Elemental aerosol

Element Aerosol concentrations (nmolm 3) Rainwater concentrations (nmol F -1)... 

Element Aerosol Generation System (a) Per cent Std. Dev. Analytical Precision (b)... 

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. 

Organic compounds are a major constituent of the FPM at all sites. The major sources of OC are combustion and atmospheric reactions involving gaseous VOCs. As is the case with VOCs, there are hundreds of different OC compounds in the atmosphere. A minor but ubiquitous aerosol constituent is elemental carbon. EC is the nonorganic, black constituent of soot. Combustion and pyrolysis are the only processes that produce EC, and diesel engines and wood burning are the most significant sources. 

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... 

The existing variety of means and methods of micro-element analysis is used worldwide for the determination of element contents in atmospheric aerosols when they ai e collected at aspiration filters, sediment and natural surfaces and biota objects where toxic substances migration can be observed. 

Standardized techniques atomic absorption (AAA) and photometric (FMA) of the analysis and designed by us a technique X-Ray fluorescence of the analysis (XRF) for metals definition in air of cities and the working areas of plants to production of non-ferrous metals are applied. The samples of aerosols were collected on cellulose (AFA-HA) and perchlorovinyl (AFA-VP and FPP) filters (Russia). The techniques AAA and FMA include a stage of an acid-temperature ashing of a loaded filter or selective extraction of defined elements from filter by approaching dissolvent. At XRF loaded filters were specimens. 

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. 

The theory of filtration of aerosols from a gas stream is much more involved than the sieving action which removes particles in a liquid medium. Figure 29-1 shows three of the mechanisms of aerosol removal by a filter. In practice, the particles and filter elements are seldom spheres or cylinders. 

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. 

In Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES), a gaseous, solid (as fine particles), or liquid (as an aerosol) sample is directed into the center of a gaseous plasma. The sample is vaporized, atomized, and partially ionized in the plasma. Atoms and ions are excited and emit light at characteristic wavelengths in the ultraviolet or visible region of the spectrum. The emission line intensities are proportional to the concentration of each element in the sample. A grating spectrometer is used for either simultaneous or sequential multielement analysis. The concentration of each element is determined from measured intensities via calibration with standards. 

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%. 

Althoi h nonspectral interference effects are generally less severe in ICP-OES than in GFAA, FAA, or ICPMS, they can occur. In most cases the effects produce less than a 20% error when the sample is introduced as a liquid aerosol. High concentrations (500 ppm or greater) of elements that are highly ionized in the... 

The tapered-element oscillating microbalance (TEOM) sensor, as described by Patashnick and Rupprecht, consists of an oscillating tapered tube with a filter at its free end (Fig. 13.40). The mass of the filter increases due to the collected aerosol and produces a shift in the oscillation frequency of the tapered tube that is directly related to mass. 

Interest in the elemental composition of aerosol particles arises from concerns about health effects and the value of these elements to trace the sources of suspended particles. The following physical analysis methods have been applied for the elemental measurements of aerosol samples. A schematic drawing of an x-ray fluorescence system is presented in Fig. 13.42. 

Table in Proposed Sources of Elements in Remote Aerosols ... 

Since the majority of the elements in surface dust arise from deposited aerosol and added soil it is not surprising to find strong linear relationships between the concentrations of the elements in an atmospheric dust and street or house dust. This is illustrated by the two examples given in Fig. 8 for remote house dust vs urban atmospheric dust and street dust vs rural atmospheric dust. As discussed above crustal/soil material is a major component of atmospheric dust and the soil based elements in the atmospheric dust are Al, Ca, Fe, Mg, Mn, Ni, K, Si and Ti. The elements As, Br, Cd, Cl, Co, Cu, Pb, Rb, Se, V, and Zn are, on the other hand, enriched in atmospheric dust. The same elemental distribution applies to surface dust, but in this case their concentrations (compared on a mass basis) are reduced presumably due to dilution with soil. However, the elements enriched in the atmosphere remain enriched in the surface dusts. 

Table V Methods of Identifying Sources of Elements in Aerosols and Surface Dust...

Table VI. Sources of Elements, Anions and Cations in Urban and Rural Aerosols ...

Perhaps because the unpolluted atmosphere can appear to be perfectly free of turbidity, it is not immediately obvious that it is a mixture of solid, gaseous, and liquid phases - even in the absence of clouds. Particles in the aerosol state constitute only a miniscule portion of the mass of the atmosphere - perhaps 10 or 10 ° in im-polluted cases. However, the condensed phases are important intermediates in the cycles of numerous elements, notably ammonia-N, suT... 

The evaporite source is characterized by covariation of sulfate (from gypsum) and chloride (from halite). That elements can be recycled from the ocean to land by movement of saltbearing aerosols (so-called "cyclic salts") has confused the interpretation of river flux data somewhat. While this cycling generally follows the ratio of salts in the sea, the S/Cl ratio is an exception. Taking the S/Cl ratio of the cyclic component to be 2 (based on compositional data for marine rains) and assuming that all chloride in rivers is cyclic, an upper limit for the cyclic influence can be calculated. 

About half the manmade emissions of sulfur dioxide become sulfate aerosol. That implies that currently 35 Tg per year of sulfur in sulfur dioxide is converted chemically to sulfate. Because the molecular weight of sulfate is three times that of elemental sulfur, Q is about 105 Tg per year. Studies of sulfate in acid rain have shown that sulfates persist in the air for about five days, or 0.014 year. The area of the Earth is 5.1 x lO m. Substituting these values into the equation for B yields about 2.8 X 10 g/m for the burden. 

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