Concentration and distribution of heavy metals in urban airborne particulate matter in Frankfurt am Main, Germany

Heavy metal concentrations were measured in airborne dust collected at three sites with different traffic densities from August 2001 to July 2002 in the Frankfurt am Main area. Bulk samples of particulate matter (PM) with an aerodynamic equivalent diameter of <22 microm were collected on cellulose nitrate filters using air filtration devices. Fractionated samples of PM with an aerodynamic equivalent diameter of <10 microm were collected using an eight-stage Andersen impactor. Pb, Cd, Mn, Ni, Zn, V, As, Sb, Cu, Cr, Co, and Ce were determined by inductively coupled plasma sector field mass spectrometry, Pt and Rh were determined by adsorptive voltammetry, and Pd was determined by total reflection X-ray fluorescence analysis. The results show that the highest airborne heavy metal concentrations occurred at the main street with a large volume of traffic. With the exception of Co, V, Ce, and Mn, the heavy metals had an elevated enrichment factor compared to their concentrations in the continental crust. The main street site was especially contaminated with Sb, Zn, Cu, V, and Ni. Motor vehicles are the likely source of emissions. With the exception of Cr, Cu, and Zn, most of the airborne heavy metal concentrations determined for impactor samples deviate slightly from the results for total airborne dust. Heavy metal particle size distributions can be divided into three groups. For metals such as As, Cd, Pb, and V, the main fraction can be found in fine particles with a diameter of <2.1 microm, whereas Ce, Cr, Co, and Ni occur mainly in coarse particles with a diameter of >2.1 microm. Cu, Mn, Sb, Zn, Pt, Pd, and Rh occur in high concentrations in the medium range of the impactor stages (particle diameters of 1.1-4.7 microm). Metal concentrations in fine dust particles are needed to assess the human health risks of their inhalation.     

Platinum and rhodium concentrations in airborne particulate matter in Germany from 1988 to 1998

Increases in platinum group element (PGE) concentrations in ambient air and dust since the introduction of automotive catalytic converters in 1988 is a cause of concern. Until now, data derived from engine-test bench experiments have provided the basis for the assessment of human health risks associated with PGE exposure. Such experiments have provided valuable information regarding emission data that has been used to estimate ambient exposure concentrations. However, these data are not necessarily representative of typical environmental PGE exposure levels and conditions. Data on measured environmental concentrations is needed to provide a more adequate basis for the assessment of exposure and related risks. Twenty air and airborne-dust samples were provided by the Umweltbundesamt (Federal Environmental Agency, Germany) in the years 1988, 1989, 1992, 1997, and 1998. The samples were collected in Frankfurt/Main and the adjacent city of Offenbach. For this, 11 to 80 m3 of air were filtered over a 24-72 h period using a vacuum. Glass-fiber filters were used to collect samples. Sample platinum and rhodium concentrations were determined using adsorptive voltammetry. Although the number of samples collected in different years is limited, the results indicate a trend toward continuous increases in ambient concentrations of these metals between 1988 and 1998. Specifically, there were 46- and 27-fold increases in Pt and Rh concentrations, respectively. Despite these observed increases, the Pt concentrations measured (i.e., 147 pg/m3 on average, with a maximum of 246 pg/m3 in 1998) fell far below 15,000 pg/m3, which has been suggested as a guidance value (i.e., exposure at this level would be expected to be without appreciable health risk). The results of a particle-size distribution analysis of one sample (8-step impactor) that was collected 150 m away from a street show that approximately 75% of Pt and 95% of Rh occurs in association with large particulate matter of > 2 microns, with concentrations reaching a maximum in particles of 4.7 to 5.8 microns. The remaining 25% of Pt and 5% of Rh is present in fine particulate matter of < 2 microns. An approximate 10% of Pt and < 38% of Rh in airborne particles was found to be soluble in 0.1 molar HCl. Further, the results indicate that most of the emitted PGE particles from automotive catalytic converters, particularly those bound to fine particulate matter, are capable of being airborne. As a result, PGEs are not only present in areas close to emissions (e.g., roads), but can be transported over longer distances.     

Events affecting levels and seasonal evolution of airborne particulate matter concentrations in the Western Mediterranean

Time series (1996-2000) of levels of PM (PM10 and TSP) and gaseous pollutants recorded in air quality monitoring networks from Northeastern Spain were interpreted using meteorological data and satellite observations of African dust plumes. The main objective of this study was to identify the processes affecting time variations of PM levels on a day-to-day and seasonal basis. From March to October PM levels at rural, urban, and industrial sites vary as a function of the concatenation of Atlantic air mass advections (Atlantic episodes with low PM levels) and regional circulations (regional events with high PM levels, very often associated with high ozone levels), which favor the aging of air masses in the Western Mediterranean basin. During these regional episodes, PM is transported from urban/industrial to rural sites by meso-scale circulations. From November to February low PM levels are recorded at rural sites, and variations in PM levels at urban/industrial sites are governed by the successive occurrence of Atlantic episodes and local urban/industrial pollution events. The African dust outbreaks take place throughout the year and may induce PM levels to increase simultaneously in large areas of the Iberian peninsula. The difference between PM concentrations measured at urban and rural sites experiences a seasonal trend similar to that of levels of NO(x) and CO, which is characterized by a winter maximum due to the higher frequency of intensive local urban pollution events. However, maximum PM levels are recorded in summer at rural sites owing to the frequent occurrence of regional episodes. Furthermore, in three years of the study period (1997, 1998, and 2000), a second-order PM maximum was also recorded at rural sites in March owing to intensive African dust outbreaks.     

DDT-related compounds bound to the nonextractable particulate matter in sediments of the Teltow Canal,Germany

Sediment samples of the Teltow Canal (Berlin, Germany) were analyzed with respect to extractable and nonextractable organic compounds. The study focused on the identification and quantitation of bound 2,2-bis(chlorophenyl)-1,1,1-trichlorethane (DDT) residues in order to obtain further information about the fate of DDT-derived compounds within the particulate matter of the aquatic environment. Various chemical degradation techniques and a complementary online pyrolysis-GC/MS method were applied to the pre-extracted sediment residues. Generally, the distribution of the bound DDT-related compounds was found to differ distinctly from the substances distribution within the extractable fraction. The main metabolite of the anaerobic degradation pathway (2,2-bis(chlorophenyl)-1,1-dichlorethane, DDD) is most abundant in the sediment extracts but occurred only in insignificant concentrations in the degradation products of all procedures applied. The most abundant DDT-metabolites released after the degradation procedures were 4,4'-DBP, 4,4'-DDA, and 4,4'-DDM. In addition, 4,4'-DDM was detected at rather high concentrations by pyrolytic analysis. The results imply a weak association to the nonextractable particulate matter based on noncovalent interactions for the observed DDT-related contaminants. The release of these compounds was initiated by the modification and degradation of the organic macromolecular matrix as well as of the inorganic material. Furthermore, numerous methoxychlor-related compounds were detected not only in the extracts but also in parts of the hydrolysis products.     

Novel Amperometric Xanthine Biosensors Based on REGO-NP (Pt,Pd, and Au) Bionanocomposite Film

Amperometric biosensor was fabricated using nanocomposite film which is constructed by separate embedding of reduced expanded graphene oxide (REGO), REGO-gold, REGO-palladium, and REGO-platinum into poly(glycidyl methacrylate-co-vinylferrocene) (P(Vfc_0.4-GMA)), and by covalent immobilization of xanthine oxidase (XOD) on the surface of nanocomposite-coated electrode. Using these tailored nanocomposites and surface binding of XOD, it has been systematically studied to obtain optimum and most ideal system for xanthine detection in real samples. The best performance in xanthine detection was REGO-platinum-based nanocomposite electrode which is able to detect xanthine with sensitivity of 21.98 μA/μM it has linear range of 1 to 40 μM, low detection limit of 0.003 μM, and excellent response time of 2 s. At the end, fabricated electrode was subjected to real sample testing by measuring xanthine concentration in chicken and meat. Biosensor was found to be very reliable and with minimum interference applicable in meat freshness control as well.     

Characterization of saccharides in size-fractionated ambient particulate matter and aerosol sources: the contribution of primary biological aerosol particles (PBAPs) and soil to ambient particulate matter

Size-fractionated (equivalent to ambient PM2.5 and PM10) local soil, plant, and spore samples were collected in the Sonoran Desert near Phoenix, AZ and measured for saccharide content with the goal of characterizing ambient particulate matter sources including soil and primary biological aerosol particles (PBAPs) from plants and fungi. Different saccharide compositions were observed among soil, plant, and spore samples and between PM2.5 and PM10 fractions. The total measured nonlevoglucosan saccharide content relative to PM mass in ambient aerosols collected in a Phoenix suburb (Higley) was much higher compared to the local soil samples but much lower compared to the PBAP. The enrichment of saccharides from two saccharide-dominated PM source factors resolved by a positive matrix factorization model is also higher than the saccharide content in the size-fractionated local soil samples, but lower than that measured in the size-segregated PBAP samples. This indicates that ambient concentration of particulate saccharides at Higley was dominated by contributions from PBAPs directly injected into the atmosphere from plants and spores rather than from soil and associated biota. Our results also suggest the contribution to the fine size fraction of ambient PM from the primary biologically derived sources may be greater than previously acknowledged.     

On-road particulate matter (PM2.5 and PM10) emissions in the Sepulveda Tunnel, Los Angeles, California

Total and speciated particulate matter (PM2.5 and PM10) emission factors from in-use vehicles were measured for a mixed light- (97.4% LD) and heavy-duty fleet (2.6% HD) in the Sepulveda Tunnel, Los Angeles, CA. Seventeen 1-h test runs were performed between July 23, 1996, and July 27, 1996. Emission factors were calculated from mass concentration measurements taken at the tunnel entrance and exit, the volume of airflow through the tunnel, and the number of vehicles passing through the 582 m long tunnel. For the mixed LD and HD fleet, PM2.5 emission factors in the Sepulveda Tunnel ranged from 0.016 (+/-0.007) to 0.115 (+/-0.019) g/vehicle-km traveled with an average of 0.052 (+/-0.027) g/vehicle.km. PM10 emission factors ranged from 0.030 (+/-0.009) to 0.131 (+/-0.024) g/vehicle. km with an average of 0.069 (+/-0.030) g/vehicle.km. The PM2.5 emission factor was approximately 74% of the PM10 factor. Speciated emission rates and chemical profiles for use in receptor modeling were also developed. PM2.5 was dominated by organic carbon (OC) (31.0 +/- 19.5%) and elemental carbon (EC) (48.5 +/- 20.5%) that together account for 79% (+/-24%) of the total emissions. Crustal elements (Fe, Mg, Al, Si, Ca, and Mn) contribute approximately 7.8%, and the ions Cl-, NO3-, NH3+, SO4(2-), and K+ together constitute another 9.8%. In the PM10 size fraction the particulate emissions were also dominated by OC (31 +/- 12%) and EC (35 +/- 13%). The third most prominent species was Fe (18.5 +/- 9.0%), which is greater than would be expected from purely geological sources. Other geological components (Mg, Al, Si, K, Ca, and Mn) accounted for an additional 12.6%. PM10 emission factors showed some dependence on vehicle speed, whereas PM2.5 did not. For test runs in which the average vehicle speed was 42.6 km/h a 1.7 times increase in PM10 emission factor was observed compared to those runs with an average vehicle speed of 72.6 km/h. Speciated emissions were similar. However, there is significantly greater mass attributable to geological material in the PM10, indicative of an increased contribution from resuspended road dust. The PM2.5 shows relatively good correlation with NOx emissions, which indicates that even at the low percent of HD vehicles, which emit significantly more NOx than LD vehicles, they may also have a significant impact on the PM2.5 levels.     

Variation in the sensitivity of predicted levels of atmospheric organic particulate matter (OPM)

This study examines the sensitivity in predicted levels of atmospheric organic particulate matter (M(o), microg m(-3)) to changes in the governing gas/particle partitioning constants and the tau(I) (levels of condensable organic compounds, microg m(-3)). M(o) is given by the difference between sigma tau(i) and the corresponding sum for the gas-phase levels. It is demonstrated that the sensitivity in predicted M(o) levels increases rapidly as M(o) becomes very small relative to sigma tau(i): as the tau(i), decrease, the gas phase becomes increasingly capable of holding the majority of all tau(i) and small changes in system parameters can cause large relative changes in M(o). These effects are illustrated using predictions for two values of the reacted hydrocarbon concentration (deltaHC) for each of three secondary organic aerosol systems for relative humidity (RH) = 20-80%. Specific structures for the oxidation products allows consideration of the effects of varying activity coefficients and water uptake. At low M(o)/sigma tau(i) (as may be found in the atmosphere away from sources and at warm temperatures), relatively small errors in model input parameters (e.g., vapor pressures, vaporization enthalpies, activity coefficient parameters, and the tau(i) values for low volatility compounds) will be amplified into large errors in the predicted M(o) values.     

Fractionation of platinum group elements in aqueous systems: comparative kinetics of palladium and platinum removal from seawater by Ulva lactuca L

A marine macroalga, Ulva lactuca L., was used as a substrate to compare the kinetics of palladium (Pd) and platinum (Pt) removal from seawater. This work indicates that, while the equilibrium behaviors of Pd and Pt are in many respects similar, their kinetic behaviors are quite distinct. The removal of both Pt(II) and Pt(IV) from seawater by U. lactuca is slower than the removal of Pd(II) by approximately an order of magnitude. Relative Pd and Pt removal rates are strongly influenced by system hydrodynamics. Under quiescent conditions, lambda(Pd)/lambda(Pt), the ratio of Pd and Pt removal rates, is 7 +/- 2, whereas under turbulent conditions lambda(Pd)/lambda(Pt) can be as large as 27. These observations suggest that the disparate kinetic behaviors of Pd and Pt may produce considerable differences in the environmental dispersion of these elements.     

Collection of ultrafine diesel particulate matter (DPM) in cylindrical single-stage wet electrostatic precipitators

Long-term exposures to diesel particulate matter (DPM) emissions are linked to increasing adverse human health effects due to the potential association of DPM with carcinogenicity. Current diesel vehicular particulate emission regulations are based solely upon total mass concentration, albeit it is the submicrometer particles that are highly respirable and the most detrimental to human health. In this study, experiments were performed with a tubular single-stage wet electrostatic precipitator (wESP) to evaluate its performance for the removal of number-based DPM emissions. A nonroad diesel generator utilizing a low sulfur diesel fuel (500 ppmw) operating under varying load conditions was used as a stationary DPM emission source. An electrical low-pressure impactor (ELPI) was used to quantify the number concentration distributions of diesel particles in the diluted exhaust gas at each tested condition. The wESP was evaluated with respect to different operational control parameters such as applied voltage, gas residence time, etc., to determine their effect on overall collection efficiency, as well as particle size dependent collection efficiency. The results show that the total DPM number concentrations in the untreated diesel exhaust are in the magnitude of approximately108/cm(3) at all engine loads with the particle diameter modes between 20 and 40 nm. The measured collection efficiency of the wESP operating at 70 kV based on total particle numbers was 86% at 0 kW engine load and the efficiency decreased to 67% at 75 kW due to a decrease in gas residence time and an increase in particle concentrations. At a constant wESP voltage of 70 kV and at 75 kW engine load, the variation of gas residence time within the wESP from approximately 0.1 to approximately 0.4 s led to a substantial increase in the collection efficiency from 67% to 96%. In addition, collection efficiency was found to be directly related to the applied voltage, with increasing collection efficiency measured for increases in applied voltage. The collection efficiency based on particle size had a minimum for sizes between 20 and 50 nm, but at optimal wESP operating conditions it was possible to remove over 90% of all particle sizes. A comparison of measured and calculated collection efficiencies reveals that the measured values are significantly higher than the predicted values based on the well-known Deutsch equation.     

Changes in palladium, platinum, and rhodium concentrations, and their spatial distribution in soils along a major highway in Germany from 1994 to 2004

Soil samples were collected along the highway A5 from the major junctions Frankfurter Kreuz to Darmst?der Kreuz from July to September, 2004 and analyzed for palladium (Pd), platinum (Pt), and rhodium (Rh). The results were compared to analyses of platinum group elements (PGE) in soils collected along this same stretch of highway in 1994. The goal of this study is to detect any changes that may have occurred in the concentration and environmental distribution patterns of these metals over this 10 year period. The concentrations of Pd in soils along the highway were found to be about 15 times higher on average than those measured in 1994. Pt and Rh concentrations increased 2 and 1.6 times, respectively, during this time period. The significant rise in Pd concentrations in soils observed for the time period of analysis is likely due to its use in automobile catalytic converters in Germany since 1993. The results also show a strong positive relationship between PGE emissions and traffic density and speed. The results indicate that increases in the concentrations of Pd, Pt, and Rh in soils along the highway are not limited to the soil surface. Pt was measured as deep as 12 cm. Pd was determined at even greater depths of 12-16 cm. The presence of Pd at lower depths compared to Pt suggests that this element has a higher solubility. Pd, Pt, and Rh concentrations display a strong inverse relationship with distance from the road, with decreasing levels with increasing distance from the highway. Nonetheless, Pd and Pt were detected in a meadow as far as 50 m from the highway, a much greater distance compared to that measured for these metals in 1994. Pt concentrations were also found to significantly correlate with levels of Rh and Pd. The ratios between the PGE analyzed (Pt/Rh and Pd/Rh) display a shift toward Pt and Pd. The results clearly show that PGE concentrations have increased over time. Observed increases in Pd concentrations are particularly a cause of concern.     

Concentration and particle size of airborne toxic algae (brevetoxin) derived from ocean red tide events

Red tides in the Gulf of Mexico are formed by blooms of the dinoflagellate Karenia brevis, which produces brevetoxins (PbTx). Brevetoxins can be transferred from water to air in the wind-powered whitecapped waves during red tide episodes. Inhalation exposure to marine aerosol containing PbTx causes respiratory problems. A liquid chromatograph/ tandem mass spectrometric method was developed for the detection and quantitation of several PbTxs in ambient samples collected during red tide events. This method was complemented by a previously developed antibody assay that analyzes the entire class of PbTx compounds. The method showed good linearity, accuracy, and reproducibility, allowing quantitation of PbTx compounds in the 10 pg/m3 range. Air concentrations of PbTxs and brevenal for individual samples ranged from 0.01 to 80 ng/m3. The particle size showed a single mode with a mass median diameter between 6 and 10 microm, which was consistent for all of the PbTx species that were measured. Our results imply that individual PbTxs were from the same marine aerosol or from marine aerosol that was produced from the same process. The particle size indicated the likelihood of high deposition efficiency in the respiratory tract with the majority of aerosol deposited in the upper airways and small but not insignificant deposition in the lower airways.     

Single-particle SEM-EDX analysis of iron-containing coarse particulate matter in an urban environment: sources and distribution of iron within Cleveland, Ohio

The physicochemical properties of coarse-mode, iron-containing particles and their temporal and spatial distributions are poorly understood. Single-particle analysis combining X-ray elemental mapping and computer-controlled scanning electron microscopy (CCSEM-EDX) of passively collected particles was used to investigate the physicochemical properties of iron-containing particles in Cleveland, OH, in summer 2008 (Aug-Sept), summer 2009 (July-Aug), and winter 2010 (Feb-March). The most abundant classes of iron-containing particles were iron oxide fly ash, mineral dust, NaCl-containing agglomerates (likely from road salt), and Ca-S containing agglomerates (likely from slag, a byproduct of steel production, or gypsum in road salt). The mass concentrations of anthropogenic fly ash particles were highest in the Flats region (downtown) and decreased with distance away from this region. The concentrations of fly ash in the Flats region were consistent with interannual changes in steel production. These particles were observed to be highly spherical in the Flats region, but less so after transport away from downtown. This change in morphology may be attributed to atmospheric processing. Overall, this work demonstrates that the method of passive collection with single-particle analysis by electron microscopy is a powerful tool to study spatial and temporal gradients in components of coarse particles. These gradients may correlate with human health effects associated with exposure to coarse-mode particulate matter.     

The distribution of trace elements in cocksfoot (Dactylis glomerata) at flowering

Comparison of the contents of 24 trace and major elements in the various parts of cocksfoot at the flowering stage shows marked diversity in the distribution of the elements. The different plant parts contribute very different amounts of different elements. The stem, which accounts for 54% of the dry matter, generally contributes most, although on a dry matter basis there is seldom concentration in the stem. Concentration occurs mainly in the leaves and the spikelets which respectively contribute 9 per cent and 20 per cent of the dry matter. The spikelets contain nearly half of the Ni, Zn and Si. Calcium is relatively most abundant in the leaf: only Ni, Se and P do not show concentration in this organ. The contributions of elements by the sheath seldom differ much from its dry matter contribution of 17 per cent. Considerable differences also occur between the same organs from different nodes: the rachis leaf contains 8 times as much Zn as the lowest leaves. The possible significance to animal nutrition of the distribution in different plant parts is pointed out.     

Mobilization, adsorption, and bioavailability of Pt and Pd in coastal sediments: the role of the polychaete, Arenicola marina

The biogeochemical behavior of Pt and Pd in coastal sediments has been examined in a series of microcosms, both in the presence and absence of the deposit-feeding invertebrate, Arenicola marina. When metals were introduced to the overlying water column as solutes from acidified standards, A. marina dramatically enhanced their sorption to sediment throughout the core depth (14 cm) compared with an unfaunated control by exposing a greater surface area of particles to more rapidly ventilating contaminated water. After a 10 day incubation period, the assimilation efficiency (AE) by A. marina was about 10% for Pt and 1% for Pd. Calculations based on either partition constants or operational measures of metal bioaccessibility in sediment (using the protein, BSA) suggested that both aqueous and dietary sources of metal were important When Pt and Pd were introduced to the sediment-water interface as components of ground catalytic converter particles, significant subduction was effected by A. marina, and metals were solubilized to a greater extent than in an unfaunated control. AE in these experiments was < 0.1% for Pt and about 1% for Pd, and the most important vector for assimilation appeared to be from the aqueous phase via partial solubilization of metal from catalytic material. The findings of this study improve our understanding of the availability, cycling, and fate of Pt and Pd in contaminated estuaries and coastal waters.     

Latitudinal gradient of airborne polyfluorinated alkyl substances in the marine atmosphere between Germany and South Africa (53 degrees N-33 degrees S)

Neutral, volatile polyfluorinated alkyl substances (PFAS) were determined in high-volume air samples collected onboard the German research vessel Polarstern during cruise ANTXXIII-1 between Bremerhaven, Germany (53 degrees N) and Capetown, Republic of South Africa (33 degrees S) in fall 2005. An optimized and validated analytical protocol was used for the determination of several fluorotelomer alcohols (FTOHs) as well as N-alkylated fluorooctane sulfonamides and sulfonamidoethanols (FOSAs/FOSEs). Quantitative analyses were done by gas chromatography-mass spectrometry. This study provides the first concentration data of airborne PFAS from the Southern Hemisphere. Results indicate a strongly decreasing concentration gradient from the European continent toward less industrialized regions. The study confirms that airborne PFAS are mainly restricted to the Northern Hemisphere with a maximum concentration of 190 pg/m3 (8:2 FTOH) in the first sample collected in the channel between the European mainland and the UK. However, south of the equator, trace amounts of several FTOHs and FOSAs with a maximum of 14 pg/m3 (8:2 FTOH) could still be detected. Furthermore, a selection of ionic PFAS including perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) were determined in the particulate phase of high-volume air samples by liquid chromatography-mass spectrometry. Levels of ionic PFAS were almost 2 orders of magnitude lower than those of neutral PFAS, with maximum concentrations in the first sample of 2.5 pg/m3 (PFOS) and 2.0 pg/m3 (PFOA).     

Carbon speciation of diesel exhaust and urban particulate matter NIST standard reference materials with C(1s) NEXAFS spectroscopy

The U.S. National Institute of Standards and Technology (NIST) provides a number of particulate matter (PM) standard reference materials (SRM) for use in environmental and toxicological methodology and research. We present here the first analysis with respect to the molecular structure of the carbon in three such NIST SRM samples, i.e., diesel engine exhaust soot from heavy duty equipment engines (SRM 1650), diesel soot from a forklift engine (SRM 2975), and urban PM collected in St. Louis, MO (SRM 1648), with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The NEXAFS spectra of the two diesel soot samples appear quite similar, while they differ significantly from the urban PM spectrum, in agreement with X-ray diffraction data published recently. Such comparison is made in terms of aromatic and aliphatic carbon species, as well as by a general comparison with graphitic materials. Both diesel soot SRM samples contain basic graphitic structures, but the presence of exciton resonance and extended X-ray absorption fine structure oscillations in SRM 1650 and the lack therof in SRM 2975 suggest that SRM 1650 is the more graphitic material.The presence of polycyclic aromatic hydrocarbons, which have a characteristic NEXAFS resonance at the same position as graphite, can obscure the graphitic character of soot, unless an extraction of the organic matter is made. Our NEXAFS data do not suggest that the urban PM sample SRM 1648 contains a substantial amount of graphite-like material.     

Chemical characterization and redox potential of coarse and fine particulate matter (PM) in underground and ground-level rail systems of the Los Angeles Metro

A campaign was conducted to assess personal exposure of coarse (2.5 μm < d(p) < 10 μm) and fine (d(p) < 2.5 μm) PM for two lines of the L.A. Metro-a subway (red) and light-rail (gold) line. Concurrent measurements were taken at University of Southern California (USC) to represent ambient conditions. A comprehensive chemical analysis was performed including total and water-soluble metals, inorganic ions, elemental and organic carbon, and organic compounds. Mass balance showed that in coarse PM, iron makes up 27%, 6%, and 2% of gravimetric mass for the red line, the gold line, and USC, respectively; in fine PM, iron makes up 32%, 3%, and 1%. Ambient air is the primary source of inorganic ions and organic compounds for both lines. Noncrustal metals, particularly Cr, Mn, Co, Ni, Mo, Cd, and Eu, were elevated for the red line and, to a lesser degree, the gold line. Mo exhibited the greatest crustal enrichment factors. The enriched species were less water-soluble on the red line than corresponding species on the gold line. Bivariate analysis showed that reactive oxygen species (ROS) activity is strongly correlated with water-soluble Fe (R(2) = 0.77), Ni (R(2 )= 0.95), and OC (R(2 )= 0.92). A multiple linear regression model (R(2) = 0.94, p < 0.001) using water-soluble Fe and OC as predictor variables was developed to explain the variance in ROS. In addition, PM from the red line generates 65% and 55% more ROS activity per m(3) of air than PM from USC and the gold line, respectively; however, one unit of PM mass from the gold line may be as intrinsically toxic as one unit of PM from the red line.     

Temporal and spatial studies of autocatalyst-derived platinum, rhodium, and palladium and selected vehicle-derived trace elements in the environment

The distribution of platinum, rhodium, and palladium (platinum-group elements; PGEs) adjacent to two major U.K. roads shows a rapid decrease (more than 1 order of magnitude) away from the road and reflects patterns shown by other traffic-derived trace elements such as Pb and Zn. However, ratios of Pt:Rh remain relatively constant from 0 to 10 m distance, suggesting that at least some of the PGEs are transported away from the source. A temporal study over a 12-month period, of road dust and surface samples, reveals elevated concentrations above background levels, with maximum values of Pt >500 ng g(-1), Rh 70 ng g(-1), and Pd 70 ng g(-1). Concentrations vary considerably throughout the year and show some tentative correlation with rainfall. Element speciation, an essential control on mobility and hence distribution, was investigated, and the results of solubility experiments show that up to 30% of the Pd present dissolves in acid solutions. This indicates that at least some of the Pd is present in a soluble form and is therefore potentially highly mobile.