Multi-channel statistical analysis of combustion aerosols. Part II: Negative correlations of particle modes and fragmentation theorem

This paper develops a new method of statistical analysis of interaction and transformation between different modes in the particle size distribution in atmospheric aerosols in the presence of strong stochastic fluctuations of the environmental and meteorological parameters. Fast processes of mode transformation are investigated in combustion aerosols near a busy road on the basis of the fragmentation mechanism of particle evolution. A unique anti-symmetric correlation pattern between different modes is described and explained by means of the formulated fragmentation theorem. This provides yet another confirmation of the fragmentation mechanisms of aerosol evolution.     

Growth of ultrafine particles by brownian coagulation

Current atmospheric observations tend to support the view that continental tropospheric aerosols (particularly urban aerosols) show multimodal mass distributions in the size range of 0.01–100 μm. The origin of these aerosols is both natural and anthropogenic. Recently, trimodal sub-μm size distributions from combustion measurements at 0.008, 0.035 and 0.15 μm were also observed. Our interest in the present study is the secondary process of growth of sub-μm size aerosols by the coagulation process alone. Using the ‘J-space’ (integer-space) distribution method of Salk (Suck) and Brock (1979, J. Aerosol Sci.10, 58–590), we report an accurate numerical simulation study of the evolution of ultrafine to fine particle size distributions. Comparision with the analytic solution of Scott (1968, J. atmos. Sci.25, 54–64) was made to test the accuracy of our J-space or integer-space distribution method. Our multimodal sub-μ particle size distribution study encompassed the particle size range of 0.001–0.20 μm. Details of particle growth in each mode and interaction between different modes in the multimodal distribution were qualitatively analyzed.     

Number size distribution of atmospheric aerosols during ACE-Asia dust and precipitation events

Measurements of size-resolved particle number concentrations during the Asian Pacific Regional Aerosol Characterization Experiment (ACE-Asia) field campaign were made at the Gosan super-site, South Korea. In East Asia, dust and precipitation phenomena play a crucial role in atmospheric environment and climate studies because they are major sources and sinks of atmospheric aerosols, especially in the springtime. Total Ozone Mapping Spectrometer (TOMS) Aerosol Index and backward trajectories are analyzed to investigate the spatial and temporal evolution of dust storms. The size distributions between dust and non-dust periods and times with and without precipitation are compared. In order to understand the temporal evolution of the aerosol size distribution during dust and precipitation events, a simple aerosol dynamics model is employed. The model predicted and observed size distributions are compared with the measured data. The results show that the coarse mode particle number concentrations increase by a factor of 10–16 during dust events. During precipitation, however, particles in the coarse mode are scavenged by impaction mechanism. It is found that the larger particles are more efficiently scavenged. The degree of scavenged particle varies depending on the rainfall rate, raindrop size distribution and aerosol size distribution.     

Characterization of aerosols from biomass burning--a case study from Mizoram (Northeast), India

Physical and optical properties of biomass burning aerosols in Northeastern region, India analyzed based on measurements made during February 2002. Large spatial extent of Northeastern Region moist tropical to moist sub-tropical forests in India have high frequency of burning in annual dry seasons. Characterization of resultant trace gases and aerosols from biomass burning is important for the atmospheric radiative process. Aerosol optical depth (AOD) observed to be high during burning period compared to pre- and post-burning days. Peak period of biomass burning is highly correlated with measured AOD and total columnar water vapor. Size distribution of aerosols showed bimodal size distribution during burning day and unimodal size distribution during pre- and post-burning days. Size distribution retrievals from biomass burning aerosols show dominance of accumulation mode particles. Weighted mean radius is high (0.22 microm) during burning period. Columnar content of aerosols observed to be high during burning period in addition to the drastic reduction of visibility. During the burning day Anderson sampler measurements showed dominance of accumulation mode particles. The diurnal averaged values of surface shortwave aerosol radiative forcing af biomass burning aerosols varies from -59 to -87 Wm(-2) on different days. Measured and modeled solar irradiances are also discussed in the paper.     

Historical evolution of radiative forcing of climate

We have compiled the evolution of the radiative forcing for several mechanisms based on our radiative transfer models using a variety of information sources to establish time histories. The anthropogenic forcing mechanisms considered are well-mixed greenhouse gases, ozone, and tropospheric aerosols (direct and indirect effect). The natural forcing mechanisms taken into account are the radiative effects of solar irradiance variation and particles of volcanic origin. In general there has been an increase in the radiative forcing during the 20th century. The exception is a decline in the radiative forcing in the 1945–1970 period. We have found that the evolution of anthropogenic particle emissions in the same period may have been a major cause of this decline in the forcing. We have discussed uncertainties in the various forcings and their evolution. The uncertainties are large for many forcing mechanisms, especially the impact of anthropogenic aerosols. In particular the indirect effect of aerosols on clouds is difficult to quantify. Several evolutions of their effect may have been possible, strongly influencing the evolution of the total anthropogenic radiative forcing.     

Atmospheric aerosol measurements over North America and the North Atlantic Ocean

Measurements of atmospheric aerosol, obtained during thirty-nine transit flights within North America and across the North Atlantic Ocean, are presented and analyzed. The measurements comprise Aitken nucleus concentrations, particle size distributions, and the particle component of the light-scattering coefficient. Measurements of ozone are also presented.These data provide information on the ‘background’ and average values of the atmospheric aerosol in the lower and middle troposphere in continental, marine and high-latitude airmasses. The effects of temperature inversions, vertical mixing, clouds and precipitation, and stratospheric intrusions are illustrated. Time and spatial scales are derived for the transformations of the aerosol from those characteristic of a marine airmass into those characteristic of a continental airmass and vice versa.     

Iron isotopic fractionation in industrial emissions and urban aerosols

A study on tropospheric aerosols involving Fe particles with an industrial origin is tackled here. Aerosols were collected at the largest exhausts of a major European steel metallurgy plant and around its near urban environment. A combination of bulk and individual particle analysis performed by SEM–EDX provides the chemical composition of Fe-bearing aerosols emitted within the factory process (hematite, magnetite and agglomerates of these oxides with sylvite (KCl), calcite (CaCO₃) and graphite carbon). Fe isotopic compositions of those emissions fall within the range (0.08‰ < δ⁵⁶Fe < +0.80‰) of enriched ores processed by the manufacturer (−0.16‰ < δ⁵⁶Fe < +1.19‰). No significant evolution of Fe fractionation during steelworks processes is observed. At the industrial source, Fe is mainly present as oxide particles, to some extent in 3–4 μm aggregates. In the close urban area, 5 km away from the steel plant, individual particle analysis of collected aerosols presents, in addition to the industrial particle type, aluminosilicates and related natural particles (gypsum, quartz, calcite and reacted sea salt). The Fe isotopic composition (δ⁵⁶Fe = 0.14 ± 0.11‰) measured in the close urban environment of the steel metallurgy plant appears coherent with an external mixing of industrial and continental Fe-containing tropospheric aerosols, as evidenced by individual particle chemical analysis. Our isotopic data provide a first estimation of an anthropogenic source term as part of the study of photochemically promoted dissolution processes and related Fe fractionations in tropospheric aerosols.     

Long-term assessment of particulate matter using CHIMERE model

Particulate matter (PM) and aerosols have became a critical pollutant and object of several research applications, due to their increasing levels, especially in urban areas, causing air pollution problems and thus effects on human health. The main purpose of this study is to perform a first long-term air quality assessment for Portugal, regarding aerosols and PM pollution. The CHIMERE chemistry-transport model, forced by the MM5 meteorological fields, was applied over Portugal for 2001 year, with 10 km horizontal resolution, using an emission inventory obtained from a spatial top-down disaggregation of the 2001 national inventory database. The evaluation model exercise shows a model trend to overestimate particulate pollution episodes (peaks) at urban sites, especially in winter season. This could be due to an underprediction of the winter model vertical mixing and also to an overestimation of PM emissions. Simulated inorganic components (ammonium and sulfate) and secondary organic aerosols (SOA) were compared to measurements taken at Aveiro (northwest coast of Portugal). An underestimation of the three components was verified. However, the model is able to predict their seasonal variation. Nevertheless, as a first approach, and despite the complex topography and coastal location of Portugal affected by sea salt natural aerosols emissions, the results obtained show that the model reproduces the PM levels, temporal evolution, and spatial patterns. The concentration maps reveal that the areas with high PM values are covered by the air quality monitoring network.     

Impact of stratospheric volcanic aerosols on climate: Evidence for aerosol shortwave and longwave forcing in the Southeastern U.S.

Major volcanic eruptions inject massive amounts of dust and gases into the lower stratosphere and upper troposphere. Stratospheric volcanic aerosols can scatter incoming solar radiation to space, increasing planetary albedo, reducing the total amount of solar energy reaching the troposphere and the earth's surface, and decreasing the daytime maximum temperature (aerosol shortwave forcing). They can also absorb and scatter outgoing terrestrial longwave radiation, increasing the nighttime minimum surface temperature (longwave forcing). However, persuasive evidence of climate response to this forcing has thus far been lacking. Here we examine patterns of annual and seasonal variations in mean maximum and minimum temperature trend during the periods 1992–1994 and 1985–1987 relative to that during the period 1988–1990 at 47 stations in the southeastern U.S. for evidence of such climate responses. The stratospheric volcanic aerosol optical depths over the southeastern U.S. during the period 1985–1994 were inferred from the Stratospheric Aerosol and Gases Experiment (SAGE) 11 satellite extinction measurement. After the long-term trend signals are removed, it is shown that the dominant decreasing trend of mean maximum temperature and the dominant increasing trend of mean minimum temperature over periods 1992–1994 and 1985–1987 relative to that over the period 1988–1990 are consistent with the distribution of stratospheric volcanic aerosols and predictions from aerosol radiative forcing in the southeastern U.S.     

Multi-channel statistical analysis of combustion aerosols. Part I: Canonical correlations and sources of particle modes

A major problem with the analysis and investigation of combustion aerosols in the real-world environment is related to strong stochastic variations of the external and environmental parameters and factors (e.g., atmospheric turbulence, traffic fluctuations, etc.). Therefore, this paper develops new powerful statistical methods based on the canonical correlation analysis and the moving average technique, applied to combustion aerosols near a busy road. As a result, a new physical insight into the evolution of combustion aerosols and possible sources of nano-particle modes is presented and discussed. Several new particle modes are identified, analysed and associated either with trucks or cars on the road. In particular, liquid and solid particle modes are identified, and the mechanism of thermal fragmentation of solid nano-particles is used for the interpretation of the obtained results.     

Approximate determination of particulate mass loading by using junge-type extinction models for continental and rural aerosol particles

Sets of mass extinction coefficients at visible and near infrared wavelengths were calculated for four aerosol particle polydispersions of continental and rural origins, which are characterized by Junge-type size distribution curves with different radius intervals. The calculations were made by using a very accurate computer programme for Mie extinction. The results show that the mass extinction coefficients are closely related to the upper limit of the radius range as well as to the right wing features of the particle size distribution curves. A procedure is suggested for determining the vertical particulate mass loading from multispectral sun photometer measurements taken in very clear atmospheres. The examination of atmospheric particle extinction measurements in terms of the various extinction models shows that our model CR (based on continental and rural aerosol particle size distributions characterized by different values of Junge parameter in six contiguous radius subintervals from 0.003 to 20 μm) should give realistic estimates of the particulate mass loading in cases in which Angström's exponent α is nearly equal to or higher than 1.4. However, for the majority of real cases giving values of α smaller than 1.4, the model CR gives a good estimate of the lower limit for the particulate mass loading.     

On radiative effects of black carbon and sulphate aerosols

Most aerosol particles, such as sulphate and sea-salt particles, mainly scatter solar radiation, whilst soot (in the form of elemental carbon or “black” carbon, BC) in addition leads to considerable absorption. This scattering and absorption by the aerosol particles constitute the so-called direct aerosol effect. In this paper, we present results from a study of possible direct effects of tropospheric BC and sulphate aerosols, with an emphasis on BC aerosols, along a line from North Africa through Europe into the Arctic. Radiative budgets in a cloud-free atmosphere are estimated. Based on model-calculated distributions of BC and sulphate (provided by Seland and Iversen, 1998) and assumed size distributions of the background aerosol, new size distributions are obtained by adding natural, biomass burning and fossil fuel contributions to the background aerosol. Added nucleation mode particles are assumed externally mixed, whereas added accumulation mode BC and sulphate is internally mixed with the background according to condensational growth and Brownian coagulation theory. Humidity effects are taken into account by use of the Köhler equation. Mie calculations provide the resulting optical parameters, and the forcing is finally estimated by use of a radiative transfer model. A reference run and a series of eleven test-runs are performed to investigate the sensitivity of various assumptions on the contribution to upward TOA irradiance from BC and non-sea-salt sulphate. The tests suggest a high sensitivity to presence of BC and to particle swelling due to humidity. The sensitivity to assumed distribution of BC on particle size is more moderate. The same is true for the vertical resolution and the number concentration of the background aerosol. The effect of mixing organic carbon (OC) internally with biomass burning BC nucleation mode particles is characterized as moderate. The role of OC is, however, still uncertain. The same holds true for the optical thickness of the background atmosphere, for which we found a high sensitivity in this study. Other assumptions that were investigated had only small effects on the forcing. For the reference run we find a minimum in the aerosol forcing of approximately −5 W m^-2 near the most polluted areas in Europe, and a maximum of approximately 2 W m^-2 over North Africa. A warming effect is also found for the Arctic region, with forcing values up to 0.4 W m^-2.     

The modality of particle size distributions of environmental aerosols

Knowledge of the distribution of airborne particulate matter into size fractions has become an increasing area of focus when examining the effects of air pollution. While total number and mass concentrations may play an important role in exposure and risk assessment analyses, often an understanding of the particle size distributions provides more information on the type of atmospheric processes resulting in the distributions. The modality of the particle size distribution is one such aspect that has been associated with the aerosol formation mechanisms. The aim of this work is to provide a detailed analysis of the modal characteristics of a large number of particle size spectra collected over a period of three years for a range of ambient aerosol types. Measurements of over 6000 size distributions in the size range 0.016–30 μm were made using a scanning mobility particle sizer and an aerodynamic particle sizer for various ambient aerosols including: traffic influenced, urban, vegetation burning influenced, marine, modified background and suburban. Advanced data analytical procedures were adopted to combine the distributions from the two instruments for the calculation of the volume size distributions to allow clear interpretation of the modal characteristics. It was determined that, while in most cases there is a distinct nuclei mode in the number size distribution, this does not translate to a nuclei mode in the volume size distribution. Furthermore, while many of the number size distributions were different for each aerosol studied, the volume distributions were similar. This finding has serious implications for the setting of mass-based air quality standards.     

Source apportionment of urban fine and ultra-fine particle number concentration in a Western Mediterranean city

Extensive measurements on particle number concentration and size distribution (13–800 nm), together with detailed chemical composition of PM_2.5 have constituted the main inputs of the database used for a source apportionment analysis. Data were collected at an urban background site in Barcelona, Western Mediterranean.The source identification analysis helped us to distinguish five emission sources (vehicle exhausts, mineral dust, sea spray, industrial source and fuel-oil combustion) and two atmospheric processes (photochemical induced nucleation and regional/urban background particles derived from coagulation and condensation processes). After that, a multilinear regression analysis was applied in order to quantify the contribution of each factor.This study reveals that vehicle exhausts contribute dominantly to the number concentration in all the particle sizes (52–86%), but especially in the range 30–200 nm. This work also points out the importance of the regional and/or urban formed aerosols (secondary inorganic particles) on the total number concentration (around 25% of the total number), with a higher impact on the accumulation mode. The photo-chemically induced nucleation of aerosols only represents a small proportion of the total number as an annual mean (3%), but is very relevant when considering only the nucleation mode (13–20 nm) fraction (23%). The other sources recognized registered sporadic contributions to the total number, coinciding with specific meteorological scenarios.This study discloses the main sources and features affecting and controlling the fine and ultra-fine aerosols in a typical city in the Western Mediterranean coast. Whereas the road traffic appears to be the most important source of sub-micrometric aerosols, other sources may not be negligible under specific meteorological conditions.     

Simulation of the evolution of particle size distributions containing coarse particulate in the atmospheric surface layer with a simple convection-diffusion-sedimentation model

The Fugitive Dust Model (FDM) and Industrial Source Complex (ISC), widely used coarse particulate dispersion models, have been shown inaccurate due to the neglect of vertical variations in atmospheric wind speed and turbulent diffusivity (Vesovic et al., 2001), omission of the gravitational advection velocity, and an underestimation of the ground deposition velocity (Kim and Larson, 2001). A simple, transient two-dimensional convection-diffusion-sedimentation model is proposed to simulate the evolution in particle size distribution of an aerosol ‘puff’ containing coarse particulate in the atmospheric surface layer. Monin-Okhubov similarity theory, accompanied by empirical observations made by Businger et al. (1971), is adopted to characterize the surface layer wind speed and turbulent diffusivity profiles over a wide range of atmospheric conditions. A first order analysis of the crossing trajectories effect suggests simulation data presented here are not significantly affected by particle inertia. The model is validated against Suffield experimental data in which coarse particulate deposition was measured out to a distance of 800 m from the source (Walker, 1965). Good agreement is found for the decay in ground deposits with distance from the source for stable atmospheres. Deposition data was also simulated for unstable atmospheric stratification and the current model was determined to modestly underestimate the peak concentration with increasing accuracy further downwind of the release. The current model's effective deposition velocity was compared to that suggested by Kim et al. (2000) and shows improvement with respect to FDM. Lastly, the model was used to simulate the dispersion of nine lognormal aerosol puffs in the lowest 50 m of the atmospheric surface layer for four classes of atmospheric stability. The simulated mass median aerodynamic diameters (MMAD) at multiple downwind sampling locations were calculated and plotted with distance from the source. The first 50 m from the source was found to have a substantial impact on the evolution of MMAD for stable atmospheric conditions. Away from the source, it was observed that particle size distributions were truncated by removal of all particles larger than about 60 μm. A particle Peclet number was also defined to quantify the relative importance of turbulent dispersion and sedimentation on particle motion in the vertical direction.     

A quantitative assessment of source contributions to inhalable particulate matter pollution in metropolitan Boston

In this paper, source apportionment techniques are employed to identify and quantify the major particle pollution source classes affecting a monitoring site in metropolitan Boston, MA. A Principal Component Analysis (PCA) of paniculate elemental data allows the estimation of mass contributions for five fine mass panicle source classes (soil, motor vehicle, coal related, oil and salt aerosols), and six coarse panicle source classes (soil, motor vehicle, refuse incineration, residual oil, salt and sulfate aerosols). Also derived are the elemental characteristics of those source aerosols and their contributions to the total recorded elemental concentrations (i.e. an elemental mass balance). These are estimated by applying a new approach to apportioning mass among various PCA source components: the calculation of Absolute Principal Component Scores, and the subsequent regression of daily mass and elemental concentrations on these scores.One advantage of the PCA source apportionment approach developed is that it allows the estimation of mass and source particle characteristics for an unconventional source category: transported (coal combustion related) aerosols. This particle class is estimated to represent a major portion of the aerosol mass, averaging roughly 40 per cent of the fine mass and 25 per cent of the inhalable particle mass at the Watertown, MA site. About 45 per cent of the fine particle sulfur is ascribed to this one component, with only 20 per cent assigned to pollution from local sources. The composition of the coal related aerosol at this site is found to be quite different from particles measured in the stacks of coal-fired power plants. Sulfates were estimated to comprise a much larger percentage of the ambient coal related aerosol than has been measured in stacks, while crustal element percentages were much reduced. This is thought to be due to primary panicle deposition and secondary aerosol accretion experienced during transport. Overall, the results indicate that the application of further emission controls to local point sources of particles would have less influence on fine aerosol and sulfate concentrations than would the control of more distant emissions causing aerosols transported into the Boston vicinity.     

Iron isotopic fractionation in industrial emissions and urban aerosols

A study on tropospheric aerosols involving Fe particles with an industrial origin is tackled here. Aerosols were collected at the largest exhausts of a major European steel metallurgy plant and around its near urban environment. A combination of bulk and individual particle analysis performed by SEM–EDX provides the chemical composition of Fe-bearing aerosols emitted within the factory process (hematite, magnetite and agglomerates of these oxides with sylvite (KCl), calcite (CaCO₃) and graphite carbon). Fe isotopic compositions of those emissions fall within the range (0.08‰ < δ⁵⁶Fe < +0.80‰) of enriched ores processed by the manufacturer (−0.16‰ < δ⁵⁶Fe < +1.19‰). No significant evolution of Fe fractionation during steelworks processes is observed. At the industrial source, Fe is mainly present as oxide particles, to some extent in 3–4 μm aggregates. In the close urban area, 5 km away from the steel plant, individual particle analysis of collected aerosols presents, in addition to the industrial particle type, aluminosilicates and related natural particles (gypsum, quartz, calcite and reacted sea salt). The Fe isotopic composition (δ⁵⁶Fe = 0.14 ± 0.11‰) measured in the close urban environment of the steel metallurgy plant appears coherent with an external mixing of industrial and continental Fe-containing tropospheric aerosols, as evidenced by individual particle chemical analysis. Our isotopic data provide a first estimation of an anthropogenic source term as part of the study of photochemically promoted dissolution processes and related Fe fractionations in tropospheric aerosols.     

Influence of Saharan dust outbreaks and atmospheric stability upon vertical profiles of size-segregated aerosols and water vapor

Vertical profiles of aerosols and meteorological parameters were obtained using a hot air balloon and motorized paraglider. They were studied under anticyclonic conditions in four different contexts. Three flights occurred near sunrise, and one took place in the central hours of the day. The effects of North African dust intrusions were analyzed, whose entrance to the study area took place above the Stable Boundary Layer (SBL) in flight 1 and below it in flight 2. These flights have been compared with a non-intrusion situation (flight 3). A fourth flight characterized the profiles in the central hours of the day with a well-formed Convective Boundary Layer (CBL). With respect to the particle number distribution, the results show that not all sizes increase within the presence of an intrusion; during the first flight the smallest particles were not affected. The particle sizes affected in the second flight fell within the 0.35–2.5 μm interval. Under situations of convective dynamics, the reduction percentage of the particle number concentration reduces with increasing altitude, independently of their size, with respect to stability conditions. The negative vertical gradient for aerosols and water vapor, characteristic of a highly stable SBL (flight 3) becomes a constant profile within a CBL (flight 4). There are two situations that seem to alter the negative vertical gradient of the water vapor mixing ratio within the SBL: the presence of an intrusion and the possible stratification of the SBL based on different degrees of stability.     

Acid aerosols in the Pittsburgh Metropolitan area

This article presents data on ambient concentrations of selected acidic aerosols at four existing monitoring sites in the Pittsburgh PA metropolitan area. The data were collected by staff of the Allegheny County Health Department, Division of Air Quality during the summer and fall of 1993. The sampling protocol was focused on obtaining 24 h-average ammonia, ammonium, acidic sulfates, and particle strong acids data on a 2 to 3 day cycle. The data were obtained using Harvard University School of Public Health's “Short-HEADS” annular denuder sampling train. The Pittsburgh area is of interest because it is downwind of a major regional source of sulfur and nitrogen emissions from coal-burning power plants: the Ohio River Valley. The data presented here indicate that ground-level concentrations of acidic aerosols in Pittsburgh are highly correlated spatially and that many pollutants are higher on days when ground-level wind direction vectors indicate that wind is coming from the southwest rather than from the Pittsburgh source area itself. The monitoring site that is most upwind of the Pittsburgh source area – South Fayette – has particle strong acid levels about twice those of sites closer in to the Pittsburgh central business district.