Secondary organic aerosol formation from the oxidation of aromatic hydrocarbons in the presence of dry submicron ammonium sulfate aerosol

A laboratory study was conducted to examine formation of secondary organic aerosols. A smog chamber system was developed for studying gas–aerosol interactions in a dynamic flow reactor. These experiments were conducted to investigate the fate of gas and aerosol phase compounds generated from hydrocarbon–nitrogen oxide (HC/NO_x) mixtures irradiated in the presence of fine (<2.5 μm) particulate matter. The goal was to determine to what extent photochemical oxidation products of aromatic hydrocarbons contribute to secondary organic aerosol formation through uptake on pre-existing inorganic aerosols in the absence of liquid water films. Irradiations were conducted with toluene, p-xylene, and 1,3,5-trimethylbenzene in the presence of NO_x and ammonium sulfate aerosol, with propylene added to enhance the production of radicals in the system. The secondary organic aerosol yields were determined by dividing the mass concentration of organic fraction of the aerosol collected on quartz filters by the mass concentration of the aromatic hydrocarbon removed by reaction. The mass concentration of the organic fraction was obtained by multiplying the measured organic carbon concentration by 2.0, a correction factor that takes into account the presence of hydrogen, nitrogen, and oxygen atoms in the organic species. The mass concentrations of ammonium, nitrate, and sulfate concentrations as well as the total mass of the aerosols were measured. A reasonable mass balance was found for each of the aerosols. The largest secondary organic aerosol yield of 1.59±0.40% was found for toluene at an organic aerosol concentration of 8.2 μm⁻³, followed by 1.09±0.27% for p-xylene at 6.4 μg m⁻³, and 0.41±0.10% for 1,3,5-trimethylbenzene at 2.0 μg m⁻³. In general, these results agree with those reported by Odum et al. and appear to be consistent with the gas–aerosol partitioning theory developed by Pankow. The presence of organic in the aerosol did not affect significantly the hygroscopic properties of the aerosol.     

Modeling the spectral optical properties of ammonium sulfate and biomass burning aerosols: parameterization of relative humidity effects and model results

The importance of including the global and regional radiative effects of aerosols in climate models has increasingly been realized. Accurate modeling of solar radiative forcing due to aerosols from anthropogenic sulfate and biomass burning emissions requires adequate spectral resolution and treatment of spatial and temporal variability. The variation of aerosol spectral optical properties with local relative humidity and dry aerosol composition must be considered. Because the cost of directly including Mie calculations within a climate model is prohibitive, parameterizations from off-line calculations must be used. Starting from a log-normal size distribution of dry ammonium sulfate, we developed optical properties for tropospheric sulfate aerosol at 15 relative humidities up to 99%. The resulting aerosol size distributions were then used to calculate bulk optical properties at wavelengths between 0.175 and 4 μm. Finally, functional fits of optical properties were made for each of 12 wavelength bands as a function of relative humidity. Significant variations in optical properties occurred across the total solar spectrum. Relative increases in specific extinction and asymmetry factor with increasing relative humidity became larger at longer wavelengths. Significant variation in single-scattering albedo was found only in the longest near-IR band. This is also the band with the lowest single scattering albedo. A similar treatment was done for aerosols from biomass burning. In this case, two size distributions were considered. One was based on a distribution measured for Northern Hemisphere temperate forest fires while the second was based on a measured size distribution for tropical fires. Equilibrium size distributions and compositions were calculated for 15 relative humidities and five black carbon fractions. Mie calculations and band averages of optical properties were done for each of the resulting 75 cases. Finally, fits were made for each of 12 spectral bands as functions of relative humidity and black carbon fraction. These optical properties result in global average forcing from anthropogenic sulfate aerosols of −0.81 Wm^-2. The global average forcing for biomass aerosols ranged from −0.23 to −0.25 Wm^-2 depending on the assumed size distribution, while fossil fuel organic and black carbon are estimated to heat the atmosphere by about 0.16 Wm^-2.     

Characterization of size-fractionated particulate mercury in Shanghai ambient air

The size-fractionated particulate mercury in ambient air was collected at the top of a university campus building in Shanghai from March 2002 to September 2003. Wet digestion followed by cold vapor atom adsorption spectroscopy (CVAAS) was employed to analyze total particulate mercury concentration. Two-step extraction was performed to differentiate volatile particle-phase mercury (VPM), reactive particle-phase mercury (RPM) and inert particle-phase mercury (IPM). The average concentrations of mercury in PM_1.6, PM₈ and total suspended particle (TSP) were 0.058–0.252, 0.148–0.398 and 0.233–0.529 ng m⁻³, respectively. About 50%–60% of mercury in PM₈ was in PM_1.6, and about 60%–70% of mercury in TSP was in PM₈. Particulate mercury was mainly concentrated on fine particles. The mercury fraction in fine particulate matters (<1.6 μm) was over 4 μg g⁻¹ while 1–2 μg g⁻¹ in TSP. Both were much higher than background values, suggesting that anthropogenic sources are the predominant emission contributors. Seasonal variation indicated that the mercury in TSP in spring was higher than that in summer; however, the mercury in fine particles (<1.6 μm) varied little. The fact that fine particulate mercury (<1.6 μm) was well correlated with sulfate and elemental carbon, but not with fluoride, chloride, nitrate and organic carbon, demonstrates that fine particulate mercury is closely associated with stationary sources and gas–particle transformation. Speciation analysis of mercury showed that VPM fraction decreased with the decrease of particle size, while IPM fraction increased and occupied over 50% in particle <1.6 μm. The detailed species in VPM, RPM and IPM were discussed. Coal burning was estimated to contribute approximately 80% of total atmospheric mercury.     

Size-resolved,real-time measurement of water-insoluble aerosols in metropolitan Atlanta during the summer of 2004

During the month of August 2004, the size-resolved number concentration of water-insoluble aerosols (WIA) from 0.25 to 2.0 μm was measured in real-time in the urban center of Atlanta, GA. Simultaneous measurements were performed for the total aerosol size distribution from 0.1 to 2.0 μm, the elemental and organic carbon mass concentration, the aerosol absorption coefficient, and the aerosol scattering coefficient at a dry (RH=30%) humidity. The mean aerosol number concentration in the size range 0.1–2.0 μm was found to be 360±175 cm⁻³, but this quantity fluctuated significantly on time scales of less than one hour and ranged from 25 to 1400 cm⁻³ during the sample period. The mean WIA concentration (0.25–2.0 μm) was 13±7 cm⁻³ and ranged from 1 to 60 cm⁻³. The average insoluble fraction in the size range 0.25–2.0 μm was found to be 4±2.5% with a range of 0.3–38%. The WIA population was found to follow a consistent diurnal pattern throughout the month with concentration maxima concurring with peaks in vehicular traffic flow. WIA concentration also responded to changes in meteorological conditions such as boundary layer depth and precipitation events. The temporal variability of the absorption coefficient followed an identical pattern to that of WIA and ranged from below the detection limit to 55 Mm⁻¹ with a mean of 8±6 Mm⁻¹. The WIA concentration was highly correlated with both the absorption coefficient and the elemental carbon mass concentration, suggesting that WIA measurements are dominated by fresh emissions of elemental carbon. For both the total aerosol and the WIA size distributions, the maximum number concentration was observed at the smallest sizes; however the WIA size distribution also exhibited a peak at 0.45 μm which was not observed in the total population. Over 60% of the particles greater than 1.0 μm were observed to be insoluble in the water sampling stream used by this instrumentation. Due to the refractive properties of black carbon, it is highly unlikely that these particles could be composed of elemental carbon, suggesting a crustal source for super-micron WIA.     

Particulate size distributions and mass measured at a motorway during the BAB II campaign

From 1 May to 25 May 2001, the BAB II campaign was carried out at the motorway BAB (656) near Heidelberg. Atmospheric concentrations of particulate matter and gases were measured together with the meteorological conditions. This paper is focused on the particulate matter measured upwind and downwind from the motorway at ground level. In order to determine the source contribution from the motorway traffic, it was necessary to measure upwind and downwind simultaneously due to variations in background concentrations. The particle number contribution from the motorway was found to be 35,000 particles cm⁻³ for particles with diameters close to 20 nm and 5000 particles cm⁻³ for particles with diameters close to 70 nm. Bimodal size distributions were observed on the downwind side, whereas the upwind side showed unimodal size distributions. For particulate mass, it can be estimated that the contribution from the motorway to the PM₁ concentrations is in a range 0.6–1.3 μg m⁻³ for the chosen measurement sites approximately 60 m from the road at a height of 6 m. The soot measurements showed diurnal variation; however, the upwind downwind difference was not measured. Correlation factors showed good correlation between total particle number and number of particles with diameters below 80 nm, CO and NO. There was no correlation between particle number and PM₁₀, which is due to the observation that particle number was dominated by the 20 nm particles.     

The impact of biomass burning on the environmental aerosol concentration in Gaborone,Botswana

Biomass burning, in the form of savanna fires and firewood for cooking and warmth, is widespread during the dry winter months in Southern Africa. This study was carried out to investigate its impact on the environment in Gaborone, Botswana, which is a small-sized city with very little pollution from industrial sources. Measurements of aerosol size and number concentrations were carried out at the University of Botswana campus in Gaborone from September 1999 to July 2000 using two automatic laser scattering particle counters. Particles were monitored in eight size ranges from 0.1 to 5.0 μm. The mean daily particle concentrations were found to vary from about 200 cm⁻³ on clear visibility days during the summer to a high of over 9000 cm⁻³ on cold winter evenings, when there was a significant smoke haze over the city. Particle concentrations were noticeably higher during the winter than in the summer. During a typical winter day, the total particle concentration peaked between 18 and 23 h, often showing an increase of over four-fold from mid-morning minimum values. The aerosol number size distributions under various conditions were investigated and the corresponding surface area and volume distributions were derived. In general, both the surface and volume distributions were bimodal with peaks close to 0.2 μm and at 5.0 μm or greater. A hand-held counter with a minimum detectable particle size of 0.3 μm was used to monitor the size and number concentrations of aerosols across the city. The results indicate a consistent pattern of maximum concentration in the highly populated areas close to the city centre, falling significantly in the sparsely populated outlying areas by up to an order of magnitude during peak biomass burning, suggesting that much of the smoke particles in the city are removed by wind.     

Measurement of the 210Po/210Pb activity ratio in size fractionated aerosols from the coast of the Japan sea

The seasonal variation of the ²¹⁰Po/²¹⁰Pb activity ratio in aerosols, as a function of particle size, have been studied at Kamo, on the west coast of Japan from July 1995 to June 1996. It was shown that 70% of ²¹⁰Po and 77% of ²¹⁰Pb activities were measured in aerosols with a diameter smaller than 0.7 μm. On the other hand, the abundances of ²¹⁰Po and ²¹⁰Pb in aerosols with a diameter larger than 10.9 μm were 3 and 1%, respectively. In general, the maxima of the ²¹⁰Po/²¹⁰Pb ratio were observed in aerosols of 5.4–10.9 μm, but the maxima in January and April 1996 appeared in the largest and the smallest size fractions, respectively. The results suggest that the size distribution of the ²¹⁰Po/²¹⁰Pb activity ratio may be modified by changes in the nature and intensity of aerosol sources.     

Origin of low-molecular-weight dicarboxylic acids and their concentration and size distribution variation in suburban aerosol

The concentrations and size distributions of low molecular weight dicarboxylic acids in suburban particulate matter collected in early and mid-autumn 2002 and early and mid-summer 2003 in Tainan, Taiwan, were analyzed. PM_2.5 contained, on average, 449.3 ng m⁻³ oxalic acid, 53.0 ng m⁻³ malic acid, 45.5 ng m⁻³ maleic acid, 29.6 ng m⁻³ succinic acid, 20.8 ng m⁻³ malonic acid, and 11.6 ng m⁻³ tartaric acid. Bar tartaric acid, concentrations were higher during the day, indicating that these acids are photochemical products. Furthermore, the malonic acid–succinic acid ratio of 0.79 during daytime and 0.60 during nighttime demonstrates that more succinic acid is converted to malonic acid during daytime, and that aerosol dicarboxylic acids predominantly originate from photochemical oxidation during daytime. The concentration peak of oxalic acid occurred in the condensation and droplet modes (0.32–1.0 μm), as did that of sulfate. In early summer, succinic acid, malonic acid, and oxalic acid major concentration peaks occurred at 0.32–0.54 μm, indicative of the relationship created by photochemical decomposition of succinc acid into malonic acid into oxalic acid. This photochemical decomposition accelerated in mid-summer such that most concentration peaks for succinic and malonic acids also occurred at 0.32–1.0 μm. Mid-summer is also the wettest period of the four in Tainan, with 85% RH. As a result of hygroscopic reactions in mid-summer, malonic acid and oxalic acid major concentration peaks shifted from 0.32–0.54 μm or 0.54–1.0 μm to 1.0–1.8 μm, thus extending the range in which these species were found to larger particle sizes, and this shift was highly correlated with a shift in succinic acid size distribution. This latter observation offers additional evidence that succinic acid is photochemically decomposed into malonic acid and oxalic acid and that the presence of malonic and oxalic acids in the wet mid-summer atmosphere is made more obvious via hygroscopic growth. Close correlation between succinic acid and Na⁺ and succinic acid and NO₃⁻ in the coarse mode is related to sea spray.     

Inorganic element concentrations in near surface aerosols sampled on the northwest slopes of Mount Kenya

Eight trace elements, Si, Cl, K, Ca, Ti, Mn, Fe and Zn in the near-ground atmospheric aerosols were evaluated in the northwestern part of Mount Kenya using a dichotomous sampler and an EDXRF spectrometer. The samples were taken at 2 sites situated in Nanyuki area, which is roughly on the Equator. The sampler segregated the aerosol into two aerodynamic diameter (ad) size fractions, fine (<3.5 μm ad) and coarse (>3.5 and <18 μm ad). The elemental concentrations in the two size fractions were quantified and the elements assigned to known sources. Local wind blown dust related to agricultural activities and fire burning was found to dominate the lower tropospheric aerosols. There was inconclusive evidence of long range-transported aerosols being moved by night transport from the middle to the lower parts of the troposphere. Influence of the Indian Ocean marine aerosol was suggested but conclusive evidence was lacking.     

Aerosol mass-size distributions at a tropical coastal environment: response to mesoscale and synoptic processes

Regular measurements of total mass concentration and mass-size distribution of near-surface aerosols, made using a ten-channel Quartz Crystal Microbalance (qcm) Impactor for the period October 1998–December 1999 at the tropical coastal station Trivandrum (8.5°N, 77°E), are used to study the response of aerosol characteristics to regional mesoscale and synoptic processes. Results reveal that aerosol mass concentrations are generally higher under land breeze conditions. The sea breeze generally has a cleansing effect, depleting the aerosol loading. The continental air (LB regime) is richer in accumulation mode (submicron) aerosols than the marine air. On a synoptic scale, aerosol mass concentration in the submicron mode decreased from an average high value of ∼86 μg m⁻³ during the dry months (January–March) to ∼11 μg m⁻³ during the monsoon season (June–September). On the contrary mass concentration in the supermicron mode increased from a low value of ∼15 μg m⁻³ during the dry months to reach a comparatively high value of ∼35 μg m⁻³ during April, May. Correspondingly, the effective radius (R_eff) increased from a low value of 0.15–0.17 μm to ∼0.3 μm indicating a seasonal change in the size distribution. The mass-size distribution shows mainly three modes, a fine mode (∼0.1 μm); a large mode (∼0.5 μm) and a coarse mode (∼3 μm). The fine mode dominates in winter. In summer the large mode becomes more conspicuous and the coarse mode builds up. The fine mode is highly reduced in monsoon and the large and coarse modes continue to remain high (replenished) so that their relative dominance increases. The size distribution tends to revert to the winter pattern in the post-monsoon season. Accumulation (submicron) aerosols account for ∼98% of the total surface area and ∼70% of the total volume of aerosols during winter. During monsoon, even though they still account for ∼90% of the area, their contribution to the volume is reduced to ∼50%; the coarse aerosols account for the rest.     

The physical characteristics of sulfur aerosols

A review of the physical characteristics of sulfur-containing aerosols, with respect to size distribution of the physical distributions, sulfur distributions, distribution modal characteristics, nuclei formation rates, aerosol growth characteristics, and in situ measurement, has been made.Physical size distributions can be characterized well by a trimodal model consisting of three additive lognormal distributions.When atmospheric physical aerosol size distributions are characterized by the trimodal model, the following typical modal parameters are observed:1. Nuclei mode – geometric mean size by volume, DGV_n, from 0.015 to 0.04 μm. σ_gn=1.6, nucler mode volumes from 0.0005 over the remote oceans to 9 μm³ cm⁻³ on an urban freeway.2. Accumulation mode – geometric mean size by volume, DGV_a, from 0.15 to 0.5 μm, σ_ga=1.6–2.2 and mode volume concentrations from 1 for very clean marine or continental backgrounds to as high as 300 μm³ cm⁻³ under very polluted conditions in urban areas.3. Coarse particle mode – geometric mean size by volume, DGV_c, from 5 to 30 μm, σ_gn=2–3, and mode volume concentrations from 2 to 1000 μm³ cm⁻³.It has also been concluded that the fine particles (D_p<2 μm) are essentially independent in formation, transformation and removal from the coarse particles (D_p>2 μm).Modal characterization of impactor-measured sulfate size distributions from the literature shows that the sulfate is nearly all in the accumulation mode and has the same size distribution as the physical accumulation mode distribution.Average sulfate aerodynamic geometric mean dia. was found to be 0.48±0.1 μm (0.37±0.1 μm vol. dia.) and σ_g=2.00±0.29. Concentrations range from a low of about 0.04 μg m⁻³ over the remote oceans to over 8 μg m⁻³ under polluted conditions over the continents.Review of the data on nucleation in smog chambers and in the atmosphere suggests that when SO₂, is present, SO₂-to-aerosol conversion dominates the Aitken nuclei count and, indirectly, through coagulation and condensation, the accumulation mode size and concentration. There are indications that nucleation is ubiquitous in the atmosphere, ranging from values as low as 2 cm⁻³ h⁻¹ over the clean remote oceans to a high of 6×10⁶ cm⁻³ h⁻¹ in a power plant plume under sunny conditions.There is considerable theoretical and experimental evidence that even if most of the mass for the condensational growth of the accumulation mode comes from hydrocarbon conversion, sulfur conversion provides most of the nuclei.     

The continuous field measurements of soluble aerosol compositions at the Taipei Aerosol Supersite,Taiwan

The characteristics of ambient aerosols, affected by solar radiation, relative humidity, wind speed, wind direction, and gas–aerosol interaction, changed rapidly at different spatial and temporal scales. In Taipei Basin, dense traffic emissions and sufficient solar radiation for typical summer days favored the formation of secondary aerosols. In winter, the air quality in Taipei Basin was usually affected by the Asian continental outflows due to the long-range transport of pollutants carried by the winter monsoon. The conventional filter-based method needs a long time for collecting aerosols and analyzing compositions, which cannot provide high time-resolution data to investigate aerosol sources, atmospheric transformation processes, and health effects. In this work, the in situ ion chromatograph (IC) system was developed to provide 15-min time-resolution data of nine soluble inorganic species (Cl⁻, NO₂⁻, NO₃⁻, SO₄²⁻, Na⁺, NH₄⁺, K⁺, Mg²⁺ and Ca²⁺). Over 89% of all particles larger than approximately 0.056 μm were collected by the in situ IC system. The in situ IC system is estimated to have a limit of detection lower than 0.3 μg m⁻³ for the various ambient ionic components. Depending on the hourly measurements, the pollutant events with high aerosol concentrations in Taipei Basin were associated with the local traffic emission in rush hour, the accumulation of pollutants in the stagnant atmosphere, the emission of industrial pollutants from the nearby factories, the photochemical secondary aerosol formation, and the long-range transport of pollutants from Asian outflows.     

Sources and concentrations of gaseous and particulate reduced nitrogen in the city of Münster (Germany)

Atmospheric ammonia mixing ratios and the main inorganic ions NH₄⁺, NO₃⁻ and SO₄²⁻ of size-resolved particles in the range from 0.05 to 10 μm were measured at an urban site in Münster, Germany. High mixing ratios of ammonia with a median of 5.2 ppb and a maximum of 50 ppb were detected. The mass fraction of submicron particles was much higher during the day than at night. At night, a greater particle mass and an increased presence of particulate nitrate was measured. Recurring patterns of particle distribution were distinguished and their characteristics analysed. In half of the measurements, the accumulation mode was clearly dominating, which is an indication of aged aerosol. In some measurements, higher concentrations of fine particles were found indicating particle formation. In these cases, a smaller particle mass and about four times greater ratios of ammonia versus ammonium concentrations were observed. These data show that ammonia contributes considerably to the formation of secondary particulate material.     

Visibility impairment during Yellow Sand periods in the urban atmosphere of Kwangju,Korea

For continuous monitoring of atmospheric visibility in the city of Kwangju, Korea, a transmissometer system consisting of a transmitter and a receiver was installed at a distance of 1.91 km across the downtown Kwangju, Korea. At the transmitter site a nephelometer and an aethalometer were also installed to measure the scattering and absorption coefficients of the atmosphere, respectively. Unusually high number of Yellow Sand events had occurred in the Northeast Asia during the spring of 2000. Visibility in Kwangju under such conditions was greatly impaired over large area for a few days. In order to investigate the effects of Yellow Sand on visibility impairment, chemical and elemental analyses of aerosol samples were performed along with the optical measurement of visibility. Hourly averaged visual range decreased from 61.7 to 1.9 km when hourly averaged concentration of PM10 varied from 32.9 to 601.8 μg/m³ during Yellow Sand periods. Fine particulate (<2.5 μm) concentrations were relatively lower than coarse particulate matters. Results of the data analyses show that mineral dusts originated from continental sources were simultaneously transported along with anthropogenic sulfate aerosols and marine aerosols. Total light extinction coefficient, b_ext, proposed by the IMPROVE network showed poor correlation with b_ext measured by transmissometer. Coarse mass scattering efficiency was classified into three categories; E_NHSOc, E_mineral, and E_sea-salt, which were determined as ammonium sulfate combined with nss-sulfate of 1.0, sea-salt of 0.4, and mineral of 0.77 m²/g, respectively. Mass fraction of NHSOc, sea-salt, and mineral dust was 0.20, 0.14, and 0.66, respectively.     

Size distribution of metals in urban aerosols in Seville (Spain)

The size distribution of metals in aerosols has been studied in 12 areas of the city of Seville. Urban particles were collected with a high-volume sampling system equipped with a cascade impactor, which effectively separates the particulate matter into six-size ranges. Forty-one samples were collected in spring 1996. Each filter was extracted with a mixture of nitric and percloric acids. The acid solutions of the samples were analysed in six-particle fractions by inductively coupled plasma atomic emission spectrometry (ICP-AES). The impactor stage fractionation of particles shows a typical bimodal distributions, one corresponding to the fine mode below 1 μm (55%), and the other to the coarse mode around 10 μm (32%). With regard to the size distribution of metals, we concluded that potentially toxic metals, such as nickel, lead and cadmium are mainly accumulated in the smaller particles, with percentages of 72.6, 69.4 and 63.8%, respectively. Lead have a concentration of 63.7 ng m⁻³, more than copper and manganese (26.7 and 16.5 ng m⁻³) and above all more than nickel, cobalt and cadmium (1.97, 0.54 and 0.32 ng m⁻³).     

The composition of individual aerosol particle in the troposphere and stratosphere over Xianghe (39.45°N, 117.0°E), China

A balloon observation was carried out on 22 August in 1993 from Xianghe Scientific Balloon Base (39.75°N, 117.0°E) near Beijing in China. Individual aerosol particles in the five samples collected in the troposphere and lower stratosphere were analyzed by using a transmission electron microscope equipped with an energy-dispersive X-ray (EDX) analyzer. Types of particles were classified by the quantitative EDX analysis and particle morphology. Following results were obtained by the analyses of aerosol particles in the radius range of 0.1–0.5 μm: (1) Sulfate particles were dominant (80%) in aerosol particles collected between 4 and 6 km altitude. (2) Sulfuric acid particles were present in 74% of particles at ∼8 km altitude, 91% at 11 km, 95% at 17 km and 88% at 21.2 km. (3) “S-rich” particles with K were collected both in the troposphere and lower stratosphere. It was considered that the particles containing K found at ∼5, ∼8 km altitude could originate from burning processes in the continent including the Tibetan plateau and be transported to the middle troposphere. (4) Sulfuric acid particles with Fe were present in 20–30% of sulfuric acid particles in the lower stratosphere. (5) Particles mainly composed of minerals were present in 6, 11% of particles at ∼5, ∼8 km, indicating the vertical transport to the upper troposphere. (6) Mineral particles which contain sulfuric acid and sulfate suggest the formation of sulfuric acid and sulfate on mineral particles by heterogeneous processes in the troposphere. (7) Sea-salt particles with and without minerals were collected in the troposphere and lower stratosphere, suggesting the vertical transport by convective clouds.     

Source apportionment of time and size resolved ambient particulate matter measured with a rotating DRUM impactor

Ambient particulate chemical composition data acquired from samples collected using a three-stage Davis Rotating-drum Universal-size-cut Monitoring (DRUM) impactor in Detroit, MI, between February and April 2002 were analyzed through the application of a three-way factor analysis model. PM_2.5 (particulate matter ⩽2.5 μm in aerodynamic diameter) was collected by a DRUM impactor with 3-h time resolution and three size modes (2.5 μm>D_p>1.15 μm, 1.15 μm>D_p>0.34 μm and 0.34 μm>D_p>0.1 μm). A novel three-way factor analysis model was applied to these data where the source profiles are a three-way array of size, composition and source while the contributions are a matrix of sample by source. Nine factors were identified: road salt, industrial (Fe+Zn), cloud processed sulfate, two types of metal works, road dust, local sulfate source, sulfur with dust, and homogeneously formed sulfate. Road salt had high concentrations of Na and Cl. Mixed industrial emissions are characterized by Fe and Zn. The cloud processed sulfate had a high concentration of S in the intermediate size mode. The first metal works represented by Fe in all three size modes and by Zn, Ti, Cu, and Mn. The second included a high concentration of small size particle sulfur with intermediate size Fe, Zn, Al, Si, and Ca. Road dust contained Na, Al, Si, S, K, and Fe in the large size mode. The local and homogeneous sulfate factors show high concentrations of S in the smallest size mode, but different time series behavior in their contributions. Sulfur with dust is characterized by S and a mix of Na, Mg, Al, Si, K, Ca, Ti, and Fe from the medium and large size modes. This study shows that the utilization of time and size resolved DRUM data can assist in the identification of sources and atmospheric processes leading to the observed ambient concentrations.     

Sources of sodium in atmospheric fine particles

Concentrations of size fractionated particulate sodium and potassium were measured in both marine and urban air. Marine air sampling was conducted during a cruise on R/V Hakuho-maru in the northwestern North Pacific in the summer of 1998. Urban air sampling was performed in the central part of Tokyo in 1997 and 1998. The fine sodium concentration (D<1.1 μm) in “Urban” air (180 ng m⁻³) was 3 times higher than that in “Marine” air (56 ng m⁻³). In the urban air samples, the size distributions of sodium and potassium showed bimodal peaks in the fine particle range (D<1.1 μm) and in the coarse particle range (D>1.1 μm). The existence of anthropogenic sodium in the fine particle range was detected in the urban air. The K/Na weight ratios in the fine particle range of the urban air (1.8–2.7) was 50–75 times higher than that in seawater (0.036). Potassium in the urban air is thought to be derived largely from anthropogenic sources. In the urban air samples, a high correlation between fine sodium and fine potassium concentrations suggests that they have the same anthropogenic source. Reevaluating the K/Na ratios in marine air to be relatively higher than that in seawater, we can estimate that several percents of anthropogenic sodium can be transported from land to remote marine air.     

Direct measurements and parameterisation of aerosol flux,concentration and emission velocity above a city

Articles have recently been published on aerosol size distributions and number concentrations in cities, however there have been no studies on transport of these particles. Eddy covariance measurements of vertical transport of aerosol in the size range 11 nm<D_p<3 μm are presented here. The analysis shows that typical average aerosol number fluxes in this size range vary between 9000 and 90,000 cm⁻² s⁻¹. With concentrations between 3000 and 20,000 cm⁻³ this leads to estimates of particle emission velocity between 20 and 75 mm s⁻¹. The relationships between number flux and traffic activity, along with emission velocity and boundary layer stability are demonstrated and parameterised. These are used to derive an empirical parameterisation for aerosol concentration in terms of traffic activity and stability. The main processes determining urban aerosol fluxes and concentrations are discussed and quantified where possible. The difficulties in parameterising urban activity are discussed.     

Fine particle concentrations and composition during wintertime inversions in Logan,Utah, USA

During Winter 2004, a series of elevated PM_2.5 events occurred in Logan, Utah, coinciding with strong winter inversions. This period resulted in 17 exceedances of the 24-h PM_2.5 standard, and some of the highest PM_2.5 mass loadings recorded in the United States, including 9 days of 24-h PM_2.5 measurements over 100 μg m⁻³. During the 3-month period, we monitored the size and mass concentrations of airborne particles using an aerosol mass spectrometer. PM_2.5 concentrations were dominated by the formation of ammonium nitrate, accounting for over 50% of the non-refractory aerosol matter throughout the study and 80% on the highest pollution days. Another 15–20% of the particulate matter was composed of organic carbon. The high particle concentration loadings in Utah's Cache Valley result from a combination of unfavorable meteorology dominated by a severe cold-temperature inversion, a mix of rural and urban emission sources, and a confined geographical area. As a rapidly growing formerly rural area, the Cache Valley is representative of future air pollution problems facing areas of the interior west undergoing rapid urbanization.