Atomization problems in atomic absorption spectroscopy—IV: Impact devices, spray chambers and interferences

A study is made of the effect of the design and position of impact devices on the nebulization efficiency and the extent of volatilization interferences in atomic absorption measurements using an air-acetylene flame. Experiments are described using new designs of spray chamber, either alone or following a tapered spray chamber. The most effective way of reducing volatilization interferences is to force the aerosol to pass through a jet and impinge on a flat surface, either at an impact device or in a spray chamber. This always involves a decrease in the analytical signal, but the signal-to-noise ratio is essentially unchanged. The aerosol transport model of Browner, Boorn and Smith is applied, with modifications where necessary, to calculate the cut-off characteristics of some of the systems studied. Drop-size distribution measurements made on some of the spray chambers substantiate the conclusion that reduction of volatilization interferences and the concomitant loss of analytical signal are due to the selective removal of the larger droplets of the aerosol. For several well-known volatilization interferences, values are derived for the limiting diameters of droplets which can be effectively vaporized in the air-acetylene flame under the experimental conditions used.     

Deliquescence and efflorescence behavior of ternary inorganic/organic/water aerosol particles

The deliquescence behavior of ternary inorganic (ammonium sulfate and ammonium nitrate)/organic (glutaric acid and malonic acid)/water aerosol particles has been investigated at 293 K using a novel surface aerosol microscopy (SAM) technique. The results obtained for the deliquescence relative humidities (DRH) for particles of variable inorganic/organic contents show a eutectic behavior with the mixed particles showing deliquescence at lower DRH compared to the pure inorganic and organic components, respectively. This behavior has been quantitatively modeled using the extended aerosol inorganics (E-AIM) thermodynamic model of Clegg et al. in combination with the UNIFAC group activity approach to account for organic molecular solutes. In addition, we have investigated the crystallization behavior of supersatured and formerly deliquesced ternary solution droplets using space resolved Raman spectroscopy. It is found that such droplets produce solid particles in which the inorganic and organic phases show some spatial separation with the organic component being predominantly found at the outer part of the particle. Independent measurements of the contact angles of such ternary droplets reveal that their angles are within experimental error identical to those of the purely organic/water solutions.     

Effect of sodium during the aerosol transport and filtering in inductively coupled plasma atomic emission spectrometry

Robust conditions, i.e. high R.F. power and low carrier gas flow rate were used to minimize the role of the plasma and to emphasize the contribution of the sample introduction system in the effect of Na in ICP-AES. Two combinations of pneumatic nebulizers and spray chambers were selected to obtain different Na effects. A conespray nebulizer was used with a cyclone spray chamber, and a cross-flow nebulizer was coupled to a double-pass spray chamber. A decrease in the ICP-AES analyte signal was observed with Na solutions under so-called robust conditions, irrespective of the sample introduction system employed. The cross-flow nebulizer associated with the double-pass spray chamber was more sensitive to Na presence than the other combination. These observations can be partially explained by a decrease in the solvent transport rate observed in presence of Na. It has been found that, in every case, the presence of Na did not modify the characteristics of the primary aerosol, while the tertiary aerosol is significantly modified. Finer droplets were obtained at the exit of the spray chamber when Na was present. Also, recirculation of the aerosol led to a significant element enrichment of the largest droplets for the Na solutions. It can be concluded that the effect of Na occured during the aerosol transport and filtering through the spray chamber.     

A strategy for characterizing the mixing state of immiscible aerosol components and the formation of multiphase aerosol particles through coagulation

We demonstrate that the coagulation of two aerosol droplets of different chemical composition can be studied directly through the unique combination of optical tweezers and Raman spectroscopy. Multiple optical traps can be established, allowing the manipulation of multiple aerosol droplets. Spontaneous Raman scattering allows the characterization of droplet composition and mixing state, permitting the phase segregation of immiscible components in multiphase aerosol to be investigated with spatial resolution. Stimulated Raman scattering allows the integrity of the droplet and uniformity of refractive index to be probed. The combination of these spectroscopic probes with optical tweezers is shown to yield unprecedented detail in studies of the coagulation of decane and water droplets.     

Modelling of ionic concentrations and sulfate production in cloud droplets: use of published aerosol data

Summary In this study a cloud model describing an ascending, adiabatically closed parcel was used to show the influence of the quality of data about the chemical composition of aerosol particles on the model results. The input data for the model were based on measured aerosol chemical compositions which were compiled from literature data. Model results influenced by incomplete chemical characterization of the particles are the radii of the large droplets, which depend on the activation parameter, and the pH-values of the droplets, which depend on the ionic balance of the particles.     

Water aerosols spraying for SO2 and NOx removal from gases under E-beam irradiation

The gas-phase transport process of an admixture to the surface of spraying aerosol droplets has been experimentally investigated with reference to E-beam gas cleaning processes. The rate of SO₂ uptake by alkali aerosol droplets with average radius 30 μm has been measured in gas-aerosol jet using light absorption technique. It has been shown that the rate of gas-phase transport is described by the molecular flux of the admixture. Gas-liquid reactions are considered to explain the observed improvement of radiation-induced NO removal in the presence of spraying alkali aerosol.     

Guiding, distribution, and storage of trains of shape-dependent droplets

We present a simple method of guiding, distributing, and storing of a train of shape-dependent droplets by using side flows, cavity guiding tracks, and storage chambers. The squeezing flow makes a train of flattened droplets to align to one side of the wall and the pushing flow guides it to one of the designated guiding tracks. Then the guided droplets move along the guiding track due to the lowered surface energy when they flow along the track. In addition, simultaneous droplet guiding and storing process has been demonstrated. An array of storage chambers placed in each track could store each train containing differently concentrated droplets. The proposed method will be useful for distribution of droplets for further processes or storing for multiplex, large-scale, dynamic assays over time.     

Infrared optical constants of highly diluted sulfuric acid solution droplets at cirrus temperatures

Complex refractive indices for supercooled sulfuric acid solution droplets in the mid-infrared spectral regime (wavenumber range 6000-800 cm(-1)) have been retrieved for acid concentrations ranging from 33 to 10 wt % H2SO4 at temperatures between 235 and 230 K, from 36 to 15 wt % H2SO4 at temperatures between 225 and 219 K, and from 37 to 20 wt % H2SO4 at temperatures between 211 and 205 K. The optical constants were derived with a Mie inversion technique from measured H2SO4/H2O aerosol extinction spectra that were recorded during controlled expansion cooling experiments in the large coolable aerosol chamber AIDA of Forschungszentrum Karlsruhe. The new data sets cover a range of atmospherically relevant temperatures and compositions in the binary sulfuric acid/water system for which infrared refractive indices have not been published so far, namely, the regime when supercooled H2SO4/H2O solution droplets at T < 235 K are subjected to an environment that is supersaturated with respect to the ice phase. With increasing ice supersaturation, the H2SO4/H2O aerosol particles will continuously dilute by the uptake of water vapor from the gas phase until freezing of the solution droplets eventually occurs when the acid concentration has dropped below a critical, temperature-dependent threshold value. With the aid of the new measurements, the homogeneous freezing process of supercooled H2SO4/H2O solution droplets at cirrus temperatures can be quantitatively analyzed by means of Fourier transform infrared spectroscopy, thereby overcoming a major drawback from previous studies: the need to use complex refractive indices that were measured at temperatures well above 235 K to deduce the composition of the low-concentrated H2SO4/H2O aerosol particles. As in the case of the complex refractive indices for sulfuric acid solutions with acid concentrations greater than 37 wt % H2SO4, the new low-temperature optical constants for highly diluted droplets also reveal significant temperature-induced spectral variations in comparison with the refractive indices for higher temperatures, which are associated with a change in the equilibrium between sulfate and bisulfate ions.     

The role of natural and man-made ice-forming nuclei in the atmosphere

Water-soluble and insoluble, organic and inorganic, natural and man-made aerosol particles participate in vapor-liquid, vapor-solid (ice), and liquid-solid phase transitions in the atmosphere. Hydrosol particles (aerosol particles that have been transferred into water droplets) nucleate ice through freezing. A small without scavenging or being scavenged by another aerosol particle. It is also difficult to imagine that pure mineral particles can be lifted from soil surfaces. In view of this, an ice-nucleating site may be a much smaller particle attached to a larger clay particle. To this category belong, e.g., silver iodide-clay mixed particles. Limited studies indicate that decaying leaves and forest litter under the surface of soils are a potential source of biogenic ice-forming nuclei but that their contribution to the atmosphere is very limited. Research should be directed to study possible relations between cloud condensation nuclei and ice-forming nuclei derived from natural organic compounds (terpenes, leaf-derived nuclei, bacteria, etc.).

A balance must be maintained between large cloud chambers, in which duplication of in-cloud processes is possible, and the special instrumentation which provides information about the modes of ice nucleation on aerosol particles. The two modes of instrumentation should supplement each other.

The greatest difficulty in attempting to make a comparison between the number of ice-forming nuclei estimated in the laboratory and the number in a cloud is the lack of knowledge of the time-temperature-humidity history of the aerosol particles. In nature, the ability of an aerosol particle to nucleate ice may be destroyed or“poisoned“ in the presence of pollutants. An aerosol particle may, on the other hand, become an activated or warmer ice-forming nucleus, e.g.,after the sublimation of ice once formed on it. The temperature of ice nucleation is not a singular property of a particle; the warmest temperatures of ice nucleation of, e.g., particles of a certain soil 10cm in diameter are-15°C,-10°C, and-8°C for nucleation through freezing, condensation followed by freezing and contact, respectively (ref.26). The progress made in instrumentation permits studies of the modes of ice nucleation. Understanding the physical and chemical processes taking place in clouds makes estimates of the rates of ice particle formation more realistic (Young [ref.157]).

The reader should examine two previous reviews written by Mossop (1963) and Montefinale . (1971) for a more complete list of references.     

RAMAN STUDIES OF AEROSOL CHEMICAL REACTIONS

Since Professor Matijevité and his colleagues published pioneering work on aerosol chemical reactions, based on experiments with monodisperse aerosol generators and laminar flow reactors, there has been considerable progress in the chemical characterization of aerosol particles and the study of their chemical reactions. This paper surveys recent developments and new research on the application of Raman spectroscopy to gas/liquid and gas/solid aerosol reactions. Of particular interest are applications of the vibrating orifice aerosol generator and electrodynamic and optical levitators coupled to Raman spectrometers to explore aerosol chemistry. The systems examined include the production of polymeric microsphcrcs, the generation of metal oxide particles from alkoxide droplets, SQ2/sorbent particle reactions used for demilitarization of stick gases, chemical characterization of particle arrays, and reactions following collisions of dissimilar particles. The complications associated with the interpretation of Raman data introduced by morphology-dependent resonances in the elastically scattered light are also examined.     

Characterizing the formation of organic layers on the surface of inorganic/aqueous aerosols by Raman spectroscopy

We demonstrate that nonlinear Raman spectroscopy coupled with aerosol optical tweezers can be used to probe the evolving phase partitioning in mixed organic/inorganic/aqueous aerosol droplets that adopt a core-shell structure in which the aqueous phase is coated in an organic layer. Specifically, we demonstrate that the characteristic fingerprint of wavelengths at which stimulated Raman scattering is observed can be used to assess the phase behavior of multiphase decane/aqueous sodium chloride droplets. Decane is observed to form a layer on the surface of the core aqueous droplet, and from the spectroscopic signature the aqueous core size can be determined with nanometer accuracy and the thickness of the decane layer with an accuracy of +/-8 nm. Further, the presence of the organic layer is observed to reduce the rate at which water evaporates from the core of the droplet with an increasing rate of evaporation observed with diminishing layer thickness.     

Comparison of two different approaches to calibrate an energy-dispersive x-ray fluorescence spectrometer for the analysis of aerosol-loaded filters

The quantitative analysis of aerosol loaded filters by x-ray fluorescence spectroscopy implies the use of calibration curves obtained from synthetic standards. Two preparation methods to obtain these calibration samples are described and compared, showing that matrix and enhancement effects are neglible for membranous filters and that both calibrations lead to acceptable results. Calibration standards produced via an aerosol generator always lead to a greater sensitivity compared to the standard produced with droplets. The filters resist the conditions of replicated measurements.     

Comparison of two different approaches to calibrate an energy-dispersive x-ray fluorescence spectrometer for the analysis of aerosol-loaded filters

The quantitative analysis of aerosol loaded filters by x-ray fluorescence spectroscopy implies the use of calibration curves obtained from synthetic standards. Two preparation methods to obtain these calibration samples are described and compared, showing that matrix and enhancement effects are neglible for membranous filters and that both calibrations lead to acceptable results. Calibration standards produced via an aerosol generator always lead to a greater sensitivity compared to the standard produced with droplets. The filters resist the conditions of replicated measurements.     

Observation and modelling of clamshell droplets on vertical fibres subjected to gravitational and drag forces

Extensive experimental investigation of the wetting processes of fibre-liquid systems during air filtration (when drag and gravitational forces are acting) has shown many important features, including droplet extension, oscillatory motion, and detachment of drops from fibres as airflow velocity increases, and also movement or flow of droplets along fibres. A detailed experimental study of the processes was conducted using stainless steel filter fibres and H2O aerosol, which coalesce on the fibre to form clamshell droplets. The droplets were predominantly observed in the Reynolds transition flow region, since this is the region where most of the above features occur. The droplet oscillation is believed to be induced by the onset of the transition from laminar to turbulent flow as the increasing droplet size increases Reynolds number for the flow around the droplet. Two-dimensional flow in this region is usually modelled using the classical Karman vortex street, however there exist no 3D equivalents. Therefore to model such oscillation it was necessary to create a new conceptual model to account for the forces both inducing and preventing such oscillation. The agreement between the model and experimental results is very good for both the radial and transverse oscillations.     

Manipulation and characterization of aqueous sodium dodecyl sulfate/sodium chloride aerosol particles

Aerosol optical tweezers coupled with Raman spectroscopy can allow the detailed investigation of aerosol dynamics. We describe here measurements of the evolving size, composition, and phase of single aqueous aerosol droplets containing the surfactant sodium dodecyl sulfate and the inorganic salt sodium chloride. Not only can the evolving wet particle size be probed with nanometer accuracy, but we show that the transition to a metastable microgel particle can be followed, demonstrating that optical tweezers can be used to manipulate both spherical and non-spherical aerosol particles. Further, through the simultaneous manipulation and characterization of two aerosol droplets of different composition in two parallel optical traps, the phase behavior of a surfactant-doped particle and a surfactant-free droplet can be compared directly in situ. We also illustrate that the manipulation of two microgel particles can allow studies of the coagulation and interaction of two solid particles. Finally, we demonstrate that such parallel measurements can permit highly accurate comparative measurements of the evolving wet particle size of a surfactant-doped droplet with a surfactant-free droplet.     

Influence of surfactant vapor on the spectrum of cloud drops forming in the process of condensation growth

Introduction of a highly disperse aerosol of higher fatty alcohols into the zone of an ascending current under cumuli results in that a greater part of droplets are passivated, and in cumuli there are provided conditions for the preferred growth of large drops. One has numerically solved a system of equations describing variations in the supersaturation of a cloud system, condensational growth of drops, and kinetics of adsorption of surfactant vapor on the surface of drops. The calculation results indicate that small droplets are passivated, the number of growing drops increases, and the growth of large drops is accelerated.     

Heterogeneous atmospheric aerosol chemistry: laboratory studies of chemistry on water droplets

Heterogeneous chemical reactions on aerosol particles play a pivotal role in atmospheric chemistry. In this review, the fundamental concepts underlying the chemical dynamics of liquid aerosol droplets are discussed, with particular emphasis on the properties of the aqueous-air interface and the reaction mechanisms of key chemical processes. Recent laboratory studies of heterogeneous chemistry on aqueous aerosol particles are reviewed, with techniques that probe the gas phase, liquid phase and the interface directly, discussed in turn.     

High-performance flow atomic spectrometry: New nebulization techniques,on-line speciation and on-line sample pretreatment

An interface-free combination of HPLC separation techniques and methods for element determination by atomic spectrometry can be achieved by hydraulic high-pressure nebulization (HHPN). With high-temperature HHPN (300 ( degrees )C) super heated liquids can be nebulized providing aerosol yields of up to 90% in flame AAS. This new nebulization method combines the advantages of HHPN and thermospray techniques (very small aerosol droplets, high aerosol yield, nebulization of saturated salt solutions).     

Preparation of polymer colloids by chemical reactions in aerosols. I. Poly(p-tertiarybutylstyrene)

A procedure was developed by which polymer colloids can be prepared by polymerizing aerosol droplets of monomers with an initiator in the vapor state. This work describes the formation of poly(p-tertiarybutylstyrene) particles by exposing the corresponding monomer droplets to trifluoromethanesulfonic acid. It was found that the monomer-to-initiator mass ratio is the critical factor in determining the uniformity and morphology of the particles. Under ideal conditions spheres of narrow size distribution are obtained. Otherwise porous particles or soft particles with whiskers may develop. The aerosol was prepared in a falling film generator, but other procedures for producing monomer droplets may be used.     

Challenges in measuring the δ13C of the soil surface CO2 efflux

The δ13C of the soil surface efflux of carbon dioxide (δ13CRS) has emerged as a powerful tool enabling investigation of a wide range of soil processes from characterising entire ecosystem respiration to detailed compound-specific isotope studies. δ13CRS can be used to trace assimilated carbon transfer below ground and to partition the overall surface efflux into heterotrophic and autotrophic components. Despite this wide range of applications no consensus currently exists on the most appropriate method of sampling this surface efflux of CO2 in order to measure δ13CRS. Here we consider and compare the methods which have been used, and examine the pitfalls. We also consider a number of analysis options, isotope ratio mass spectrometry (IRMS), tuneable diode laser spectroscopy (TDLS) and cavity ring-down laser spectroscopy (CRDS). δ13CRS is typically measured using chamber systems, which fall into three types: closed, open and dynamic. All are imperfect. Closed chambers often rely on Keeling plots to estimate δ13CRS, which may not be appropriate without free turbulent air mixing. Open chambers have the advantage of being able to maintain steady-state conditions but analytical errors may become limiting with low efflux rates. Dynamic chambers like open chambers are complex, and controlling pressure fluctuations caused by air movement is a key concern. Both open and dynamic chambers in conjunction with field portable TDLS and CRDS analysis systems have opened up the possibility of measuring δ13CRS in real time permitting new research opportunities and are on balance the most suited to this type of measurement.