Particulate matter analyses

To examine a sample by inductively coupled plasma mass spectrometry (ICP/MS) or inductively coupled plasma atomic-emission spectroscopy (ICP/AES) the sample 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, as finely dispersed droplets of a solution, or as fine particulate matter. 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 discusses specifically substances that are normally liquids at ambient temperatures. This sort of inlet is the commonest in analytical work. 

In operation, a spark source is normally first flushed with argon to remove loose particulate matter from any previous analysis. The argon flow is then reduced, and the cathode is preheated or conditioned with a short bum time (about 20 sec). The argon flow is then reduced once more, and the source is ran for sufficient time to build a signal from the sample. The spark is then stopped, and the process is repeated as many times as necessary to obtain a consistent series of analyses. The arc source operates continuously, and sample signal can be taken over long periods of time. 

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. 

For mass spectrometric analysis of an analyte solution using a plasma torch, it is necessary to break down the solution into a fine droplet form that can be swept into the flame by a stream of argon gas. On the way to the flame, the droplets become even smaller and can eventually lose all solvent to leave dry analyte particulate matter. This fine residual matter can be fragmented and ionized in the plasma flame without disturbing its operation. 

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. 

As the gas stream proceeds through the sampling apparatus, the particulate matter is trapped on a filter, the moisture is removed, and the volume of the sample is measured. Upon completion of samphng, the collec ted material is recovered and sent to a laboratory for a gravimetric determination or analysis. 

Method 25 applies to the measurement of volatile organic compounds (VOC) as nonmethane organics (TGNMO), reported as carbon. Organic particulate matter will interfere with the analysis, and, therefore, in some cases, an in-stack particulate filter will be required. The method requires an emission sample to be withdrawn at a con-... 

The methods just noted tell something about the physical characteristics of atmospheric particulate matter but nothing about its chemical composition. One can seek this kind of information for either individual particles or all particles en masse. Analysis of particles en masse involves analysis of a mixture of particles of many different compounds. How much of... 

Because there has been no recent analysis of the relationship between the concentration of total suspended particulate matter in the air of cities with populations of different sizes, we are forced to use data for the decade... 

Pretreatment of the collected particulate matter may be required for chemical analysis. Pretreatment generally involves extraction of the particulate matter into a liquid. The solution may be further treated to transform the material into a form suitable for analysis. Trace metals may be determined by atomic absorption spectroscopy (AA), emission spectroscopy, polarogra-phy, and anodic stripping voltammetry. Analysis of anions is possible by colorimetric techniques and ion chromatography. Sulfate (S04 ), sulfite (SO-, ), nitrate (NO3 ), chloride Cl ), and fluoride (F ) may be determined by ion chromatography (15). 

For sources having a large component of emissions from low-level sources, the simple Gifford-Hanna model given previously as Eq. (20-19), X = Cqju, works well, especially for long-term concentrations, such as annual ones. Using the derived coefficients of 225 for particulate matter and 50 for SO2, an analysis of residuals (measured minus estimated) of the dependent data sets (those used to determine the values of the coefficient C) of 29 cities for particulate matter and 20 cities for SOj and an independent data set of 15 cities for particulate matter is summarized in Table 20-1. For the dependent data sets, overestimates result. The standard deviations of the residuals and the mean absolute errors are about equal for particulates and sulfur dioxide. For the independent data set the mean residual shows... 

Samples of particulate matter can be subjected to many of the above analytical techniques in chemical characterization. The following methods are, however, particularly applicable to analysis of physical characteristics of particulate matter isolated from air sampling. 

EP.A. Air Quality Criteria for Particulate Matter, 4. Sampling and Analysis Methods for Partic-niitte Matter and Add Deposition. Research Triangle Park, NC. http //www.ep.i.gov/nceawwwl/pin vol 1. htm. 

The first method used for wear particle analysis is routine monitoring and trending of the solids content of machine lubricant. In simple terms the quantity, composition and size of particulate matter in the lubricating oil is indicative of the mechanical condition of the machine. A normal machine will contain low levels of solids with a size less than 10 microns. As the machine s condition degrades, the number and size of particulate matter will increase. 

A second source of plutonium, dispersed more locally, is liquid effluent from fuel reprocessing facilities. One such is the fuel reprocessing plant at Windscale, Cumbria in the United Kingdom where liquid waste is released to the Irish Sea(6). Chemical analysis of this effluent shows that about one percent or less of the plutonium is in an oxidized form before it contacts the marine water(7). Approximately 95 percent of the plutonium rapidly adsorbs to particulate matter after discharge and deposits on the seabed while 5 percent is removed from the area as a soluble component ). Because this source provided concentrations that were readily detected, pioneering field research into plutonium oxidation states in the marine environment was conducted at this location. 

The network is implemented by the participating countries through WHO. Sulfur Dioxide (SO,) and suspended particulate matter (SPN) data are routinely reported from each of the participating countries to WHO for entry into the global data base, which is maintained by the United States Environmental Protection Agency (U.S. EPA) at Research Triangle Park, North Carolina. Methods of collection and analysis varies by country. SPN is reported either as a gravimetric or a photometric (transmittance or reflectance) measurement converted to mass units. Since the accuracy of the conversion of the photometric measurement to mass units is... 

Figure 11. Reversed-phase HPLC analysis of total PAH s extracted from SRM 1648, urban particulate matter, with programmed fluorescence detection. (Reprinted from reference 72.

For aerobic degradation, uptake of oxygen or the evolution of carbon dioxide is most widely used. Use of the concentration of dissolved organic carbon may present technical problems when particulate matter is present, though analysis of dissolved inorganic carbon in a closed system has been advocated (Birch and Fletcher 1991), and may simultaneously overcome problems with poorly soluble or volatile compounds. 

US NIST (1991) Certificate of Analysis. SRM 1648 Urban Particulate Matter. US National Institute of Standards and Technology, Gaithersburg, August 30,1991. 

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