Ultrafine Size Range Research Articles

Size-resolved source apportionment of ambient particles by positive matrix factorization at Gosan background site in East Asia

Abstract. Size- and time-resolved aerosol samples were collected using an eight-stage Davis rotating unit for monitoring (DRUM) sampler from 29 March to 29 May in 2002 at Gosan, Jeju Island, Korea, which is one of the representative background sites in East Asia. These samples were analyzed using synchrotron X-ray fluorescence for 3-h average concentrations of 19 elements consisting of S, Si, Al, Fe, Ca, Cl, Cu, Zn, Ti, K, Mn, Pb, Ni, V, Se, As, Rb, Cr, Br. The size-resolved data sets were then analyzed using the positive matrix factorization (PMF) technique in order to identify possible sources and estimate their contribution to particulate matter mass. PMF analysis uses the uncertainty of the measured data to provide an optimal weighting. Fifteen sources were resolved in eight size ranges (0.07~12 μm) and included continental soil, local soil, sea salt, biomass/biofuel burning, coal combustion, oil heating furnace, residual oil fired boiler, municipal incineration, nonferrous metal source, ferrous metal source, gasoline vehicle, diesel vehicle, copper smelter and volcanic emission. PMF analysis of size-resolved source contributions showed that natural sources represented by local soil, sea salt and continental soil contributed about 79% to the predicted primary particulate matter (PM) mass in the coarse size range (1.15~12 μm). On the other hand, anthropogenic sources such as coal combustion and biomass/biofuel burning contributed about 60% in the fine size range (0.56~2.5 μm). The diesel vehicle source contributed the most in the ultra-fine size range (0.07~0.56 μm) and was responsible for about 52% of the primary PM mass.

Weak correlation of ultrafine aerosol particle concentrations <800 nm between two sites within one city

Ambient aerosol has been identified as a major pollutant affecting human health. Standards to reduce particles mass concentrations have therefore been established in many countries. Recent studies suggest that the number concentration of aerosol particles, which is dominated by the ultrafine size range smaller than 100 nm in diameter, may be independently associated with health effects. Currently, epidemiological evidence for such effects is conflicting. We have measured aerosol size distributions at two stations (urban background, street canyon) located at a distance of 1.5 km for a time period of 1 year. Number concentrations and particle size distributions at both sites were significantly different. Short-term correlation between the two sites was weak for individual measurements of number concentrations and size bins of ultrafine particles (0.19-0.46). Correlation coefficients for hourly and daily averages in selected size ranges ranged from 0.35 to 0.46. On the other hand, the correlation coefficient for daily average particle volume concentrations was found to be 0.67. About 10% to 20% of the population of European cities lives close to roads with traffic densities comparable to our site. The underestimation of the exposure of a considerable part of a study population may therefore severely influence the outcome of epidemiological studies focused on health effects associated with ultrafine particles. A single background measurement site may not be sufficient for exposure assessment in these studies without taking spatial and temporal variability into account.

Determination of Single Particle Mass Spectral Signatures from Light-Duty Vehicle Emissions

In this study, 28 light-duty gasoline vehicles (LDV) were operated on a chassis dynamometer at the California Air Resources Board Haagen-Smit Facility in El Monte, CA. The mass spectra of individual particles emitted from these vehicles were measured using aerosol time-of-flight mass spectrometry (ATOFMS). A primary goal of this study involves determining representative size-resolved single particle mass spectral signatures that can be used in future ambient particulate matter source apportionment studies. Different cycles were used to simulate urban driving conditions including the federal testing procedure (FTP), unified cycle (UC), and the correction cycle (CC). The vehicles were selected to span a range of catalytic converter (three-way, oxidation, and no catalysts) and engine technologies (vehicles models from 1953 to 2003). Exhaust particles were sampled directly from a dilution and residence chamber system using particle sizing instruments and an ATOFMS equipped with an aerodynamic lens (UF-ATOFMS) analyzing particles between 50 and 300 nm. On the basis of chemical composition, 10 unique chemical types describe the majority of the particles with distinct size and temporal characteristics. In the ultrafine size range (between 50 and 100 nm), three elemental carbon (EC) particle types dominated, all showing distinct EC signatures combined with Ca, phosphate, sulfate, and a lower abundance of organic carbon (OC). The relative fraction of EC particle types decreased as particle size increased with OC particles becoming more prevalent above 100 nm. Depending on the vehicle and cycle, several distinct OC particle types produced distinct ion patterns, including substituted aromatic compounds and polycyclic aromatic hydrocarbons (PAH), coupled with other chemical species including ammonium, EC, nitrate, sulfate, phosphate, V, and Ca. The most likely source of the Ca and phosphate in the particles is attributed to the lubricating oil. Significant variability was observed in the chemical composition of particles emitted within the different car categories as well as for the same car operating under different driving conditions. Two-minute temporal resolution measurements provide information on the chemical classes as they evolved during the FTP cycle. The first two minutes of the cold start produced more than 5 times the number of particles than any other portion of the cycle, with one class of ultrafine particles (EC coupled with Ca, OC, and phosphate) preferentially produced. By number, the three EC with Ca classes (which also contained OC, phosphate, and sulfate) were the most abundant classes produced by the nonsmoking vehicles. The smoker category produced the highest number of particles, with the dominant classes being OC comprised of substituted monoaromatic compounds and PAHs, coupled with Ca and phosphate, thus suggesting used lubricating oil was associated with many of these particles. These studies show, by number, EC particles dominate gasoline emissions in the ultrafine size range particularlyforthe lowest emitting newer vehicles, suggesting the EC signature alone cannot be used as a unique tracer for diesels. This represents the first report of high time- and size-resolved chemical composition data showing the mixing state of nonrefractory elements in particles such as EC for vehicle emissions during dynamometer source testing.

Ultrafine particle deposition in subjects with asthma.

Ambient air particles in the ultrafine size range (diameter < 100 nm) may contribute to the health effects of particulate matter. However, there are few data on ultrafine particle deposition during spontaneous breathing, and none in people with asthma. Sixteen subjects with mild to moderate asthma were exposed for 2 hr, by mouthpiece, to ultrafine carbon particles with a count median diameter (CMD) of 23 nm and a geometric standard deviation of 1.6. Deposition was measured during spontaneous breathing at rest (minute ventilation, 13.3 +/- 2.0 L/min) and exercise (minute ventilation, 41.9 +/- 9.0 L/min). The mean +/- SD fractional deposition was 0.76 +/- 0.05 by particle number and 0.69 +/- 0.07 by particle mass concentration. The number deposition fraction increased as particle size decreased, reaching 0.84 +/- 0.03 for the smallest particles (midpoint CMD = 8.7 nm). No differences between sexes were observed. The deposition fraction increased during exercise to 0.86 +/- 0.04 and 0.79 +/- 0.05 by particle number and mass concentration, respectively, and reached 0.93 +/- 0.02 for the smallest particles. Experimental deposition data exceeded model predictions during exercise. The deposition at rest was greater in these subjects with asthma than in previously studied healthy subjects (0.76 +/- 0.05 vs. 0.65 +/- 0.10, p < 0.001). The efficient respiratory deposition of ultrafine particles increases further in subjects with asthma. Key words: air pollution, asthma, deposition, dosimetry, inhalation, ultrafine particles.

Oxidative stress and NFκB activation in the lungs of rats: a synergistic interaction between soot and iron particles

Particulate matter (PM) has been associated with a variety of adverse health effects primarily involving the cardiopulmonary system. However, the precise biological mechanisms to explain how exposure to PM exacerbates or directly causes adverse effects are unknown. Particles of varying composition may play a critical role in these effects. To study such a phenomenon, a simple, laminar diffusion flame was used to generate aerosols of soot and iron particles in the ultrafine size range. Exposures of healthy adult rats were for 6 h/day for 3 days. Conditions used included exposure to soot only, iron only, or a combination of soot and iron. We found animals exposed to soot particles at 250 μg/m 3 had no adverse respiratory effects. Exposure to iron alone at a concentration of 57 μg/m 3 also had no respiratory effects. However, the addition of 45 μg/m 3 of iron to soot with a combined total mass concentration of 250 μg/m 3 demonstrated significant pulmonary ferritin induction, oxidative stress, elevation of IL-1β, and cytochrome P450s, as well as activation of NFκB. These findings suggest that a synergistic interaction between soot and iron particles account for biological responses not found with exposure to iron alone or to soot alone.

Airborne particles of the california central valley alter the lungs of healthy adult rats.

Epidemiologic studies have shown that airborne particulate matter (PM) with a mass median aerodynamic diameter < 10 microm (PM10) is associated with an increase in respiratory-related disease. However, there is a growing consensus that particles < 2.5 microm (PM2.5), including many in the ultrafine (< 0.1 microm) size range, may elicit greater adverse effects. PM is a complex mixture of organic and inorganic compounds; however, those components or properties responsible for biologic effects on the respiratory system have yet to be determined. During the fall and winter of 2000-2001, healthy adult Sprague-Dawley rats were exposed in six separate experiments to filtered air or combined fine (PM2.5) and ultrafine portions of ambient PM in Fresno, California, enhanced approximately 20-fold above outdoor levels. The intent of these studies was to determine if concentrated fine/ultrafine fractions of PM are cytotoxic and/or proinflammatory in the lungs of healthy adult rats. Exposures were for 4 hr/day for 3 consecutive days. The mean mass concentration of particles ranged from 190 to 847 microg/m3. PM was enriched primarily with ammonium nitrate, organic and elemental carbon, and metals. Viability of cells recovered by bronchoalveolar lavage (BAL) from rats exposed to concentrated PM was significantly decreased during 4 of 6 weeks, compared with rats exposed to filtered air (p< 0.05). Total numbers of BAL cells were increased during 1 week, and neutrophil numbers were increased during 2 weeks. These observations strongly suggest exposure to enhanced concentrations of ambient fine/ultrafine particles in Fresno is associated with mild, but significant, cellular effects in the lungs of healthy adult rats.

Pronounced decrease of ambient particle number emissions from diesel traffic in Denmark after reduction of the sulphur content in diesel fuel

Measurements of particle number concentration and size distributions in a Copenhagen street canyon in January–March 1999, and one year later in 2000, have revealed that the number of particles in the ultrafine size range below 100 nm decreased significantly in the period between the two campaigns. The decrease was especially large in the size range below 30 nm. By two common factors, we found high co-variance between ultrafine particles, nitrogen oxides, and carbon monoxide. The co-variation can be used to assess the contributions and size distributions of particles from the two main sources, petrol traffic and diesel traffic. Here, we show that the drop in particle concentrations can be consistently explained by a 56% fall in the average particle emission from the diesel vehicles in the street. In the same period, we found no change in the particle emission from petrol cars. The change is probably due to the reduction of the sulphur content in diesel fuel from approximately 0.05% to less than 0.005%, implemented in all parts of Denmark in July 1999.

Detection of alkaline ultrafine atmospheric particles at Bakersfield, California.

Two collected micro-orifice uniform deposit impactors (MOUDIs) and a filter-based sampler were used to measure the size distribution and chemical composition of atmospheric particulate matter at Bakersfield, CA, between January 14 and 23, 1999. The peak number concentration of airborne ultrafine particles measured was 1.45 x 10(11) m-3, which is a factor of approximately 3 higher than the peak airborne ultrafine-particle number concentration measured previously in Pasadena, CA. Chemical analysis revealed that airborne ultrafine particles (Dp < 0.1 micron) at Bakersfield contained significant amounts of water-soluble species, including calcium, sodium, ammonium ion, nitrate, and sulfate. Other chemical species detected in the ultrafine size range included potassium, iron, copper, zinc, and strontium. A balance of aqueous ions showed that ultrafine particles were alkaline in nature with calcium acting as the dominant cation. Bulk samples of airborne particles with diameter less than 2.0 microns (PM2.0) were essentially neutral, but particle acidity was found to be a strong function of particle size. The results of this experiment suggest that areas deep in the human lung that preferentially collect particles in the ultrafine size range could be exposed to locally acidic or alkaline conditions even if the integrated airborne particle complex is essentially neutral.

Number concentration and size of particles in urban air: effects on spirometric lung function in adult asthmatic subjects.

Daily variations in ambient particulate air pollution are associated with variations in respiratory lung function. It has been suggested that the effects of particulate matter may be due to particles in the ultrafine (0.01-0.1 microm) size range. Because previous studies on ultrafine particles only used self-monitored peak expiratory flow rate (PEFR), we assessed the associations between particle mass and number concentrations in several size ranges measured at a central site and measured (biweekly) spirometric lung function among a group of 54 adult asthmatics (n = 495 measurements). We also compared results to daily morning, afternoon, and evening PEFR measurements done at home (n = 7,672-8,110 measurements). The median (maximum) 24 hr number concentrations were 14,500/cm(3) (46,500/cm(3)) ultrafine particles and 800/cm(3) (2,800/cm(3)) accumulation mode (0.1-1 microm) particles. The median (maximum) mass concentration of PM(2.5) (particulate matter < 2.5 microm) and PM(10) (particulate matter < 10 microm in aerodynamic diameter) were 8.4 microg/m(3) (38.3 microg/m(3)) and 13.5 microg/m(3) (73.7 microg/m(3)), respectively. The number of accumulation mode particles was consistently inversely associated with PEFR in spirometry. Inverse, but nonsignificant, associations were observed with ultrafine particles, and no associations were observed with large particles (PM(10)). Compared to the effect estimates for self-monitored PEFR, the effect estimates for spirometric PEFR tended to be larger. The standard errors were also larger, probably due to the lower number of spirometric measurements. The present results support the need to monitor the particle number and size distributions in urban air in addition to mass.

Hygroscopic growth of ultrafine ammonium sulphate aerosol measured using an ultrafine tandem differential mobility analyzer

An ultrafine tandem differential mobility analyzer has been developed for measurements of the hygroscopicity of ultrafine aerosol particles, between 8 and 50 nm in mobility diameter. In this paper, the main operation features of the device are presented along with a detailed evaluation for the limits of its operation. The instrument is suitable for both laboratory‐generated and atmospheric aerosol measurements. Hygroscopic growth data are presented for ammonium sulphate particles in the ultrafine size range, and comparisons are made with both experimental literature data and with theory. The data include determination of hygroscopic growth curves, deliquescence behavior, and hysteresis. These data will find applications in studies of the formation and growth of atmospheric aerosols.

Concentrations and Estimated Soot Content of PM1, PM2.5, and PM10in a Subarctic Urban Atmosphere

Mass concentrations of ambient particulate matter were measured in terms of daily average values of PM1, PM2.5, and PM10 for 6 months during the winter of 1996−1997 at a fixed sampling site in Helsinki, Finland, along with meteorological parameters and particle number concentra tions in the size range 0.01−1 μm. In addition, the PM filters were subjected to reflectometric analysis to determine absorption coefficients for the various fractions of urban particulate matter. The data were divided into two periods (winter and spring) in order to study more closely seasonal phenomena that have an effect on air pollution patterns. The variations in PM10 and PM2.5 concentrations differed in pattern during resuspended dust episodes, whereas those in PM1 concentrations followed those in PM2.5 fairly well throughout the 6-month measurement period. Thus it seems that PM1 does not provide much additional information on mass concentrations relative to PM2.5. Number concentrations in the ultrafine particle size range fr...

Determination of Differential Mobility Analyzer Transfer Functions Using Identical Instruments in Series

The differential mobility analyzer (DMA) is an important tool for determining particle size distributions. The physical performance of a DMA is quantified by the concept of the transfer function. Therefore, knowledge of the transfer function is important to interpret the mobility distributions recorded by a DMA. During a calibration workshop in preparation for the Aerosol Characterization Experiment 1 (ACE1) field campaign, the transfer functions of five types of different mobility analyzers (Vienna-type DMA short, medium, and long, CIT radial, and TSI long; CIT = California Institute of Technology, Pasadena, CA; TST = TSI Inc., St. Paul, MN) were experimentally characterized by height, width, and area of their transfer functions. Different particles size ranges between 3 and 200 nm were investigated. The transfer function was determined by scanning a DMA across the mobility distribution produced by another, identical DMA. Subsequently, the data were processed by a deconvolution algorithm assuming a triangular shape for the transfer function. For all DMA types, the area of the transfer function decreased with particle size, especially for ultrafine particles (d_p < 20 nm). The gradient with which this area decreases with particle size, however, is different for each of the DMA types investigated. The calibration provides an improved description of the performance of each DMA, particularly in the ultrafine size range.

Differential Electrical Mobility Analysis: A Theoretical Study

ABSTRACT The subject of this work is the theoretical investigation of slowly scanning differential mobility analyzers (DMAs) which are, e.g., utilized to determine DMA transfer functions and to measure particle mobility distributions. A model to describe such systems is introduced and applied to investigate three different regimes of input mobility distributions: 1) a mobility distribution much narrower than the DMA transfer function, 2) a mobility distribution of about the same width as the DMA transfer function, and 3) a mobility distribution much wider than the DMA transfer function. Cases 1) and 2) are relevant for DMA transfer function measurements utilizing tandem differential mobility analyzer (TDMA) systems. For either regime, it is not possible to determine DMA transfer functions directly from the concentration distributions measured at the outlet of a DMA. For these cases, a deconvolution procedure is needed. Therefore, an iterative deconvolution procedure was developed. Determining DMA transfer functions utilizing the developed deconvolution procedure, different shapes of transfer function (triangular, Gaussian) are discussed. Case 3) is relevant for particle size distribution measurements. Here, the mobility distribution upstream of the DMA can be obtained by dividing the concentration distribution measured downstream of a DMA by the DMA transfer function area. The DMA transfer function area is influenced by diffusional losses inside the DMA, and therefore is size-dependent. Neglecting this size dependence results in an underprediction of particle number concentrations in the ultrafine particle size range.

The investigations of aerosol particle formation in urban background area of Helsinki

In this study the possible conditions for new aerosol particle formation in a background area of Helsinki have been analysed. The measurements of aerosol particle size distribution, main gaseous pollutant compounds, UV spectra and meteorological parameters were performed during April–May 1993. The main interest was concentrated on the investigations of photochemical OH radical formation, the oxidation of gas phase SO 2 to H 2SO 4 and the formation of H 2SO 4H 2O aerosol particles. The measurements were analysed using a model for OH radical formation and aerosol dynamics. The analysis of aerosol size distributions was carried out using positive matrix factorization. The main conclusion is that based on our model analysis no evidence of new particle formation in the vicinity of the measurement station was found. However, the high concentrations of aerosol particles in the ultrafine size range indicate that some other particle formation pathways are to be considered.

Recent advances in the recovery of tungsten values in the fine and ultrafine size range

Recent advances in the design of fine gravity concentrators and high gradient magnetic separation devices have led to significant improvements in the recovery of tungsten values in fine and ultrafine size range. Amongst the more promising techniques of fine particles processing, encouraging results are reported on froth flotation, shear flocculation and spherical agglomeration of tungsten ore slimes. Development of highly selective reagents such as alkyl hydroxamates, phosphonic acid derivatives and alkylated nitrosonapthols is vital for enhancing separation efficiencies in the slimes size range. Froth flotation of Indian tungsten ore slimes (particularly at Degana) using appropriate reagent combinations appears promising and needs to be examined in greater detail.

A novel unipolar charger for ultrafine aerosol particles with minimal particle losses

A unipolar diffusion charger with minimal particle losses in the ultrafine size range has been developed. This charger uses two radioactive α-sources to produce ions which are drawn into the charging region by an alternating electric field. The aerosol flow in the centre of the charging region is surrounded by a particle-free sheath air flow to prevent particle losses. Charged aerosol particles move in a “zigzag” manner in the charging channel under the influence of the alternating electric field. Positive gas ions, with higher electrical mobilities than ultrafine aerosol particles, homogeneously fill the entire charging region. Here, the aerosol becomes unipolarly charged. The charging efficiency is strongly dependent on the residence time of the particles in the ion cloud. The ion current was measured in the charging region to determine the ion concentration. The residence time of the particles in the ion cloud was calculated for each stream line of the aerosol flow. The losses of ultrafine particles in the charger were experimentally determined. The unipolar charge distribution was measured and calculated by integrating the theoretical charge distribution over all stream lines of the aerosol flow.

Performance of a unipolar “square wave” diffusion charger with variable nt-product

A recently developed unipolar diffusion charger is described in detail and is investigated. A square wave voltage across the charging zone guarantees minimized electrostatic particle losses. Subsequently, ultrafine particles can be efficiently charged employing high ion concentrations. An analytical description of the spatial distribution of ions in the charging zone illustrates the strong influence of the space charge field in the charging zone. The distribution of the charging parameter nt (product of the spatial ion concentration and the residence time of particles in the charging region) is shown. This calculated charging parameter is described by an averaged single nt. An increasing discrepancy between the experimental and theoretical charging efficiency size relation is observed by varying the voltage operation parameter in the charging area. The experimental efficiency size relation is fitted to theory, leading to an effective charging parameter nt ef. An extrinsic charging efficiency E ex, which accounts for particle losses, is defined. E ex is shown to exhibit a maximum with respect to nt ef. The maximum E ex is high in comparison with conventional charger designs, especially for particles in the ultrafine size range.

Irradiation induced aerosol formation in flue gas: Experiments on low doses

Laboratory experiments on irradiation induced aerosol formation from gaseous sulphur dioxide in humid air are presented. This work is connected to the aerosol particle formation process in the electron beam technique for cleaning flue gas. As a partial process of this method primary products of the radiolysis of water vapour convert sulphur dioxide into gaseous sulphuric acid which then nucleates with water vapour forming small acid droplets. This experimental work has been performed on relatively low absorbed doses. Aerosol particle formation is strongly dependent on dose. In the experiments, the first aerosol particles were detected already on absorbed doses of 0.1–10 mGy. The particle size in these cases in the so-called ultrafine size range (1–20 nm). In this article three experimental set-ups with some characteristic results are presented.

Assessment of wire and tube penetration theories using a [formula omitted] cluster aerosol

Diffusion samplers are commonly used for the measurement of aerosol size distributions ( d p < 500 nm). In particular, wire screen methods are the only practical means currently available for the detection and measurement of ultrafine molecular cluster aerosols, d p: 0.5–3 nm, such as those associated with radon decay products. The methods have relied upon the Cheng-Yeh wire screen penetration theory [Cheng, Y. S. and Yeh, H. C. (1980) J. Aerosol Sci. 11, 313.] that has been verified for particle sizes d p > 3.5–4 nm. The validity of the theory in the ultrafine cluster size range has been assumed. In this study, a well-defined 218 PoO x cluster aerosol, D avg = 0.078 ± 0.003 cm 2 s −1 ( d p ≈ 0.6 nm) was generated for an assessment of the wire screen penetration theory for two low mesh number wire screens. The results indicated good agreement with the theory, within the domain of its underlying assumptions. In addition, a theoretical expression developed by Ingham [Ingham, D. B. (1975) J. Aerosol Sci. 6, 125.] for uniform flow tube penetration was investigated using the cluster aerosol for its applicability in the estimation of diffusional losses in the entrance of a tube.

The Kinetics and Shape Factors of Ultrafine Dry Grinding in a laboratory tumbling ball mill

AbstractThe kinetics of batch grinding quartz from a feed of 600 by 425 m̈m to a product of 80% less than 10 m̈m have been determined using screening and laser diffractometer sizing for size analysis. The specific rates of breakage decreased by a factor of about three when the material became less than about 100 m̈m in size, but the primary breakage distribution function also changed to give proportionately more fine material, so that the grinding efficiency expressed as the development of surface area (B.E.T.) per unit of energy input did not decrease. Analysis of the shape of the particles in the 25 × 38 m̈m size range showed that particles of this size produced by roll crushing or by 8 minutes of grinding of a 425 × 600 m̈m feed were not different but at long grinding times the particles were rounded. This suggests that the breakage mechanism changes to give more chipping and abrasion and less disintegrative fracture. As the material approached the ultrafine size range it adhered to the mill case and there was no further size reduction. However, a technique for striking the mill case to dislodge the particles was successful in allowing further grinding to 40% by weight less than 2 μm.