Measurements of size-segregated emission particles by a sampling system based on the cascade impactor

A special sampling system for measurements of size-segregated particles directly at the source of emission was designed and constructed. The central part of this system is a low-pressure cascade impactor with 10 collection stages for the size ranges between 15 nm and 16 microm. Its capability and suitability was proven by sampling particles atthe stack (100 degrees C) of a coal-fired power station in Slovenia. These measurements showed very reasonable results in comparison with a commercial cascade impactor for PM10 and PM2.5 and with a plane device for total suspended particulate matter (TSP). The best agreement with the measurements made by a commercial impactor was found for concentrations of TSP above 10 mg m(-3), i.e., the average PM2.5/PM10 ratios obtained by a commercial impactor and by our impactor were 0.78 and 0.80, respectively. Analysis of selected elements in size-segregated emission particles additionally confirmed the suitability of our system. The measurements showed that the mass size distributions were generally bimodal, with the most pronounced mass peak in the 1-2 microm size range. The first results of elemental mass size distributions showed some distinctive differences in comparison to the most common ambient anthropogenic sources (i.e., traffic emissions). For example, trace elements, like Pb, Cd, As, and V, typically related to traffic emissions, are usually more abundant in particles less than 1 microm in size, whereas in our specific case they were found at about 2 microm. Thus, these mass size distributions can be used as a signature of this source. Simultaneous measurements of size-segregated particles at the source and in the surrounding environment can therefore significantly increase the sensitivity of the contribution of a specific source to the actual ambient concentrations.     

Fingerprinting metals in urban street dust of Beijing, Shanghai, and Hong Kong

Street dust samples were taken between July and December 2005 at 25 locations in Shanghai, Beijing, and Hong Kong and sieved to 63 microm particle size before elemental analyses by CHN analyzer, XRF and ICP-MS. About 60% of the particles from the Beijing and Shanghai sieved samples were < 10 microm mean diameter, and approximately 20% were < 2 microm mean diameter, so that they are readily resuspendable and respirable with increased risk of adverse health impacts. The optical size distributions determined by electron microscopy were reasonably similar to the mass size distributions of total suspended particulate matter (TSP) at these two megacities. Hong Kong street dust particles were coarser with only about 3% of the sieved samples being < 10 microm. The elemental composition profile of Hong Kong street dust differs considerably from those of Beijing and Shanghai, being more abundant in C, S, Cr, Cu, Ce, and Zn due to higher traffic density. In particular, the vehicle contribution to Hong Kong street dust is shown by order-of-magnitude relative enhancements of Fe and Cr compared with those in TSP sampled nearby, attributed to vehicle iron and stainless-steel wear and tear and rusting contributing to street dust in the street canyons. The concentrations of Cr in Hong Kong street dust, measured from 52Cr and 53Cr by ICP-DRC-MS after a modified three-stage microwave-assisted acid digestion, are higher than those reported elsewhere.     

Variability of apparent particle density of an urban aerosol

The day to day and diurnal variation of apparent particle density was studied using highly time-resolved measurements of particle number distribution and fine-particle mass concentration. The study was conducted in Erfurt, Germany, from January 1, 1999, to November 22, 2000. A setup consisting of a differential mobility particle spectrometer and a laser aerosol spectrometer was used for particle number distribution measurements. PM2.5 particle mass was measured in parallel on an hourly basis using a tapered element oscillating microbalance (TEOM) and on daily base by using a Harvard marple impactor (HI). For the estimation of the mean apparent density of particles, number size distributions were converted into volume size distributions, assuming that the particles were spherically shaped. The volume size distributions were integrated over the range of 10 nm to 2.03 microm Stokes equivalent diameter to obtain volume concentrations. Mean apparent particle density was calculated as ratio of mass concentration and volume concentration. The mean apparent particle density, determined from HI and number size distribution on a daily basis was 1.6 +/- 0.5 g cm(-3). We found a strong day-to-day variation of apparent density ranging from 1.0 to 2.5 g cm(-3) (5th and 95th percentile). Furthermore, the apparent density showed pronounced diurnal pattern both in summer and in winter and also on weekdays and weekends. The apparent density was lowest in the morning and highest in the afternoon. The mean apparent density on an hourly basis was 1.4 +/- 0.5 and 1.5 +/- 0.5 g cm(-3) for PM2.5TEOM and corrected PM2.5TEOM using regression equation between daily mass concentration of HI and TEOM, respectively. The strong diurnal variation of apparent particle density was associated predominantly with the vertical temperature inversion and with traffic intensity. Thus, the apparent particle density depends on the physical particle properties and might be related to chemical composition of the sampled particle.     

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.     

The effects of the catalytic converter and fuel sulfur level on motor vehicle particulate matter emissions: gasoline vehicles

Scanning mobility and electrical low-pressure impactor particle size measurements conducted during chassis dynamometer testing reveal that neither the catalytic converter nor the fuel sulfur content has a significant effect on gasoline vehicle tailpipe particulate matter (PM) emissions. For current technology, port fuel injection, gasoline engines, particle number emissions are < or = 2 times higher from vehicles equipped with blank monoliths as compared to active catalysts, insignificant in contrast to the 90+% removal of hydrocarbons. PM mass emission rates derived from the size distributions are equal within the experimental uncertainty of 50-100%. Gravimetric measurements exhibit a 3-10-fold PM mass increase when the active catalyst is omitted, which is attributed to gaseous hydrocarbons adsorbing onto the filter medium. Both particle number and gravimetric measurements show that gasoline vehicle tailpipe PM emissions are independent (within 2 mg/mi) of fuel sulfur content over the 30-990 ppm concentration range. Nuclei mode sulfate aerosol is not observed in either test cell measurements or during wind tunnel testing. For three-way catalyst equipped vehicles, the principal sulfur emission is SO2; however a sulfur balance is not obtained over the drive cycle. Instead, sulfur is stored on the catalyst during moderate driving and then partially removed during high speed/load operation.     

Concentration and distribution of platinum group elements (Pt, Pd, Rh) in airborne particulate matter in Frankfurt am Main, Germany

The concentrations and distribution of platinum group elements (Pt, Pd, Rh) in airborne particulate matter were studied in a period of one year from August 2001 to July 2002 in urban and in nonurban areas. Airborne dust samples were collected as a total amount (particles with an aerodynamic diameter <22 microm) and classified using an eight-stage Andersen impactor (<10 microm) at three locations with different traffic density roads in the Frankfurt am Main and nonurban areas. Sampling at the three locations was performed simultaneously for total airborne dust and fractionated airborne dust. Pd was determined by total reflection X-ray fluorescence after Hg coprecipitation. Pt and Rh were analyzed by adsorptive striping voltammetry after HPA digestion. The results show that the PGE concentrations in airborne samples depend on the traffic density. The highest PGE concentrations in air were found in the vicinity of major roads with heavy traffic, and the lowest ones were found in the nonurban area. The presence of PGE at the sampling station relatively free of traffic in a nonurban area hints to a transport of some of the emitted PGE from the city to this station by wind. At all three sampling locations, a heterogeneous distribution of the Pd, Pt, and Rh concentrations during the sampling year can be observed. The sum of PGE concentrations in total airborne dust is comparable with the sum of impactor samples. However, the concentration of Pt and Rh in total airborne dust (<22 microm) is on average higher than in impactor samples (<10 microm). On the contrary, Pd concentration is higher in impactor samples in most cases. The airborne PGE distribution is dominated by Pt, followed by Pd and Rh. The impactor samples are dominated by Pd, followed by Pt and Rh. This fact indicates that palladium occurs mainly in relatively fine airborne particles. The main fraction of PGE is found on average in particle sizes between 1.1 and 4.7 microm. Knowledge of the size distribution of particles containing PGE is important with respect to risk assessment of human inhalation.     

PAHs, PAH-induced carcinogenic potency, and particle-extract-Induced cytotoxicity of traffic-related nano/ultrafine particles

Polycyclic aromatic hydrocarbons (PAHs) bound in nano/ ultrafine particles from vehicle emissions may cause adverse health effects. However, little is known about the characteristics of the nanoparticle-bound PAHs and the PAH-associated carcinogenic potency/cytotoxicity; therefore, traffic-related nano/ultrafine particles were collected in this study using a microorifice uniform deposition impactor(MOUDI) and a nano-MOUDI. For PM0.056--18, the difference in size-distribution of particulate total-PAHs between non-after-rain and after-rain samples was statistically significant at alpha = 0.05; however, this difference was not significant for PM0.01--0.056. The PAH correlation between PM0.01--0.1 and PM0.1--1.8 was lower for the after-rain samples than forthe non-after-rain samples. The average particulate total-PAHs in five samplings displayed a trimodal distribution with a major peak in the Aitken mode (0.032--0.056 microm). About half of the particulate total-PAHs were in the ultrafine size range. The BaPeq sums of BaP, IND, and DBA (with toxic equivalence factors > or = 0.1) accounted for approximately 90% of the total-BaPeq in the nano/ultrafine particles, although these three compounds contributed little to the mass of the sampled particles. The mean content of the particle-bound total-PAHs/-BaPeqs and the PAH/BaPeq-derived carcinogenic potency followed the order nano > ultrafine > fine > coarse. For a sunny day sample, the cytotoxicity of particle extracts (using 1:1 (v/v) n-hexane/dichloromethane) was significantly higher (p < 0.05) for the nano (particularly the 10-18 nm)/ultrafine particles than for the coarser particles and bleomycin. Therefore, traffic-related nano and ultrafine particles are possibly cytotoxic.     

Effect of engine load on diesel soot particles

This study concentrates on characterization of nonvolatile fraction of diesel particles. These particles have an impact on earth's radiation balance as well as on health effects of vehicle emissions. In addition to composition and size distribution of particles, an important factor affecting their health effects and properties and lifetimes in the atmosphere is their morphology. The effect of engine parameters on soot particle size distributions and also on particle morphology has been studied. It was found that the shape of the size distribution and also the structure of diesel particles depend on engine load. The number distributions were found to obey log-normal assumption. The width of the distribution increased with increasing engine load. The geometric standard deviations of measured distributions varied from 1.7 to 2.1. Simultaneously, the fractal dimension of particles decreased with increasing engine load. The values for mass fractal dimensions based on sealing of particle mass and mobility size were between 2.6 and 2.8. Both electron microscopy and measurements of aerodynamic size versus mobility size suggest that the morphology of particles in different size regimes vary, with the large particles being less compact than the small ones.     

Characteristics of nucleation and growth events of ultrafine particles measured in Rochester, NY

Number concentrations and size distributions of particles in the size range of 0.010-0.500 microm were measured in Rochester, NY, from December 2001 to December 2002. The relationships between the number concentrations, gaseous pollutants, and meteorological parameters were examined during particle nucleation events. More than 70% of measured total number concentration was associated with ultrafine particles (UFP, 0.011-0.050 microm). Morning nucleation events typically peaking UFP number concentrations at around 08:00 were apparent in winter months with CO increases. These particles appear to be formed following direct emissions from motorvehicles during morning rush hour. There were also often observed increases in this smaller-sized range particles in the late afternoon during the afternoon rush hour, particularly in winter when the mixing heights remain lowerthan in summer. Strong afternoon nucleation events (> 30,000 cm(-3)) peaking at around 13: 00 were more likely to occur in spiring and summer months. During the prominent nucleation events, peaks of SO2 were strongly associated with the number concentrations of UFP, whereas there were no significant correlations between these events and PM2.5 and CO. Increased SO2 concentrations were observed when the wind direction was northwesterly where three SO2 sources were located. It is hypothesized that UFP formed during the events are sulfuric acid and water from the oxidation of SO2. There were also a more limited number of nucleation events followed by particle growth up to approximately 0.1 microm over periods of up to 18 h. The nucleation and growth events tended to be common in spring months especially in April.     

A field-based approach for deterimining ATOFMS instrument sensitities to ammonium and nitrate

Aerosol time-of-flight mass spectrometry (ATOFMS) instruments measure the size and chemical composition of individual particles in real-time. ATOFMS chemical composition measurements are difficult to quantify, largely because the instrument sensitivities to different chemical species in mixed ambient aerosols are unknown. In this paper, we develop a field-based approach for determining ATOFMS instrument sensitivities to ammonium and nitrate in size-segregated atmospheric aerosols, using tandem ATOFMS-impactor sampling. ATOFMS measurements are compared with collocated impactor measurements taken at Riverside, CA, in September 1996, August 1997, and October 1997. This is the first comparison of ion signal intensities from a single-particle instrument with quantitative measurements of atmospheric aerosol chemical composition. The comparison reveals that ATOFMS instrument sensitvities to both NH4+ and NO3- decline with increasing particle aerodynamic diameter over a 0.32-1.8 microm calibration range. The stability of this particle size dependence is tested overthe broad range of fine particle concentrations (PM1.8) = 17.6 +/- 2.0-127.8 +/- 1.8 microg m(-3)), ambient temperatures (23-35 degrees C), and relative humidity conditions (21-69%), encountered during the field experiments. This paper describes a potentially generalizable methodology for increasing the temporal and size resolution of atmospheric aerosol chemical composition measurements, using tandem ATOFMS-impactor sampling.     

Size distribution of trace organic species emitted from light-duty gasoline vehicles

Size distributions for particulate hopanes+steranes and nonvolatile polycyclic aromatic hydrocarbons (PAHs) emitted from five classes of light-duty gasoline-powered vehicles were measured using the federal test procedure (FTP), unified cycle (UC), and correction cycle (CC) driving cycles. 17alpha(H)-21beta(H)-29-norhopane, 17alpha(H)-21beta(H)-hopane, alpha beta beta-20R-stigmastane, and alpha beta beta-20S-stigmastane were highly correlated and behaved consistently across sampling methods. Coronene and benzo[ghi]perylene were the most ubiquitous heavy PAHs detected in the vehicle exhaust. The emission rates of hopanes, steranes, and PAHs contained in particles with aerodynamic diameters of less than 1.8 ,m varied by 2 orders of magnitude between the lowest- and highest-emitting vehicle classes. Hopane+sterane size distributions emitted from vehicles without an operating catalyst (including "cold-start" emissions from catalyst-equipped vehicles) were bimodal with one mode between 0.10 and 0.18 microm and the second mode >0.32 microm particle diameter. Hopane+sterane emissions released from vehicles with a catalyst at operating temperature had a single mode between 0.1 and 0.18 microm diameter. Hopane+sterane emissions from visibly smoking vehicles had a single mode between 0.18 and 0.32 microm diameter. Heavy PAH size distributions for all vehicle classes consistently had a single mode between 0.10 and 0.18 microm particle diameter (0.1-0.32 microm diameter for smoking vehicles). The geometric standard deviations for PAH size distributions were generally smaller than the corresponding hopane+sterane distributions. These trends suggest that hopanes+steranes and heavy PAHs act as tracers for separate processes of particulate organic carbon formation. PAH and hopane+sterane emissions shifted to smaller sizes during the more aggressive UC and CC driving cycles relative to the FTP. The fraction of PAH and hopane+sterane emissions in the ultrafine (Dp < 0.1 microm) range more than doubled during "warm-start" UC and CC cycles vs the FTP cycle. The enhancement of ultrafine PAHs during "cold-start" UC driving cycles was less pronounced.     

Size distribution of particle-phase molecular markers during a severe winter pollution episode

Airborne particulate matter was collected using filter samplers and cascade impactors in six size fractions below 1.8 microm during a severe winter air pollution event at three sites in the Central Valley of California. The smallest size fraction analyzed was 0.056 < Dp <0.1 microm particle diameter, which accounts for the majority of the mass in the ultrafine (PM0.1) size range. Separate samples were collected during the daytime (10 a.m. to 6 p.m. PST) and nighttime (8 p.m. to 8 a.m. PST) to characterize diurnal patterns. Each sample was extracted with organic solvents and analyzed using gas chromatography mass spectrometry for molecular markers that can be used for size-resolved source apportionment calculations. Colocated impactor and filter measurements were highly correlated (R8 > 0.8) for retene, benzo[ghi]flouranthene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[e]pyrene, benzo[a]pyrene, perylene, indeno[1,2,3-cd]pyrene, benzo[ghi]perylene, coronene, MW302 polycyclic aromatic hydrocarbon (PAHs), 17beta(H)-21alpha(H)-30-norhopane, 17alpha(H)-21beta(H)-hopane, alphabetabeta-20R-C29-ethylcholestane, levoglucosan, and cholesterol. Of these compounds, levoglucosan was present in the highest concentration (60-2080 ng m(-3)) followed by cholesterol (6-35 ng m(-3)), PAHs (2-38 ng m(-3)), and hopanes and steranes (0-2 ng m(-3)). Nighttime concentrations were higher than daytime concentrations in all cases. Organic compound size distributions were generally similar to the total carbon size distributions during the nighttime but showed greater variability during the daytime. This may reflect the dominance of fresh emission in the stagnant surface layer during the evening hours and the presence of aged organic aerosol at the surface during the daytime when the atmosphere is better mixed. All of the measured organic compound particle size distributions had a single mode that peaked somewhere between 0.18 and 0.56 microm, but the width of each distribution varied by compound. Cholesterol generally had the broadest particle size distribution, while benzo[ghi]perylene and 17alpha(H)-21beta(H)-29-norhopane generally had sharper peaks. The difference between the size distributions of the various particle-phase organic compounds reflects the fact that these compounds exist in particles emitted from different sources. The results of the current study will prove useful for size-resolved source apportionment exercises.     

Relationship between particle mass and mobility for diesel exhaust particles

We used the aerosol particle mass analyzer (APM) to measure the mass of mobility-classified diesel exhaust particles. This information enabled us to determine the effective density and fractal dimension of diesel particles as a function of engine load. We found that the effective density decreases as particle size increases. TEM images showed that this occurs because particles become more highly agglomerated as size increases. Effective density and fractal dimension increased somewhat as engine load decreased. TEM images suggest that this occurs because these particles contain more condensed fuel and/or lubricating oil. Also, we observed higher effective densities when high-sulfur EPA fuel (approximately 360 ppm S) was used than for Fischer-Tropsch fuel (approximately 0 ppm S). In addition, the effective density provides the relationship between mobility and aerodynamic equivalent diameters. The relationship between these diameters enables us to intercompare, in terms of a common measure of size, mass distributions measured with the scanning mobility particle sizer (SMPS) and a MOUDI impactor without making any assumptions about particle shape or density. We show that mass distributions of diesel particles measured with the SMPS-APM are in good agreement with distributions measured with a MOUDI and a nano-MOUDI for particles larger than approximately 60 nm. However, significantly more mass and greater variation were observed by the nano-MOUDI for particles smaller than 40 nm than by the SMPS-APM.     

Determining the frequency of asbestos use in automotive brakes from a fleet of on-road California vehicles

Asbestos is a known human carcinogen, and recent regulation in California limits asbestiform fibers in brakes to trace levels beginning in 2014, although there is no corresponding federal requirement. In order to gauge the current prevalence of asbestos use in automotive brake applications, the California Air Resources Board tested brake linings from 137 light- and medium-duty vehicles and 54 heavy-duty vehicles. Only about 3% of the light- and medium-duty vehicle brake linings contained chrysotile asbestos. All of those brake linings were drum-type shoes, which are generally being phased out. No asbestos was found in low mileage vehicles presumed to have their original stock linings from the vehicle manufacturer. Additionally, no asbestos was found in the heavy-duty vehicle brake shoe linings sampled. Given the small percentage of vehicle brake linings with asbestos observed, it appears that the prior federal ban that was subsequently overturned, in combination with a threat of litigation, has reduced asbestos use in brake linings. However, our study was limited in scope and without a national ban, the current and future prevalence of asbestos in brakes is uncertain, suggesting the need for continued monitoring of materials released as toxic air contaminants in normal braking operations.     

On-road measurement of particle emission in the exhaust plume of a diesel passenger car

Particle size distributions were measured under real world dilution conditions in the exhaust plume of a diesel passenger car closely followed by a mobile laboratory on a high speed test track. Under carefully controlled conditions the exhaust plume was continuously sampled and analyzed inside the mobile laboratory. Exhaust particle size distribution data were recorded together with exhaust gas concentrations, i.e., CO, CO2, and NO(x), and compared to data obtained from the same vehicle tested on a chassis dynamometer. Good agreement was found for the soot mode particles which occurred at a geometric mean diameter of approximately 50 nm and a total particle emission rate of 10(14) particles km(-1). Using 350 ppm high sulfur fuel and the standard oxidation catalyst a bimodal size distribution with a nucleation mode at 10 nm was observed at car velocities of 100 km h(-1) and 120 km h(-1), respectively. Nucleation mode particles were only present if high sulfur fuel was used with the oxidation catalyst installed. This is in agreement with prior work that these particles are of semivolatile nature and originate from the nucleation of sulfates formed inside the catalyst. Temporal effects of the occurrence of nucleation mode particles during steady-state cruising and the dynamical behavior during acceleration and deceleration were investigated.     

Electrostatic precipitator performance and trace element emissions from two Kraft recovery boilers

Fine particle emissions from combustion sources have gained attention recently due to their adverse effects on human health. The emission depends on the combustion process, fuel, and particulate removal technology. Particle concentrations at Kraft recovery boiler exits are very high, and the boilers are typically equipped with electrostatic precipitators (ESP). However, little data are available on the ESP performance in recovery boilers. Particle concentrations and size distributions were determined at two modern, operating recovery boilers. In addition, we determined the fractional collection efficiency of the ESPs by simultaneous measurements at the ESP inlet and outlet and the particulate emissions of trace metals. The particle mass concentration atthe ESP inlet was 11-24 g/Nm3 at the two boilers. Particle emissions were 30-40 mg/ Nm3 at boiler A and 12-15 mg/Nm3 at boiler B. The particle size distributions had a major particle mode at around 1 microm. These fume particles contained most of the particle mass. The main components in the particles were sodium and sulfate with minor amounts of chloride, potassium, and presumably some carbonate. The ESP collection efficiency was 99.6-99.8% at boiler A and 99.9% at boiler B. The particle penetration through the ESP was below 0.6% in the entire fume particle size range of 0.3-3 microm. Trace element emissions from both boilers were well below the limit values set by EU directive for waste incineration.     

Chemical and physical properties of ultrafine diesel exhaust particles sampled downstream of a catalytic trap

The chemical and physical properties of exhaust particles produced by a Caterpillar 3176 C-12 heavy duty diesel engine equipped with a catalytic trap (CRT) are reported. The engine was operated at 600 Nm and 1500 rpm, using fuels containing 15 and 49 ppm sulfur. A two-stage dilution tunnel designed to simulate the reactions that occur when hot combustion products mix with cooler atmospheric air was used. Particle size distributions were measured using a scanning mobility particle sizer (SMPS) and nano-scanning mobility particle sizer (nano SMPS); a nanomicro-orifice uniform deposit impactor (nano MOUDI) collected size-resolved samples for gravimetric and chemical analysis. A nanometer tandem differential mobility analyzer (nano TDMA) was used to measure the volatility and hygroscopicity of 4-15 nm particles. These measurements confirm that the particles consisted primarily of sulfates.     

Trace metals in ambient air: Hourly size-segregated mass concentrations determined by synchrotron-XRF

Trace metals are ubiquitous in urban ambient air, with mass concentrations in the range of a few microg/m3 down to less than 100 pg/m3. To measure such low concentrations represents a challenge for chemical and physical analysis. In this study, ambient aerosol was collected in Zürich (Switzerland) in 1-h intervals and three size fractions (aerodynamic diameters 0.1-1 microm, 1-2.5 microm, and 2.5-10 microm), using a three-stage rotating drum impactor (RDI). The samples were analyzed by energy-dispersive Synchrotron radiation X-ray fluorescence spectrometry (SR-XRF) to obtain size-segregated hourly elemental aerosol mass concentrations for Cr, Mn, Fe, Cu, Zn, Br, and Pb, along with S, Cl, and Ca under the selected experimental conditions. The high sensitivity of SR-XRF allowed for detection limits of <50 pg/m3 for most of the above elements, with a net analysis time of only 15 s per sample. The data obtained with this technique illustrate that there is a considerable gain of relevant information when time resolution for measurements is increased from 1 day to 1 h. The individual size fractions of a specific element may show significantly different short-term patterns.