Volatile organic compounds sampling methods

For the charcoal, XAD, and PUF adsorbents discussed above, solvent extraction techniques have been developed for the removal and concentration of trapped analytes. Although thermal desorption has been used with Tenax-GC in some specialized air sampling situations [primarily with sampling volatile organic compounds (EPA, Method TO-17 )], this approach is not a viable alternative to solvent extraction for the charcoal, XAD, and PUF adsorbents. The polystyrene and PUF adsorbents are thermally unstable and the charcoal chemisorption bonding is more easily broken by... 

There are 14 analytical methods developed by U.S. EPA for measuring common organic pollutants in air. These analytes include aldehydes and ketones, chlorinated pesticides, polynuclear aromatic hydrocarbons, and many volatile organic compounds. These methods may also be applied to analyze other similar substances. All these methods are numbered from TO-1 to TO-14 and based on GC, GC/MS, and HPLC analytical techniques. Method numbers, sampling and analytical techniques, and the types of pollutants are outlined in Table 1, while individual substances are listed in Table 2. 

Automated analyzers may be used for continuous monitoring of ambient poUutants and EPA has developed continuous procedures (23) as alternatives to the referenced methods. Eor source sampling, EPA has specified extractive sampling trains and analytical methods for poUutants such as SO2 and SO [7446-11-9] sulfuric acid [7664-93-9] mists, NO, mercury [7439-97-6], beryUium [7440-41-7], vinyl chloride, and VOCs (volatile organic compounds). Some EPA New Source Performance Standards requite continuous monitors on specified sources. 

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 The method requires an emission sample to be withdrawn at a con-... 

Headspace analysis has also been used to determine trichloroethylene in water samples. High accuracy and excellent precision were reported when GC/ECD was used to analyze headspace gases over water (Dietz and Singley 1979). Direct injection of water into a portable GC suitable for field use employed an ultraviolet detector (Motwani et al. 1986). While detection was comparable to the more common methods (low ppb), recovery was very low. Solid waste leachates from sanitary landfills have been analyzed for trichloroethylene and other volatile organic compounds (Schultz and Kjeldsen 1986). Detection limits for the procedure, which involves extraction with pentane followed by GC/MS analysis, are in the low-ppb and low-ppm ranges for concentrated and unconcentrated samples, respectively. Accuracy and precision data were not reported. 

This is a relatively new technique that is used for PCBs and other nonpolar, volatile and semi-volatile organic compounds. Typically, a small aliquot of soil sample (0.5-20 g) is used for the extraction. Soil samples are extracted with one or more organic solvents using microwave energy at elevated temperature (100-115 °C) and pressure (50-175 psi). This method uses less solvent and takes significantly less time than Soxhlet extraction but is limited to thermally stable compounds. 

EPA SW-846 Method 8265, Volatile Organic Compounds in Water, Soil, Soil Gas, and Air by Direct Sampling Ion Trap Mass Spectrometry. Electronic version of EPA SW-846 Manual available at http //www.epa.gov/epaoswer/hazwaste/test/ new-meth.htm 8265. 

As discussed in Chapter 7, gas chromatography (GC) is used to separate complex mixtures of volatile organic compounds. However, unless pure authentic standards are also analyzed to compare retention times, it is not possible to identify the components by GC alone. However, by connecting the output of a GC to a mass spectrometer, and by removing the carrier gas to maintain the low pressures required, it is possible to both separate and identify these complex mixtures. This method is the gold standard for the identification of organic samples, if they are sufficiently volatile. 

Namiesnik et al. [33] have reviewed the analysis of soils and sediments for organic contaminants. They discuss methods of sample preparation and isolation-preconcentration prior to instrumental determination. Compound classes discussed include volatile organic compounds, polychlorobiphenyls, polyaromatic compounds, pesticides and polychlorodibenzo-p-dioxins and polychlorodibenzofurans. 

Various sample enrichment techniques are used to isolate volatile organic compounds from mammalian secretions and excretions. The dynamic headspace stripping of volatiles from collected material with purified inert gas and trapping of the volatile compounds on a porous polymer as described by Novotny [3], have been adapted by other workers to concentrate volatiles from various mammalian secretions [4-6]. It is risky to use activated charcoal as an adsorbent in the traps that are used in these methods because of the selective adsorption of compounds with different polarities and molecular sizes on different types of activated charcoal. Due to the high catalytic activity of activated charcoal, thermal conversion can occur if thermal desorption is used to recover the trapped material from such a trap. 

Two methods, EPA SW-846 8015 and 8015A, were, in the past, often quoted as the source of gas chromatography-based methods for measurement of the total petroleum hydrocarbons in a sample. However, the original methods were developed for nonhalogenated volatile organic compounds and were designed to measure a short target list of chemical solvents rather than petroleum hydrocarbons. Thus, because there was no universal method for total petroleum hydrocarbons, there were many variations of these methods. Recently, an updated method... 

One method (EPA 8020) that is suitable for volatile aromatic compounds is often referred to as benzene-toluene-ethylbenzene-xylene analysis, although the method includes other volatile aromatics. The method is similar to most volatile organic gas chromatographic methods. Sample preparation and introduction is typically by purge-and-trap analysis (EPA 5030). Some oxygenates, such as methyl-f-butyl ether (MTBE), are also detected by a photoionization detector, as well as olefins, branched alkanes, and cycloalkanes. 

A commonly used method of sampling and analysis for volatile organic compounds In ambient air Is by concentration of the compounds on a solid sorbent such as Tenax and subsequent thermal desorption and GC/MS analysis of the collected compounds. The analysis phase, although not trivial, can be done well If proper care Is taken. However, the sampling phase of this process apparently Introduces artifacts and unusual results due to, as yet, unknown factors. A method to detect some sampling problems has been proposed and tested (7 ). This distributed air volume method requires a set of samples of different air volumes to be collected at different flow rates over the same time period at the sampling location. Each pollutant concentration for the samples should be equal within experimental error since the same parcel of air Is sampled In each case. Differences In results for the same pollutant In the various samples Indicates sampling problems. 

The most variable aspect of carbon tetrachloride analysis is the procedure used to separate carbon tetrachloride from the medium and prepare a sample suitable for GC analysis. As a volatile organic compound of relatively low water solubility, carbon tetrachloride is easily lost from biological and environmental samples, so appropriate care must be exercised in handling and storing such samples for chemical analysis. Brief summaries of the methods available for extraction and detection of carbon tetrachloride in biological and environmental samples are provided below. 

The purge-and-trap method (see Section 6.4) is a common method to enrich volatile organic compounds from water samples. In your apparatus, you purge a 1 L water sample with a gas (air) volume flow of 1.5 L gas per minute at a temperature of 25°C. The compounds that you are interested in include tetrachloroethene, chlorobenzene and methyl-t-butylether (MTBE). Calculate the time required to purge 90% of each compound from the water. Any comments How much time would you save if you would increase the temperature from 25°C to 35°C What could be a problem when raising the temperature too much You can find all necessary data in Appendix C and in Table 6.3. 

A field blank is similar to a method blank, but it has been exposed to the site of sampling. For example, to analyze particulates in air, a certain volume of air could be sucked through a filter, which is then dissolved and analyzed. A field blank would be a filter carried to the collection site in the same package with the collection filters. The filter for the blank would be taken out of its package in the field and placed in the same kind of sealed container used for collection filters. The difference between the blank and the collection filters is that air was not sucked through the blank filter. Volatile organic compounds encountered during transportation or in the field are conceivable contaminants of a field blank. 

Hewitt, A.D., Comparison of sample preparation methods for the analysis of volatile organic compounds in soil samples solvent extraction vs. vapor partitioning, /. Environ. Sci. Technol., 32(1), 143-149, 1998. 

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