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.     

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.     

Evolution of stratospheric aerosols in the post-Pinatubo period measured by solar occultation

This paper presents particle size distributions of stratospheric aerosols derived from solar occultation data measured by the instrument ORA (an acronym for Occultation RAdiometer) during the period August 1992–May 1993. Starting from the UV-visible wavelength dependence of extinction coefficient profiles, an algorithm is developed that allows to retrieve the three parameters of an equivalent log-normal distribution and that makes use of vertical regularization. Comparison of retrieved mode radius and particle number density with existing data is found to be satisfactory. The evolution of the stratospheric aerosols is clearly influenced by sedimentation and coagulation as expected but also by vertical circulation. In a simple 1-D model, we derive the vertical wind profile and we interpret the temporal evolution of the particle mode radius.     

summary of the California aerosol characterization experiment

This report gives a brief summary of the experimental plan and the early results of field observations from the California Aerosol Characterization Experiment (ACHEX). The objectives of the program center on questions of the sources and evolution of aerosols in urban air, as they are superimposed on a natural background, particularly as they relate to visibilitydegradation. The project initially nvolved the use of an elaborately instrumented mobile laboratory combined with a fixed station in San Jose, in Pasadena, and in Riverside, and later incorporated several satellite monitoring stations in the Los Angeles Basin. Intensive field observationswere taken from July 1972 to November 1972 in several urban and nonurban locations between the San Francisco Bay area and the South Coast Basin, covering the Los Angeles area. In a second phase of the ACHEX, aerosols accompanying photochemical smog were studied intensively in the Los Angeles Basin during the period between July and October of 1973. The observations cover a wide variety of parameters including physical and chemical properties of aerosols, pollutant gas concentrations, and meteorological variables. The initial results show the great importance of sulfate, nitrate, noncarbonate carbon, and liquid water to the mass concentration of airborne particles and their relation to reduction in visibility. The anthropogenic contribution to atmospheric aerosols is consistently found to be allocated primarily to the submicron or fine particle size range.     

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.     

Classification of multiple types of organic carbon composition in atmospheric particles by scanning transmission X-ray microscopy analysis

A scanning transmission X-ray microscope at the Lawrence Berkeley National Laboratory is used to measure organic functional group abundance and morphology of atmospheric aerosols. We present a summary of spectra, sizes, and shapes observed in 595 particles that were collected and analyzed between 2000 and 2006. These particles ranged between 0.1 and 12 μm and represent aerosols found in a large range of geographical areas, altitudes, and times. They include samples from seven different field campaigns: PELTI, ACE-ASIA, DYCOMS II, Princeton, MILAGRO (urban), MILAGRO (C-130), and INTEX-B. At least 14 different classes of organic particles show different types of spectroscopic signatures. Different particle types are found within the same region while the same particle types are also found in different geographical domains. Particles chemically resembling black carbon, humic-like aerosols, pine ultisol, and secondary or processed aerosol have been identified from functional group abundance and comparison of spectra with those published in the literature.     

Tropospheric sulfate aerosol formation via ion-ion recombination

We propose a source of aerosols in the lower atmosphere associated with the creation, growth, and recombination of ubiquitous cosmogenically generated ions. This particle source should be favorable in the relatively clean, stable marine boundary layer, providing a uniform, continuous fine particle generator in the presence of dimethylsulfide emissions. Through this mechanism, new sulfate aerosols can be formed at sulfuric acid vapor partial pressures well below the supersaturations required for homogeneous binary nucleation of sulfuric acid/water solutions, which is consistent with numerous observations of new particle formation under sub-saturated conditions. The evolving aerosols in turn control the acid vapor concentration and thus modulate the sizes of the precursor ions and the rate of new particle formation. A simple model representing this nonlinear coupled system predicts that the physical and chemical processes connecting ions, vapors, and aerosols effectively constrain the particle population to a relatively narrow range of values. This self-limiting behavior may explain in part the apparent stability of the marine sulfate aerosol, with mean concentrations of the order of several hundred per cubic centimeter.     

Tropospheric Sulfate Aerosol Formation Via Ion-Ion Recombination

ABSTRACT

We propose a source of aerosols in the lower atmosphere associated with the creation, growth, and recombination of ubiquitous cosmogenically generated ions. This particle source should be favorable in the relatively clean, stable marine boundary layer, providing a uniform, continuous fine particle generator in the presence of dimethylsulfide emissions. Through this mechanism, new sulfate aerosols can be formed at sulfuric acid vapor partial pressures well below the supersaturations required for homogeneous binary nucleation of sulfuric acid/water solutions, which is consistent with numerous observations of new particle formation under sub-saturated conditions. The evolving aerosols in turn control the acid vapor concentration and thus modulate the sizes of the precursor ions and the rate of new particle formation. A simple model representing this nonlinear coupled system predicts that the physical and chemical processes connecting ions, vapors, and aerosols effectively constrain the particle population to a relatively narrow range of values. This self-limiting behavior may explain in part the apparent stability of the marine sulfate aerosol, with mean concentrations of the order of several hundred per cubic centimeter.     

Satellite observations of the seasonal cycles of absorbing aerosols in Africa related to the monsoon rainfall, 1995–2008

The link between the African Monsoon systems and aerosol loading in Africa is studied using multi-year satellite observations of UV-absorbing aerosols and rain gauge measurements.The main aerosol types occurring over Africa are desert dust and biomass burning aerosols, which are UV-absorbing. The abundance of these aerosols over Africa is characterised in this paper using residues and Absorbing Aerosol Index (AAI) data from Global Ozone Monitoring Experiment (GOME) on board ERS-2 and SCanning Imaging Absorption SpectroMeter for Atmospheric ChartograpHY (SCIAMACHY) on board Envisat.Time series of regionally averaged residues from 1995 to 2008 show the seasonal variations of aerosols in Africa. Zonally averaged daily residues over Africa are related to monthly mean precipitation data and show monsoon-controlled atmospheric aerosol loadings. A distinction is made between the West African Monsoon (WAM) and the East African Monsoon (EAM), which have different dynamics, mainly due to the asymmetric distribution of land masses around the equator in the west. The seasonal variation of the aerosol distribution is clearly linked to the seasonal cycle of the monsoonal wet and dry periods in both studied areas.The residue distribution over Africa shows two distinct modes, one associated with dry periods and one with wet periods. During dry periods the residue varies freely, due to aerosol emissions from deserts and biomass burning events. During wet periods the residue depends linearly on the amount of precipitation, due to scavenging of aerosols and the prevention of aerosol emissions from the wet surface. This is most clear over east Africa, where the sources and sinks of atmospheric aerosols are controlled directly by the local climate, i.e. monsoonal precipitation. Here, the wet mode has a mean residue of ?1.4 and the dry mode has a mean residue of ?0.3. During the wet modes a reduction of one residue unit for every 160 mm monthly averaged precipitation was found. Shielding effects due to cloud cover may also play a role in the reduction of the residue during wet periods.A possible influence of aerosols on the monsoon, via aerosol direct and indirect effects, is plausible, but cannot directly be deduced from these data.     

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.     

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.     

Design and assessment of a chamber to expose plants to simulated aerosol and rain

Increased reports of contaminants in atmospheric aerosols necessitate the development of exposure systems that can accurately simulate aerosols for research purposes. This study outlines the design, construction, cost, and performance of a simple plexiglass chamber equipped with nozzles for rain and aerosol generation. The chamber occupies approximately 152 cm x 125 cm (height x width) space and can be used to expose six large (625 cm2) plants or twelve smaller (144 cm2) ones. The total cost of the materials used in construction, including nozzles, was less than 700 dollars. Repeated analysis of the quantity and particle size distribution of the simulated aerosol and rain showed them to be highly predictable. By adjusting the volume and/or concentration of the spray, and the position of plants within the chamber, particle sizes typical of environmental aerosols (< or = 20 microm) and rains (0.7 to 1.2 mm) could be applied to experimental plants. This sample, economical system will allow for precise simulations of important aerosols and rain events in the study of their impingement on plants.     

Investigation of aerosol and gas emissions from a coal-fired power plant under various operating conditions

The concentrations of fine particles and selected gas pollutants in the flue gas entering the stack were measured under several common operation modes in an operating coal power plant producing electricity. Particle size distributions in a diameter range from 10 nm to 20 μm were measured by a scanning mobility particle sizer (SMPS), and the flue gas temperature and concentrations of CO₂ and SO₂ were monitored by a continuous emission monitoring system (CEMS). During the test campaign, five plant operating modes were studied: soot blowing, bypass of flue-gas desulfurization (FGD), reheat burner operating at 0% (turned off), 27%, and 42% (normal condition) of its full capacity. For wet and dry aerosols, the measured mode sizes were both around 40 nm, but remarkable differences were observed in the number concentrations (#/cm³, count per square centimeter). A prototype photoionizer enhanced electrostatic precipitator (ESP) showed improved removal efficiency of wet particles at voltages above +11.0 kV. Soot blowing and FGD bypass both increased the total particle number concentration in the flue gas. The temperature was slightly increased by the FGD bypass mode and varied significantly as the rating of reheat burner changed. The variations of CO₂ and SO₂ emissions showed correlations with the trend of total particle number concentration possibly due to the transitions between gas and particle phases. The results are useful in developing coal-fired power plant operation strategies to control fine particle emissions and developing amine-based CO₂ capture technologies without operating and environmental concerns associated with volatile amine emissions.

Implications: The measurement of the fine particle size distributions in the exhaust gas under several common operating conditions of a coal-fired power plant revealed different response relations between aerosol number concentration and the operating condition. A photo-ionizer enhanced ESP was demonstrated to capture fine particles with higher efficiency compared to conventional ESPs, and the removal efficiency increased with the applied voltage. The characteristic information of aerosols and main gaseous pollutants in the exhaust gas is extremely important for developing and deploying CO₂ scrubbers, whose amine emissions and operating effectiveness depends greatly on the upstream concentrations of fine particles, SO₂, from the power plant.     

The effect of temperature on the gas–particle partitioning of reactive mercury in atmospheric aerosols

Measurements of gas–particle-partitioning coefficients for reactive mercury in dry urban and laboratory aerosol were found to strongly depend on ambient temperature. Samples of atmospheric and laboratory aerosols (defined as both the gas and particle phases) were collected using filter and absorbent methods and analyzed for reactive mercury using thermal desorption combined with cold vapor atomic fluorescence spectroscopy. Synthetic ambient aerosols were generated in the laboratory from ammonium sulfate and adipic acid mixed with mercuric chloride in a purpose-built aerosol reactor. The aerosol reactor was operated in a temperature-controlled laboratory. Linear relationships between the logarithm of inverse gas–particle partitioning and inverse temperature were observed and parameterized for use in the atmospheric modeling of reactive mercury. Reactive mercury was observed to partition from the particle to the gas phase as ambient temperature increased. Good agreement between measurements made using urban and laboratory aerosols was seen after gas–particle-partitioning coefficients were normalized for surface area instead of mass. Thermodynamic analyses of the urban and laboratory gas–particle-partitioning measurements revealed that the strength of interaction between reactive mercury and particle surfaces was suggestive of chemisorption. Gas–particle-partitioning coefficients made with the Tekran ambient mercury analyzer (AMA) also showed a dependence on temperature. However, the Tekran AMA partitioning coefficients did not agree well with partitioning coefficients measured using the filter-based methods. The disagreement is consistent with the 50 °C operational temperature of the Tekran AMA.     

Columnar optical properties of tropospheric aerosol by combined lidar and sunphotometer measurements at Taipei,Taiwan

Vertical extinction profiles and columnar optical properties (optical depth, Angstrom exponent, lidar ratio, and particle depolarization) of aerosols were obtained by simultaneous measurements with a depolarization lidar and a sunphotometer at Taipei, Taiwan from February 2004 to January 2006. Columnar optical depths are high in Feb–Apr (0.61–0.75) by sunphotometer measurements. Lidar measurements show the contribution of aerosols in the free atmosphere on columnar optical depths are about 44–50% in Feb–Apr and about 26–37% in other months. Back-trajectory analyses and depolarization measurements show almost all of non-spherical aerosols originated from Northwest China which indicate Asian dusts frequently transported to Taipei from dust source regions in the free atmosphere. Aerosols with depolarization lower than 5% are found mostly originated from South China or Southeast Asia. Good correlations between columnar lidar ratio, particle depolarization, and Angstrom exponent are found for cases that columnar water vapor less than 1.5 cm. The effect of water vapor on particle depolarization is briefly discussed.     

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.     

The effects of aging processes on critical supersaturation ratios of ultrafine carbon aerosols

The condensation properties of polydisperse aged ultrafine carbon aerosols (particle diameter<1 μm) have been investigated by means of a variable supersaturation condensation nucleus counter. The critical supersaturation (S_c), as the point, where 50% of all particles have been activated and grew to droplets was compared to the median dry particle diameter for pure carbon aerosols, benzo[a]pyrene-tagged carbon aerosols and external mixtures of the carbon particles with sodium chloride and sulphuric acid aerosols. Additionally, ozone as oxidising gaseous compound was added in some of the experiments. Simple coagulation of pure and benzo[a]pyrene-tagged carbon particles resulted in only slightly lower values for S_c due to the increased median particle diameter. The formation of soluble functionalities on the particle surface, i.e. the coagulation with the soluble sodium chloride and sulphuric acid aerosols or the chemical decomposition of benzo[a]pyrene into polar, hydrophilic products due to the reaction with ozone resulted in significant lower values for S_c for the modified carbon aerosol. The necessary supersaturations for the increased hydrophilic particles dropped to atmospherically relevant values of 3% after 5 h reaction time (benzo[a]pyrene decomposition) and 15 h (coagulation with soluble particles), respectively.     

The Mass Distribution of Large Atmospheric Particles

This paper describes the results of a study to determine the total mass and the mass distribution of atmospheric aerosols, especially that mass associated with particles greater than 10 μm diameter. This study also determined what fraction of the total aerosol mass a standard high-volume air sampler collects and what fraction and size interval settle out on a dust fall plate. A special aerosol sampling system was designed for this study to obtain representative samples of large airborne particles. A suburban sampling site was selected because no local point sources of aerosols existed nearby. Samples were collected under various conditions of wind velocity and direction to obtain measurements on different types of aerosols.

Study measurements show that atmospheric particulate matter has a bimodal mass distribution. Mass associated with large particles mainly ranged from 5 to 100 μm in size, while mass associated with small particles ranged from an estimated 0.03 to 5 μm in size. Combined, these two distributions produced a bimodal mass distribution with a minimum around 5 μm diameter. The high-volume air sampler was found to collect most of the total aerosol mass, not just that fraction normally considered suspended particulate. Dust fall plates did not provide a good or very useful measure of total aerosol mass. The two fundamental processes of aerosol formation, condensation and dispersion appear to account for the formation of a bimodal mass distribution in both natural and anthropogenic aerosols. Particle size distribution measurements frequently are in error because representative samples of large airborne particles are not obtained. Considering this descrepancy, air pollution regulations should specify or be based upon an upper particle size limit.     

Technique for Measuring Dust Collector Efficiency As a Function of Particle Size

With a specially designed generator, producing an aerosol of concentration, chemical composition, and size distribution similar to incinerator aerosols, a scrubber was tested in the laboratory by sampling before and after the collector. Using an Andersen Sampler as a 7 stage cascade impactor the efficiency for 7 different size classes was determined. This technique provides a rapid and simple method for evaluating the performance of a collector as a function of particle size. The multistage impaction classifies the particles according to their aerodynamic behavior. Gravimetric analysis of each stage eliminates the need for tedious counting and sizing.     

Chemical characteristics of free tropospheric aerosols over the Japan Sea coast: aircraft-borne measurements

Atmospheric aerosol particulate matter was directly collected in the free troposphere over the Japan Sea coast between 1992 and 1994 using an aircraft-borne nine-stage cascade impactor (particle size range: 0.1–8 μm). The water-soluble components in the aerosol particulate matter were analyzed by ion chromatography. Particulate sulfate and ammonium were detected in most of the samples and their size distributions showed noticeable peaks below the 1 μm particle size range. Water-soluble calcium (Ca²⁺) was detected in half of the samples; the size distribution showed that the maximum particle size was larger than 1 μm. Highly concentrated Ca²⁺ in larger particles was possibly due to transport of Kosa aerosols from the Asian continent in the free troposphere. The concentration of fine particulate sulfate and ammonium tended to increase whenever Ca²⁺ was detected, which suggests possible mixing of Kosa aerosols and non-Kosa aerosols during long-range transport of air masses containing Kosa particles.