Mesostructured silica aerosol particles: comparison of gas-phase and powder deposit X-ray diffraction data

We report on the characterization of mesostructured aerosol silica particles in the gas phase using in situ synchrotron small-angle X-ray scattering (SAXS) in order to unveil the influence of the basic production parameters. The investigated system was based on tetraethylorthosilicate (TEOS) as the inorganic precursor and on cetyltrimethyl-ammonium bromide (CTAB) as the surfactant. The heating temperature, surfactant to silicate ratio, and particle flow rate were thoroughly investigated, and for this purpose, an in-house-built aerosol reactor equipped with a special X-ray observation chamber was used. Complementary fine structural analysis was applied on dried deposits of the silica aerosols comprising direct Fourier transforms as well as simple two-phase model fits. This resulted in robust estimates for the silica wall thickness and surfactant core radius of the hexagonally ordered mesostructure. The particle shape and size distribution were examined by scanning electron microscopy (SEM). The quality of the inner nanostructure was revealed from an analysis of the peak width. The comparison of data from the gas phase and powder deposit shows that, in general, slower drying conditions (heating temperature about 80 °C) and a medium surfactant to Si ratio (about 0.14) lead to nanostructures of the best quality in terms of well-defined long-range organization.     

Inertial deposition of aerosol particles from laminar flows in fibrous filters

The deposition of aerosol particles onto filter fibers under the effect of inertial forces is studied in a wide range of Stokes numbers (St) at Reynolds numbers close to unity (Re ∼ 1). Coefficients η of the capture of inertial particles with finite sizes in model filters composed of parallel rows of identical parallel fibers located normal to the direction of a flow are determined based on the numerical solution of the Navier-Stokes and particle motion equations. It is shown that, at Re < 1 and a constant particle-to-fiber radius ratio, R = r _p/a, number St uniquely characterizes capture coefficients η for particles with different densities, while, at Re ≥ 1, the capture coefficient depends on both St and Re. At constant R and St values, the larger Re the higher the capture coefficient. The influence of the structure of the model filter on pressure drop Δp and η is investigated. A nonuniform arrangement of fibers in rows is shown to increase the Δp/U ratio at lower Re values and to make the η -St dependence more pronounced than that for systems of uniformly ordered fibers. The results of calculations agree with the experimental data.     

Ozonolysis and photolysis of alkene-terminated self-assembled monolayers on quartz nanoparticles: implications for photochemical aging of organic aerosol particles

Photolysis of alkene-terminated self assembled monolayers (SAM) deposited on Degussa SiO(2) nanoparticles is studied following oxidation of SAM with a gaseous ozone/oxygen mixture. Infrared cavity ring-down spectroscopy is used to observe gas-phase products generated during ozonolysis and subsequent photolysis of SAM in real time. Reactions taking place during ozonolysis transform alkene-terminated SAM into a photochemically active state capable of photolysis in the tropospheric actinic window (lambda > 295 nm). Formaldehyde and formic acid are the observed photolysis products. Photodissociation action spectra of oxidized SAM and the observed pattern of gas-phase products are consistent with the well-established Criegee mechanism of ozonolysis of terminal alkenes. There is strong evidence for the presence of secondary ozonides (1,3,4-trioxalones) and other peroxides on the oxidized SAM surface. The data imply that photolysis plays a role in atmospheric aging of primary and secondary organic aerosol particles.     

Efficiency of inertial deposition of aerosol particles in fibrous filters with regard to particle rebounds from fibers

The inertial deposition of submicron aerosol nanoparticles onto fibers during gas filtration through fine-fiber filters is considered. It is shown that there is critical filtration velocity U* below which the energy loss upon collisions has no influence on the filtration efficiency. Above this critical velocity, the filtration efficiency depends on the mechanism of the inelastic energy loss and can be noticeably lower than the result of its estimation with no allowance for the particle rebound. For a rather dense fibrous medium, when not all particles that have rebounded from a fiber have time to attain the flow velocity before the next collision with another fiber, the filtration efficiency depends on the velocity distribution of the rebounding particles. It is shown that, in this case, the filtration efficiency must increase with the packing density of a filter.     

Comparison of operator- and computer-controlled scanning electron microscopy of particles from different atmospheric aerosol types

Analytical and Bioanalytical Chemistry - Individual aerosol particles from an urban background site in Mainz (Germany), a traffic hotspot site in Essen (Germany), the free troposphere in the Swiss...     

Microwave-assisted extraction of metal elements from glass fibrous filters for aerosol sampling

Atmospheric aerosols are generally collected on filters according to the International Monitoring System (IMS) designed in the Comprehensive Nuclear-Test-Ban Treaty (CTBT). More information could be revealed when the filter sample is pretreated rather than measured directly by g-ray spectrometer. Microwave-assisted extraction (MAE) is a suitable method that gives higher recoveries of elements from glass fibrous filters under different conditions. The results indicate that the MAE is a highly efficient and robust method for the treatment of glass fibrous filter samples. The recoveries of potential fission products from glass fibrous filter samples by microwave-assisted extraction meet the efficiency of the extraction by both aqua regia and 2% HCl.     

Chemical preparation and investigation of Fe-P-B ultrafine amorphous alloy particles

A series of Fe-P-B ultrafine amorphous alloy particles has been prepared by the chemical reduction method The composition and size of the particles have been effectively adjusted.Mossbauer spectroscopy in addition to sonic other techniques has been used to investigate the reaction process,the factors that influence the preparation,the crystallization of the particles,and the interactions between the components within them.The results indicate that the co-deposition of iron,phosphorus and boron atoms in the solution at room temperature forms Fe-P-B amorphous alloy particles,and a preferential bonding of Fe-P bond to Fe-B one exists in the particles.     

Laser chemical synthesis of clusters and ultrafine particles using organometallics

Gas-phase synthesis of clusters and ultrafine particles using lasers and organometallics is reviewed. The general field of laser chemistry is introduced in the context of using organometallics as reactants. Examples of particle and cluster synthesis in flowing gases and in bulk gases, and during laser chemical vapor deposition, are given. A brief introduction to the general field of random irreversible fractal coagulation provides a basis for describing how powders, clusters and ultrafine particles are synthesized. References to applications and characterization methods are given.     

Methods for characterization of organic compounds in atmospheric aerosol particles

Atmospheric aerosol particles of primary or secondary, biogenic or anthropogenic origin are highly complex samples of changing composition in time and space. To assess their effects on climate or human health, the size-dependent chemical composition of these ubiquitous atmospheric constituents must be known. The development of novel analytical methods has enabled more detailed characterization of the organic composition of aerosols. This review gives an overview of the methods used in the chemical characterization of atmospheric aerosol particles, with a focus on mass-spectrometry techniques for organic compounds, either alone or in combination with chromatographic separation. Off-line, on-site, and on-line methods are covered, and the advantages and limitations of the different methods are discussed. The main emphasis is on methods used for detailed characterization of the composition of the organic compounds in aerosol particles. We address and summarize the current state of analytical methods used in aerosol research and discuss the importance of developing novel sampling strategies and analytical instrumentation.

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Graphical Abstract Challenges in the atmospheric aerosol analytics

     

Retention of phosphorus by iron and aluminum-oxides-coated quartz particles

The capacity of adsorption of P on Fe and Al-oxides-coated quartz sand has been studied. The adsorption process has been described as Freundlich and Langmuir isotherms. In all cases Langmuir equation yields better fits than Freundlich equation. The covering quartz particles with Fe and Al oxides provide a high capacity adsorption and immobilization of P from natural and waste waters. The values obtained for adsorption, desorption and adsorption/desorption cycles show that Al oxides particles provide an excellent material for construction of a P removal system for waste waters. The characteristics of this material would allow the design of a complementary filtration system to reduce P levels in the effluent, reducing contamination risks and combating eutrophication of nearby watercourses.     

Mechanisms for the formation of secondary organic aerosol components from the gas-phase ozonolysis of alpha-pinene

Gas-phase ozonolysis of alpha-pinene was studied in static chamber experiments under 'OH-free' conditions. A range of multifunctional products-in particular low-volatility carboxylic acids-were identified in the condensed phase using gas chromatography coupled to mass spectrometry after derivatisation. The dependence of product yields on reaction conditions (humidity, choice of OH radical scavengers, added Criegee intermediate scavengers, NO(2)etc.) was investigated to probe the mechanisms of formation of these products; additional information was obtained by studying the ozonolysis of an enal and an enone derived from alpha-pinene. On the basis of experimental findings, previously suggested mechanisms were evaluated and detailed gas-phase mechanisms were developed to explain the observed product formation. Atmospheric implications of this work are discussed.     

Design of aerosol sampler to remove radon and thoron progeny interference from aerosol samples for nuclear explosion monitoring

A Nuclear Explosion Monitoring Inertial Impactor (NEMII) system was developed to physically separate naturally occurring radionuclides from those produced in nuclear weapons explosions. Studies show that aerosols containing natural activity have an aerodynamic diameter in the range of 0.1–1.0 μm. It has been established that atmospheric nuclear explosions produce radioactive aerosols with aerodynamic diameters <0.1 μm and surface explosion produce a bimodal distribution of radioactive particles with aerodynamic diameters both >1.0 μm and <0.1 μm. A high volume (66 m³ h⁻¹) impactor was designed to separate the particles into three size distributions: aerosols with aerodynamic diameters >1.0 μm, between 0.1 and 1.0 μm, and smaller than 0.1 μm. Calculations based on previous work for high-volume impactors were completed to obtain the impactor geometry that yields the desired cutoff values. The components of the aerosol impactor were manufactured or obtained and then assembled. In addition, a submicrometer aerosol generation system was assembled to benchmark the NEMII system against a commercial Micro-Orifice Uniform-Deposit Impactor (MOUDI). The MOUDI was also used to verify the naturally occurring radioactivity distribution using ²¹²Pb gamma spectra.     

Procedure for controlling size of silver particles deposited photochemically on quartz

The results of studying optical properties of silver films deposited photochemically on a quartz surface are presented. The films consist of isolated silver particles of 5–50 nm in size and of agglomerates of several micrometers in size and contain up to 7 wt % of Ag₂O. Treatment of the films with dimethylformamide solution of [Pden₂](BPh₄)₂ results in a decrease in the average particle size due to dissolution of small particles (5–15 nm) and destruction of greater agglomerates.     

"Virtual injector" flow tube method for measuring relative rates kinetics of gas-phase and aerosol species

A new method for measuring gas-phase and aerosol reaction kinetics is described in which the gas flow, itself, acts as a "virtual injector" continuously increasing the contact time in analogy to conventional movable-injector kinetics techniques. In this method a laser is directed down the length of a flow tube, instantly initiating reaction by photodissociation of a precursor species at every point throughout the flow tube. Key tropospheric reactants such as OH, Cl, NO(3), and O(3) can be generated with nearly uniform concentrations along the length of the flow tube in this manner using 355 nm radiation from the third harmonic of a Nd:YAG laser. As the flow travels down the flow tube, both the gas-phase and particle-phase species react with the photogenerated radicals or O(3) for increasingly longer time before exiting and being detected. The advantages of this method are that (1) any wall loss of gas-phase and particle species is automatically accounted for, (2) the reactions are conducted under nearly pseudo-first-order conditions, (3) the progress of the reaction is followed as a continuous function of reaction time instead of reactant concentration, (4) data collection is quick with an entire decay trace being collected in as little as 1 min, (5) relative rates of several species can be measured simultaneously, and (6) bimolecular rate constants at least as small as k = 10(-17) (cm(3)/molecule)/s, or aerosol uptake coefficients at least as small as γ = 10(-4), can be measured. Using the virtual injector technique with an aerosol chemical ionization mass spectrometer (CIMS) as a detector, examples of gas-phase relative rates and uptake by oleic acid particles are given for OH, Cl, NO(3), and O(3) reactions with most agreeing to within 20% of published values, where available.     

Phase transitions and surface morphology of surfactant-coated aerosol particles

Probe molecule spectroscopy and hygroscopic growth curves characterize the morphology of surfactant-coated aerosol particles as a function of relative humidity (RH). This study focuses on particles composed of either potassium iodide or sodium chloride and sodium dodecyl sulfate (SDS). At high RH, these mixed particles assume a reverse micelle type structure, and at low RH, they comprise a solid core of either KI or NaCl coated with SDS and water. The deliquescence relative humidity (DRH) and efflorescence relative humidity (ERH) of the inorganic fraction of the mixed particles are very similar to those of the pure salts. The surface polarity and morphology sampled by the coumarin 314 probe molecule ranges from that of a water-organic interface to that of an ionic surface and depends strongly on the RH and the amount of SDS. When the SDS coverage of the droplet just prior to efflorescence reaches approximately one monolayer, a thin soap film persists on the surface to values of RH much lower than the ERH. Both the electronic spectroscopy and photoelectric charging efficiency show a separate efflorescence for this layer at RH < 5%. The spectroscopy further reveals that there is a hysteresis associated with this low RH phase transition for both KI and NaCl cores.     

Chemical composition and reaction analysis of single aerosol particles

In situ measurements of gas-liquid surface reactions of single aerosol microdroplets are presented. By means of optical levitation in combination with elastic (Mie) and inelastic (Raman) light scattering it is possible to get information on the chemistry of e.g. acid/base reactions as well as the physical behavior of single microparticles.