Aerosol mass

Note DMS differential mobility spectrometer, SMPS scanning mobility particle sizer, CPC condensation particle counter, TDMPS twin differential mobility particle sizer, DMPS differential mobility particle sizer, OPC optical particle counter, APS aerodynamic particle sizer, MAS mass aerosol spectrometer, LAS-X optical laser aerosol spectrometer, ELPI electrical low pressure impactor... 

The kinetics of chemical interactions between fission product vapor and aerosols is mainly controlled by gas phase mass transport, by the kinetics of the chemical reaction, and by mass transport in the condensed phase. Another factor potentially influencing the kinetics of vapor deposition is that the heat liberated by condensation or by chemical reaction of vapor with aerosol must be disposed of. Because of their small masses, aerosol particles have only limited capacity for conducting away this heat, compared with the structures within the reactor coolant system. This problem may arise particularly in the deposition of water vapor onto aerosol particles which have been previously covered by hygroscopic or water-soluble compounds such as CsOH. 

Following the movement of airborne pollutants requires a natural or artificial tracer (a species specific to the source of the airborne pollutants) that can be experimentally measured at sites distant from the source. Limitations placed on the tracer, therefore, governed the design of the experimental procedure. These limitations included cost, the need to detect small quantities of the tracer, and the absence of the tracer from other natural sources. In addition, aerosols are emitted from high-temperature combustion sources that produce an abundance of very reactive species. The tracer, therefore, had to be both thermally and chemically stable. On the basis of these criteria, rare earth isotopes, such as those of Nd, were selected as tracers. The choice of tracer, in turn, dictated the analytical method (thermal ionization mass spectrometry, or TIMS) for measuring the isotopic abundances of... 

Nd in samples. Unfortunately, mass spectrometry is not a selective technique. A mass spectrum provides information about the abundance of ions with a given mass. It cannot distinguish, however, between different ions with the same mass. Consequently, the choice of TIMS required developing a procedure for separating the tracer from the aerosol particulates. 

To examine a sample by inductively coupled plasma mass spectrometry (ICP/MS) or inductively coupled plasma atomic-emission spectroscopy (ICP/AES), it must be transported into the flame of a plasma torch. Once in the flame, sample molecules are literally ripped apart to form ions of their constituent elements. These fragmentation and ionization processes are described in Chapters 6 and 14. To introduce samples into the center of the plasma flame, they must be transported there as gases or finely dispersed droplets of a solution or as fine particulate matter (aerosol). The various methods of sample introduction are described here in three parts — A, B, and C Chapters 15, 16, and 17 — to cover gases, solutions (liquids), and solids. Some types of sample inlets are multipurpose and can be used with gases and liquids or with liquids and solids, but others have been designed specifically for only one kind of analysis. However, the principles governing the operation of inlet systems fall into a small number of categories. This chapter deals specifically with substances that are normally solids at ambient temperatures. 

Samples to be examined by inductively coupled plasma and mass spectrometry (ICP/MS) are commonly in the form of a solution that is transported into the plasma flame. The thermal mass of the flame is small, and ingress of excessive quantities of extraneous matter, such as solvent, would cool the flame and might even extinguish it. Even cooling the flame reduces its ionization efficiency, with concomitant effects on the accuracy and detection limits of the ICP/MS method. Consequently, it is necessary to remove as much solvent as possible which can be done by evaporation off-line or done on-line by spraying the solution as an aerosol into the plasma flame. 

Aerosols can be produced as a spray of droplets by various means. A good example of a nebulizer is the common household hair spray, which produces fine droplets of a solution of hair lacquer by using a gas to blow the lacquer solution through a fine nozzle so that it emerges as a spray of small droplets. In use, the droplets strike the hair and settle, and the solvent evaporates to leave behind the nonvolatile lacquer. For mass spectrometry, a spray of a solution of analyte can be produced similarly or by a wide variety of other methods, many of which are discussed here. Chapters 8 ( Electrospray Ionization ) and 11 ( Thermospray and Plasmaspray Interfaces ) also contain details of droplet evaporation and formation of ions that are relevant to the discussion in this chapter. Aerosols are also produced by laser ablation for more information on this topic, see Chapters 17 and 18. 

The term nebulizer is used generally as a description for any spraying device, such as the hair spray mentioned above. It is normally applied to any means of forming an aerosol spray in which a volume of liquid is broken into a mist of vapor and small droplets and possibly even solid matter. There is a variety of nebulizer designs for transporting a solution of analyte in droplet form to a plasma torch in ICP/MS and to the inlet/ionization sources used in electrospray and mass spectrometry (ES/MS) and atmospheric-pressure chemical ionization and mass spectrometry (APCI/MS). 

In pneumatic nebulizers, the relative velocity of gas and liquid first induces a reduction in pressure above the surface of the liquid (see the calculation in Figure 19.4). The reduction in pressure is sufficient to cause liquids to flow out of capillary tubes, in accord with Poiseuille s formula (Figure 19.5). As the relative velocity of a liquid and a gas increases — particularly if the mass of liquid is small — this partial vacuum and rapid flow cause the surface of the liquid to be broken into droplets. An aerosol is formed. 

Nebulizers are used to introduce analyte solutions as an aerosol spray into a mass spectrometer. For use with plasma torches, it is necessary to produce a fine spray and to remove as much solvent as possible before the aerosol reaches the flame of the torch. Various designs of nebulizer are available, but most work on the principle of interacting gas and liquid streams or the use of ultrasonic devices to cause droplet formation. For nebulization applications in thermospray, APCI, and electrospray, see Chapters 8 and 11. 

The previous discussion has centered on how to obtain as much molecular mass and chemical structure information as possible from a given sample. However, there are many uses of mass spectrometry where precise isotope ratios are needed and total molecular mass information is unimportant. For accurate measurement of isotope ratio, the sample can be vaporized and then directed into a plasma torch. The sample can be a gas or a solution that is vaporized to form an aerosol, or it can be a solid that is vaporized to an aerosol by laser ablation. Whatever method is used to vaporize the sample, it is then swept into the flame of a plasma torch. Operating at temperatures of about 5000 K and containing large numbers of gas ions and electrons, the plasma completely fragments all substances into ionized atoms within a few milliseconds. The ionized atoms are then passed into a mass analyzer for measurement of their atomic mass and abundance of isotopes. Even intractable substances such as glass, ceramics, rock, and bone can be examined directly by this technique. 

Elastic scattering is also the basis for Hdar, in which a laser pulse is propagated into a telescope s field of view, and the return signal is collected for detection and in some cases spectral analysis (14,196). The azimuth and elevation of the scatterers (from the orientation of the telescope), their column density (from the intensity), range (from the temporal delay), and velocity (from Doppler shifts) can be deterrnined. Such accurate, rapid three-dimensional spatial information about target species is useful in monitoring air mass movements and plume transport, and for tracking aerosols and pollutants (197). 

Receptor models are powerful tools for source apportionment of particulates because a vast amount of particulate species characterization data have been collected at many sampling sites worldwide, and because many aerosol species are primary pollutants. Most of the information available is for elemental concentrations, eg, lead, nickel, and alurninum, although more recent measurements have provided data on concentrations of ionic species and carbonaceous compounds. At a sampling (or receptor) site, the aerosol mass concentration of each species i is... 

Aerosol Dynamics. Inclusion of a description of aerosol dynamics within air quaUty models is of primary importance because of the health effects associated with fine particles in the atmosphere, visibiUty deterioration, and the acid deposition problem. Aerosol dynamics differ markedly from gaseous pollutant dynamics in that particles come in a continuous distribution of sizes and can coagulate, evaporate, grow in size by condensation, be formed by nucleation, or be deposited by sedimentation. Furthermore, the species mass concentration alone does not fliUy characterize the aerosol. The particle size distribution, which changes as a function of time, and size-dependent composition determine the fate of particulate air pollutants and their... 

Fig. 6. Size distribution of an urban aerosol showing the three modes containing much of the aerosol mass. The fine mode contains particles produced by condensation of low volatility gases. The mid-range, or accumulation mode, results from coagulation of smaller aerosols and condensation of gases on preexisting particles. Coarse particulates, the largest aerosols, are usually generated mechanically.

A third screening smoke-type is white phosphoms [7723-14-0] (WP), P (see Phosphorus and THE phosphides), which reacts spontaneously with air and water vapor to produce a dense cloud of phosphoms pentoxide [1314-56-3]. An effective screen is obtained as the P2O5 hydrolyzes to form droplets of dilute phosphoric acid aerosol. WP produces smoke in great quantity, but it has certain disadvantages. Because WP has such a high heat of combustion, the smoke it produces from bulk-filled munitions has a tendency to rise in pillarlike mass. This behavior too often nullifies the screening effect, particularly in stiU air. Also, WP is very brittle, and the exploding munitions in which it is used break it into very small particles that bum rapidly. 

For exposure of reasons of observable discrepancy of results of the analysis simulated experiment with application synthetic reference samples of aerosols [1]. The models have demonstrated absence of significant systematic errors in results XRF. While results AAA and FMA depend on sort of chemical combination of an elements, method of an ashing of a material and mass of silicic acid remaining after an ashing of samples. The investigations performed have shown that silicic acid adsorbs up to 40 % (rel.) ions of metals. The coefficient of a variation V, describing effect of the indicated factors on results of the analysis, varies %) for Mn and Fe from 5 up to 20, for Cu - from 10 up to 40, for Pb - from 10 up to 70, for Co the ambassador of a dry ashing of samples - exceeds 50. At definition Cr by a method AAA the value V reaches 70 %, if element presences an atmosphere in the form of Cr O. At photometric definition Cr (VI) the value V is equal 40%, when the element is present at aerosols in the form of chromates of heavy metals. 

Coagulation, i.e., the process by which discrete particles come in contact with each other in the air and remain joined together by surface forces, represents another way in which aerosol diameter will increase. However, it does not alter the mass of material in the coagulated particle. 

Particles in the atmosphere come from different sources, e.g., combustion, windblown dust, and gas-to-particle conversion processes (see Chapter 6). Figure 2-2 illustrates the wide range of particle diameters potentially present in the ambient atmosphere. A typical size distribution of ambient particles is shown in Fig. 2-3. The distribution of number, surface, and mass can occur over different diameters for the same aerosol. Variation in chemical composition as a function of particle diameter has also been observed, as shown in Table 4-3. 

Other lesser mechanisms that result in aerosol removal by filters are (1) gravitational settling due to the difference in mass of the aerosol and the carrying gas, (2) thermal precipitation due to the temperature gradient between a hot gas stream and the cooler filter medium which causes the particles to be bombarded more vigorously by the gas molecules on the side away from the filter element, and (3) Brownian deposition as the particles are bombarded with gas molecules that may cause enough movement to permit the aerosol to come in contact with the filter element. Browruan motion may also cause some of the particles to miss the filter element because they are moved away from it as they pass by. For practical purposes, only the three mechanisms shown in Fig. 29-1 are normally considered for removal of aerosols from a gas stream. 

Electrothermal vaporization can be used for 5-100 )iL sample solution volumes or for small amounts of some solids. A graphite furnace similar to those used for graphite-furnace atomic absorption spectrometry can be used to vaporize the sample. Other devices including boats, ribbons, rods, and filaments, also can be used. The chosen device is heated in a series of steps to temperatures as high as 3000 K to produce a dry vapor and an aerosol, which are transported into the center of the plasma. A transient signal is produced due to matrix and element-dependent volatilization, so the detection system must be capable of time resolution better than 0.25 s. Concentration detection limits are typically 1-2 orders of magnitude better than those obtained via nebulization. Mass detection limits are typically in the range of tens of pg to ng, with a precision of 10% to 15%. 

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