters, in relation to polycyclic aromatic hydrocarbon (PAH) levels, elemental composition, and radical-generating capacity (RGC) as chemical characteristics. We found pronounced differences in the genotoxicity and chemical characteristics of PM from the various locations, although we could not establish a correlation between traffic intensity and any of these characteristics for any of the PM size fractions. Therefore, the differences between locations may be due to local sources of PM, other than traffic. The concentration of total (carcinogenic) PAHs correlated positively with RGC, direct and S9-mediated mutagenicity, as well as the induction of DNA adducts and oxidative DNA damage. The interaction between total PAHs and transition metals correlated positively with DNA-adduct formation, particularly from the PM(2.5) fraction. RGC was not associated with one specific PM size fraction, but mutagenicity and DNA reactivity after metabolic activation were relatively high in PM(10) and PM(2.5), when compared with TSP. We conclude that the toxicological characteristics of urban PM samples show pronounced differences, even when PM concentrations at the sample sites are comparable. This implies that emission reduction strategies that take chemical and toxicological characteristics of PM into account may be useful for reducing the health risks associated with PM exposure.

Analysis of urban particulates by means of combined electron microscopy and X-ray microanalysis

Particles from four samples of urban particulate matter collected in the U.S.A. were analysed by combined electron microscopy and microanalysis (EMMA). In the case of material collected at Baltimore, Maryland, lead was found to be present only in particles ranging from 0.05μm to about 0.3μm in size. The lead bearing particles did not seem to associate with other particles. Analysis of a fly ash specimen showed no qualitative or significant quantitative variation in chemistry as a function of size for the most prevalent type of particle found. Since it may be crucial to have information about particles smaller than 0.5μm in air pollution studies, EMMA should be included with spectrometric analysis, X-ray diffraction, scanning electron microscopy and electron probe microanalysis as a primary tool for particulate analysis.