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.     

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.     

Sampling and analysis of individual particles by aerosol mass spectrometry

Over the past decade, aerosol mass spectrometry has developed into a powerful method for characterizing individual particles in air. Recent advances in the design of inlets and mass spectrometers have extended the size range of particles that can be analyzed. In this tutorial, fundamental aspects of particle motion in sampling inlets are introduced. Basic experimental configurations for achieving a high analysis rate and the ability of laser ablation to provide chemical composition information are reviewed. An example of the use of this technology to study atmospheric phenomena is also presented. Significant opportunity exists for designing new experiments at the interface of aerosol mass spectrometry and conventional molecular mass spectrometry.     

Quantitative analysis of single aerosol particles using polycapillary X-ray optics

A laboratory micro X-ray fluorescence spectrometer based on polycapillary X-ray optics (PXRO) was used to carry out the quantitative X-ray fluorescence analysis of single aerosol particles with smaller size than that of focal spot of PXRO. The minimum detection limits measured with the thin-film reference standards were in the range from 13.3 to 0.7 ng cm^? 2 when the operating current and voltage were 70 mA and 35 kV, respectively. In order to reduce the effects of the inhomogeneous distributions of the X-ray intensity in the focal spot of the PXRO on the analysis results, the sensitivities were corrected by using a Gaussian function for the quantitative analysis of single aerosol particles. The accuracy of the analysis of single standard solution drops was on average 25% depending on the element and concentration. The precision of the analysis was better than 5%.     

Dynamics of colloidal particles in ice

We use x-ray photon correlation spectroscopy (XPCS) to probe the dynamics of colloidal particles in polycrystalline ice. During freezing, the dendritic ice morphology and rejection of particles from the ice created regions of high particle density, where some of the colloids were forced into contact and formed disordered aggregates. The particles in these high density regions underwent ballistic motion, with a characteristic velocity that increased with temperature. This ballistic motion is coupled with both stretched and compressed exponential decays of the intensity autocorrelation function. We suggest that this behavior could result from ice grain boundary migration.     

Unraveling the origin of band shapes in infrared spectra of N2O-12CO2 and 12CO2-13CO2 ice particles

Band structures in the region of strong infrared absorption bands for different N2O-12CO2 and 12CO2-13CO2 composite particles are investigated by combining quantum mechanical exciton calculations with systematic experimental investigations. The ice particles are generated by collisional cooling and characterized with rapid-scan infrared spectroscopy. The size of the particles lies between approximately 10 and 100 nm. The calculated spectra show excellent agreement with the experimental data. This work leads to a detailed understanding on a molecular level of shape effects in pure and statistically mixed particles as well as of the characteristic features observed for core-shell particles.     

Effects of pretreatment temperature on the analysis of size-fractionated aerosol particles using ToF-SIMS

Size-fractionated aerosol particles were collected with a MOUDI 10-stage cascade impactor from an urban roadside place in a downtown area of Hong Kong. Fine aerosol particulate samples from stage 6 (aerodynamic particle diameter between 0.56 and 1 μm) and stage 9 (aerodynamic particle diameter between 0.10 and 0.18 μm) were pretreated at a chosen temperature, including −100°C, −50°C, 25°C, and 60°C, in a load lock chamber and then analyzed using time-of-flight secondary ion mass spectrometry (ToF-SIMS) at the same temperature (−100°C). Principal component analysis (PCA) was applied to further analyze ToF-SIMS spectra of aerosol particles with different pretreatment temperatures from two selected stages. ToF-SIMS results showed that the intensities of aliphatic hydrocarbon ions such as C₄H₇⁺ and C₄H₉⁺ and amine ions such as C₂H₈N⁺ and C₄H₁₂N⁺ decreased with an increase of the pretreatment temperature under ultrahigh vacuum conditions. We have shown that analyses of this type of aerosol particles using ToF-SIMS should not be conducted at ambient temperature but at low temperature (eg, −50°C). In addition, we also developed a procedure that can be used to analyze aerosol particle samples under ultrahigh vacuum environment.     

Vibrational delocalization in ammonia aerosol particles

The present contribution investigates shape effects and surface effects in the infrared spectra of pure (NH(3)) and mixed (NH(3)-CO(2) and NH(3)-NH(2)D-NHD(2)-ND(3)) ammonia particles with sizes between about 1 and 50 nm. The particles investigated have been generated in a collisional cooling cell as aerosols at temperatures between 20 and 80 K. The contribution reveals that only the combination with a microscopic model leads to a comprehensive understanding of the various features observed in the experimental infrared spectra. As one of the major results, the corresponding exciton model explains why pronounced shape effects observed for pure particles only play a minor role in the case of mixed particles.     

Crystallization pathways of sulfate-nitrate-ammonium aerosol particles

Crystallization experiments are conducted for aerosol particles composed of aqueous mixtures of (NH(4))(2)SO(4)(aq) and NH(4)NO(3)(aq), (NH(4))(2)SO(4)(aq) and NH(4)HSO(4)(aq), and NH(4)NO(3)(aq) and NH(4)HSO(4)(aq). Depending on the aqueous composition, crystals of (NH(4))(2)SO(4)(s), (NH(4))(3)H(SO(4))(2)(s), NH(4)HSO(4)(s), NH(4)NO(3)(s), 2NH(4)NO(3) x (NH(4))(2)SO(4)(s), and 3NH(4)NO(3) x (NH(4))(2)SO(4)(s) are formed. Although particles of NH(4)NO(3)(aq) and NH(4)HSO(4)(aq) do not crystallize even at 1% relative humidity, additions of 0.05 mol fraction SO(4)(2-)(aq) or NO(3)(-)(aq) ions promote crystallization, respectively. 2NH(4)NO(3) x (NH(4))(2)SO(4)(s) and (NH(4))(3)H(SO(4))(2)(s) appear to serve as good heterogeneous nuclei for NH(4)NO(3)(s) and NH(4)HSO(4)(s), respectively. 2NH(4)NO(3) x (NH(4))(2)SO(4)(s) crystallizes over a greater range of aqueous compositions than 3NH(4)NO(3) x (NH(4))(2)SO(4)(s). An infrared aerosol spectrum is provided for each solid based upon a linear decomposition analysis of the recorded spectra. Small nonzero residuals occur in the analysis because aerosol spectra depend on particle morphology, which changes slightly across the range of compositions studied. In addition, several of the mixed compositions crystallize with residual aqueous water of up to 5% particle mass. We attribute this water content to enclosed water pockets. The results provide further insights into the nonlinear crystallization pathways of sulfate-nitrate-ammonium aerosol particles.     

Desorption electrospray ionization of aerosol particles

We have applied desorption electrospray ionization to aerosol particles. Ions were formed from aerosols by merging suspended dry particles with an electrospray of solvent in a modified ion trap mass spectrometer. Dry aerosol particles were generated using a fluidized bed powder disperser and directed toward the inlet of the mass spectrometer. A nanospray source was used to create a spray of solvent droplets directed at the inlet and at a right angle with respect to the aerosol. Ions generated by the interaction of the particles and electrospray were transferred into the ion trap mass spectrometer. Using this method, pure samples of caffeine and erythromycin A were analyzed. In addition, commonly available food and drug powders including instant cocoa powder, artificial sweetener and ibuprofen were analyzed.     

Uptake of phenol on aerosol particles

We present a study of the interaction between a phenol molecule and an aerosol particle. The aerosol particle is represented by a cluster of 128 water molecules. Using a classical approach, we present interaction energy surfaces for different relative distances and for three orientations of phenol relative to the particle. From the energy surfaces we find the reaction pathways with the largest interaction between the molecule and the particle. We use a quantum mechanics/molecular mechanics (QM/MM) method to calculate a potential energy curve for each reaction path. Coupled cluster methods are used for the part of the system described by quantum mechanics, while the part described by molecular mechanics is represented by a polarizable force field. We compare results obtained from the classical approach with the QM/MM results. Furthermore, we use the QM/MM results to calculate mass accommodation coefficients using a quantum-statistical (QM-ST) model and show how the mass accommodation coefficient depends on the relative orientation of phenol with respect to the aerosol particle.     

Infrared spectroscopy of acetic acid and formic acid aerosols: pure and compound acid/ice particles

Acetic acid aerosol particles, formic acid aerosol particles and mixed acid/ice particles were generated in a collisional cooling cell at a temperature of 78 K and investigated using in situ rapid scan Fourier transform infrared spectroscopy. The infrared spectra reveal that the internal structure of the particles critically depends on the particle formation conditions and, especially for the mixed particles, on the composition. The acetic acid particles are likely to have only a partially crystalline structure whereas the formic acid particles are likely to have an overall crystalline structure. The existence of acid in the mixed acid/ice particles prevents the ice from crystallization even at low acid concentrations (less than 10%). Mid-infrared refractive index data were derived from the different particle spectra, which can be helpful for remote sensing of such systems.     

Design of a doubly-curved crystal to improve X-ray fluorescence analysis of aerosol particles

Doubly-curved crystals (DCCs) can be very useful devices to focus and monochromatize radiation from an X-ray tube or a synchrotron, especially for X-ray fluorescence analysis. However, production of a DCC is somewhat difficult. In this paper we will present some basic theory about DCC geometries, different ways of DCC production and methods to test the quality of the DCCs.     

Real-time analysis of secondary organic aerosol particles formed from cyclohexene ozonolysis using a laser-ionization single-particle aerosol mass spectrometer.

A real-time analysis of secondary organic aerosol (SOA) particles formed from cyclohexene ozonolysis in a smog chamber was performed using a laser-ionization single-particle aerosol mass spectrometer (LISPA-MS). The instrument obtains both size and chemical compositions of individual aerosol particles with a high time-resolution (approximately 2 s at the maximum). Both positive and negative-ion mass spectra are obtained. Standard particles generated from dicarboxylic acid solutions using an atomizer were also analyzed. For both standard and SOA particles, the negative-ion mass spectra provided information about the molecular weights of the organic compounds in the particles, since the intense ions in the negative-ion mass spectra are mainly attributable to the molecular-related ions [M-H]-. It was demonstrated that the real-time single-particle analysis of SOA particles by the LISPA-MS technique can reveal the formation and transformation processes of SOA particle in smog chambers.     

Gas chromatographic analysis and aerosol mass spectrometer measurement of diesel exhaust particles composition

Aerosol particles have important effects on human health, climate, regional visibility, and the deposition of acidic and toxic substances. The aerosols also have significant pharmaceutical and industrial applications. Trials of gas chromatographic analysis of extracts composition of diesel exhaust particles and aerosol mass spectrometer measurement of diesel exhaust particles composition are introduced in this paper. Usually, organic fraction of automotive exhaust particles are concentrated to 1 mL by Kuderna-Danish concentrator after extracted into dichloromethane by soxhlet extraction. Then, these extracts are analyzed by GC/MS. In the extracts from the diesel exhaust particles, there are over several thousands of components, for example paraffinic hydrocarbons, aromatics, oxygenates and other hydrocarbons.     

Size spectra for trace elements in urban aerosol particles by instrumental neutron activation analysis

Size-fractionated aerosol samples collected with micro-orifice impactors at Camden, NJ, a heavily industrialized urban area, and at two sites near Washington, DC, were analyzed for elemental constituents determined instrumentally from short-lived neutron activation products. A least-squares peak-fitting method was used with impactor calibration data to determine log-normal distribution parameters, i.e., mass median aerodynamic diameter (MMAD) and geometric standard deviation (_g) for particles bearing S, V, Br, and I. For these elements, MMADs ranged from 0.24 to 0.65 m; 0.23 to 0.53 m; 0.22 to 0.61 m, and 0.20 to 0.48 m, respectively.     

Infrared spectra of dimethylphenanthrenes in the gas phase

Infrared spectra of atmospherically and astronomically important dimethylphenanthrenes (DMPs), namely 1,9-DMP, 2,4-DMP, and 3,9-DMP, were recorded in the gas phase from 400 to 4000 cm(-1) with a resolution of 0.5 cm(-1) at 110 °C using a 7.2 m gas cell. DFT calculations at the B3LYP/6-311G** level were carried out to get the harmonic and anharmonic frequencies and their corresponding intensities for the assignment of the observed bands. However, spectral assignments could not be made unambiguously using anharmonic or selectively scaled harmonic frequencies. Therefore, the scaled quantum mechanical (SQM) force field analysis method was adopted to achieve more accurate assignments. In this method force fields instead of frequencies were scaled. The cartesian force field matrix obtained from the gaussian calculations was converted to a nonredundant local coordinate force field matrix and then the force fields were scaled to match experimental frequencies in a consistent manner using a modified version of the UMAT program of the QCPE package. Potential energy distributions (PEDs) of the normal modes in terms of nonredundant local coordinates obtained from these calculations helped us derive the nature of the vibration at each frequency. The intensity of observed bands in the experimental spectra was calculated using estimated vapor pressures of the DMPs. An error analysis of the mean deviation between experimental and calculated intensities reveal that the observed methyl C-H stretching intensity deviates more compared to the aromatic C-H and non C-H stretching bands.     

Investigation of aerosol particles by atomic force microscopy

AFM has been applied for studying morphology and size distribution of nanometer-sized particles adsorbed on flat surfaces. In order to optimize imaging of these ultrafine particles different substrates were evaluated with respect to their roughness and stability under the influence of the sensing tip. Moreover, a method for calculating particle volumes from the three-dimensional AFM data is described. This greatly enhances the information content of AFM images, because a large number of particles in the raw data can be evaluated automatically in order to derive information on size distribution or surface coverage. This evaluation method has also been applied successfully to quantitatively describe changes on particles induced by different humidity of the surrounding atmosphere. Received: 15 July 1996 / Revised: 18 December 1996 / Accepted: 3 January 1997     

Characterisation of aerosol particles using combined thermoanalytical techniques

Four different artificial aerosol particles as well as one standard environmental aerosol particle (NIST SRM 1649a) were investigated. While the mass loss of the aerosol particles varies from 1.5 to 32% of the entire mass, only a small part of each volatile fraction consists of organic compounds. Due to the construction of the combined thermoanalytical system, only a small part of the evolved gases is used for the mass spectrometric investigation. This results in a restricted sensitivity which does not allow an identification of individual organic components. Additional investigations like thermal desorption GC-MS reveal up to 1600 individual components (SRM 1649a). This revised version was published online in July 2006 with corrections to the Cover Date.