Aerosol matter

It is necessary to remove the aerosol matter by hot filters, which makes the chemical processes uncertain and difficult to control. 

Particle size and surface area as well as vertical distribution are also important for heterogeneous reactions. The majority of the mass of atmospheric aerosol matter is represented by particles of size 10 -10 m [5], i.e. their surface area must be 10 m g. The specific surface area A of solid aerosols near the Earth surface is considered to be 10 m dm of air under background conditions and can increase by a factor of 100 in urban areas [3]. The vertical distribution of A is shown in Fig. 1(B). Due to sedimentation, almost all of aerosols are located in the lower layer of the troposphere. 

As a result of the Pinatubo volcano eruption in the Philippines in June 1991, great amounts of gaseous and aerosol matter were thrown into die atmosphere. 

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. 

Suffice it to say at this stage that the surfaces of most solids subjected to such laser heating will be heated rapidly to very high temperatures and will vaporize as a mix of gas, molten droplets, and small particulate matter. For ICP/MS, it is then only necessary to sweep the ablated aerosol into the plasma flame using a flow of argon gas this is the basis of an ablation cell. It is usual to include a TV monitor and small camera to view the sample and to help direct the laser beam to where it is needed on the surface of the sample. 

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. 

An aerosol produced instrumentally has similar properties, except that the aerosol is usually produced from solutions and not from pure liquids. For solutions of analytes, the droplets consist of solute and solvent, from which the latter can evaporate to give smaller droplets of increasingly concentrated solution (Figure 19.1). If the solvent evaporates entirely from a droplet, the desolvated dry solute appears as small solid particles, often simply called particulate matter. 

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). 

Solutions of solids may need to be converted into aerosols by pneumatic or sonic-spraying techniques. After solvent has evaporated from the aerosol droplets, the residual particulate solid matter can be ionized by a plasma torch. 

Some solid materials are very intractable to analysis by standard methods and cannot be easily vaporized or dissolved in common solvents. Glass, bone, dried paint, and archaeological samples are common examples. These materials would now be examined by laser ablation, a technique that produces an aerosol of particulate matter. The laser can be used in its defocused mode for surface profiling or in its focused mode for depth profiling. Interestingly, lasers can be used to vaporize even thermally labile materials through use of the matrix-assisted laser desorption ionization (MALDI) method variant. 

A liquid sample must be vaporized to a gas or, more likely, to a vapor consisting of an aerosol of gas, small droplets, and even small particles of solid matter. To be examined, the aerosol is mixed with argon gas to make up the needed flow of gas into the plasma and is then swept into the flame. 

The aerosol is swept to the torch in a stream of argon gas. During passage from the nebulizer to the plasma flame, the droplets rapidly become smaller, as solvent evaporates, and evenmally become very small. In many cases, almost all of the solvent evaporates to leave dry particulate matter of residual analyte. 

Environmental Aspects. Airborne particulate matter (187) and aerosol (188) samples from around the world have been found to contain a variety of organic monocarboxyhc and dicarboxyhc acids, including adipic acid. Traces of the acid found ia southern California air were related both to automobile exhaust emission (189) and, iadirecfly, to cyclohexene as a secondary aerosol precursor (via ozonolysis) (190). Dibasic acids (eg, succinic acid) have been found even ia such unlikely sources as the Murchison meteorite (191). PubHc health standards for adipic acid contamination of reservoir waters were evaluated with respect to toxicity, odor, taste, transparency, foam, and other criteria (192). BiodegradabiUty of adipic acid solutions was also evaluated with respect to BOD/theoretical oxygen demand ratio, rate, lag time, and other factors (193). 

B. W. Loo, J. M. JaMevic, and F. S. Goulding, "Dichotomous Virtual Impactors for Large Scale Monitoring of Airborne Particulate Matter," in B. Y. H. Liu, ed., Eine Particles, Aerosol Generation, Measurement, Sampling and Analysis, Academic Press, Inc., New York, 1976, pp. 311—350. 

Although spray-dryiag accommodates relatively high content of surfactants, certain types, such as the alkanolamides and some nonionic surfactants are best added to the product after spray-dryiag. Post additioa aot only protects the surfactant from the heat of the tower but also prevents the formation of aerosols ia the exit gas. Aerosols are more difficult to trap ia the scmbbiag system than soHd fines. They are formed by unsulfonated matter from the manufacture of LAS and nonionic surfactants with short ethylene oxide chains (120). 

When a liquid or solid substance is emitted to the air as particulate matter, its properties and effects may be changed. As a substance is broken up into smaller and smaller particles, more of its surface area is exposed to the air. Under these circumstances, the substance, whatever its chemical composition, tends to combine physically or chemically with other particles or gases in the atmosphere. The resulting combinations are frequently unpredictable. Very small aerosol particles (from 0.001 to 0.1 Im) can act as condensation nuclei to facilitate the condensation of water vapor, thus promoting the formation of fog and ground mist. Particles less than 2 or 3 [Lm in size (about half by weight of the particles suspended in urban air) can penetrate the mucous membrane and attract and convey harmful chemicals such as sulfur dioxide. In order to address the special concerns related to the effects of very fine, iuhalable particulates, EPA replaced its ambient air standards for total suspended particulates (TSP) with standards for particlute matter less than 10 [Lm in size (PM, ). 

Mineral matter derived from ash constituents of liquid and solid fuels can vaporize and condense as sub-micron-size aerosols. Larger mineral matter fragments are formed from mineral inclusions which melt and resolidify downstream. 

The most widely used pulping process is the kraft process, as shown in Fig. 6-11, which results in recovery and regeneration of the chemicals. This occurs in the recovery furnace, which operates with both oxidizing and reducing zones. Emissions from such recovery furnaces include particulate matter, very odorous reduced sulfur compounds, and oxides of sulfur. If extensive and expensive control is not exercised over the kraft pulp process, the odors and aerosol emissions will affect a wide area. Odor complaints have been reported over 100 km away from these plants. A properly controlled and operated kraft plant will handle huge amounts of material and produce millions of kilograms of finished products per day, with little or no complaint regarding odor or particulate emissions. 

ITie major component of atmospheric haze is sulfate particulate matter (particularly ammonium sulfate), along with varying amounts of nitrate particulate matter, which in some areas can equal the sulfate. Other components include graphitic material, fine fly ash, and organic aerosols. 

Dry aerosols, or particulate matter, differ so much from the carrying gas stream that their removal should present no major difficulties. The aerosol is different physically, chemically, and electrically. It has vastly different inertial properties than the carrying gas stream and can be subjected to an electric charge. It may be soluble in a specific liquid. With such a variety of removal mechanisms that can be applied, it is not surprising that particulate matter, such as mineral dust, can be removed by a filter, wet scrubber, or electrostatic precipitator with equally satisfactory results. 

Opacity reduction is the control of fine particulate matter less than 1 ixm). It can be accomplished through the application of the systems and devices discussed for control of particulate matter and by use of combustion control systems to reduce smoke and aerosol emission. In addition, operational practices such as continuous soot blowing and computerized fuel and air systems should be considered. 

Airborne partieulate matter may eomprise liquid (aerosols, mists or fogs) or solids (dust, fumes). Refer to Figure 5.2. Some eauses of dust and aerosol formation are listed in Table 4.3. In either ease dispersion, by spraying or fragmentation, will result in a eonsiderable inerease in the surfaee area of the ehemieal. This inereases the reaetivity, e.g. to render some ehemieals pyrophorie, explosive or prone to spontaneous eombustion it also inereases the ease of entry into the body. The behaviour of an airborne partiele depends upon its size (e.g. equivalent diameter), shape and density. The effeet of partiele diameter on terminal settling veloeity is shown in Table 4.4. As a result ... 

Exposures to chemicals may involve solids, liquids, or airborne matter as mists, aerosols, dusts, fumes (i.e. pm-sized particulates), vapours or gases in any combination. Many situations, e.g. exposure to welding fumes or to combustion products from fossil fuels, include mixtures both of chemicals and of physical forms. Quantification of exposure is then difficult. 

Health effects attributed to sulfur oxides are likely due to exposure to sulfur dioxide, sulfate aerosols, and sulfur dioxide adsorbed onto particulate matter. Alone, sulfur dioxide will dissolve in the watery fluids of the upper respiratory system and be absorbed into the bloodstream. Sulfur dioxide reacts with other substances in the atmosphere to form sulfate aerosols. Since most sulfate aerosols are part of PMj 5, they may have an important role in the health impacts associated with fine particulates. However, sulfate aerosols can be transported long distances through the atmosphere before deposition actually occurs. Average sulfate aerosol concentrations are about 40% of average fine particulate levels in regions where fuels with high sulfur content are commonly used. Sulfur dioxide adsorbed on particles can be carried deep into the pulmonary system. Therefore, reducing concentrations of particulate matter may also reduce the health impacts of sulfur dioxide. Acid aerosols affect respiratory and sensory functions. 

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