Sampling particulate matter

For sampling particulate matter, one is dealing with pollutants that have very different inertial and other characteristics from the carrying gas stream. It becomes important, therefore, to sample so that the same velocity is maintained in the probe tip as exists in the adjacent gas stream. Such sampling is called isokinetic. Isokinetic sampling, as well as anisokinetic sampling, is illustrated in Fig. 13-3. 

Another method, not specifically described as an asphaltene separation method, is designed to remove pentane- or heptane-insoluble constituents by membrane filtration (ASTM D-4055). In the method, a sample of oil is mixed with pentane in a volumetric flask, and the oil solution is filtered through a 0.8-p.m membrane filter. The flask, funnel, and filter are washed with pentane to completely transfer any particulate matter onto the filter, after which the filter (with the particulate matter) is dried and weighed to give the pentane-insoluble constituents as a percent by weight of the sample. Particulate matter in the extracts can also be determined by membrane filtration (ASTM D-2276 ASTM D-5452 ASTM D-6217 IP 415). 

Before storing water samples, particulate matter must be removed to avoid species condensation and a shift in elemental speciation. Filtration is necessary, but this probably causes adsorption or contamination at membranes (Batley 1989). Pre-deaning by filtration of dilute nitric acid followed by bi-distilled water overcomes or minimizes contamination. On the other hand, colloids must not be removed as they are considered to be spedes by themselves. Precaution must also be taken to minimize wall effects. 

As a consequence, accumulation of Pd and other PGE has been detected in road dust as well as soil and grass samples collected along highways (Barefoot 1999 Zereini and Alt 2000 Ravindra et al. 2004). Pd concentrations in airbome particulate matter (APM) samples (particulate matter <10 xm, PMIO) were reported to be in the range of 2.6-32 pg m on urban sampling sites (Gomez et al. 2003 Kanitsar et al. 2003 Zereini et al. 2005). 

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. 

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. 

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. 

The calculation shows how rapidly a droplet changes in diameter with time as it flows toward the plasma flame. At 40°C, a droplet loses 90% of its size within alxtut 1.5 sec, in which time the sweep gas has flowed only about 8 cm along the tube leading to the plasma flame. Typical desolvation chambers operate at 150°C and, at these temperatures, similar changes in diameter will be complete within a few milliseconds. The droplets of sample solution lose almost all of their solvent (dry out) to give only residual sample (solute) particulate matter before reaching the plasma flame. 

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. 

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. 

U. S. EPA Regulations on Standards ofPeformanceforNeir Stationay Sources, 40 CER 60, Appendix A, Reference Methods, Washington, D.C., 1993. ASTM D3685-92, Standard Test Methodfor Sampling and Determination of Particulate Matter in Stack Gases, American Society for Testing Materials, Philadelphia, Pa., 1992. 

The instrumental analyzer procedure, EPA Method 3A, is commonly used for the determination of oxygen and carbon dioxide concentrations in emissions from stationary sources. An integrated continuous gas sample is extracted from the test location and a portion of the sample is conveyed to one or more instrumental analyzers for determination of O9 and CO9 gas concentrations (see Fig. 25-30). The sample gas is conditioned prior to introduction to the gas analyzer by removing particulate matter and moisture. Sampling is conducted at a constant rate for the entire test run. Performance specifications and test procedures are provided in the method to ensure reliable data. 

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-... 

Because a filter sample includes particles both larger and smaller than those retained in the human respiratory system (see Chapter 7, Section III), other types of samplers are used which allow measurement of the size ranges of particles retained in the respiratory system. Some of these are called dichotomous samplers because they allow separate measurement of the respirable and nonrespirable fractions of the total. Size-selective samplers rely on impactors, miniature cyclones, and other means. The United States has selected the size fraction below an aerodynamic diameter of 10 /xm (PMiq) for compliance with the air quality standard for airborne particulate matter. 

Mean Chemical Composition and Atmospheric Concentrations of Suspended Particulate Matter Sampled by the United States Environmental Protection Agency s Inhalable Particle and National Air Surveillance Networks—/rg/m and Percentage of Total Mass Sampled, 1980... 

Special techniques are employed to sample for gases and particulate matter simultaneously (3). Sampling systems have been developed which permit the removal of gas-phase molecules from a moving airstream by diffusion to a coated surface and permit the passage of particulate matter... 

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