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4 Sampling and Chemical Chamctenzation This chapter presents a set of general guidelines and strategies to consider when designing a scheme for sampling and analyzing complex mixtures. No protocol or group of protocols for sampling or analysis will be applicable or appropriate for all types of mixtures. What follows is not intended to constitute a handbook of sampling and analytic methods for complex mixtures. Rather, researchers should design or modify methods as appropriate in each particular instance. However, some general rules can be followed. All of them are based on the approach in which sampling of a complex mixture has three components: the relevance of the material collected to the human situation, the use to which the material will be put, and the potential for human exposure, including routes and extent of exposure and bioavailability. CLASSIFICATION It is important to know as much as possible about the chemical composition of a mixture before any useful toxicologic prediction can be undertaken (toxi- cologic testing can be performed on a mixture in the absence of chemical knowledge if prediction is not the objective). Information on the chemical and physical properties of a mixture can have a direct impact on the selection of testing strategies. Once the mixture has been partially defined, sampling tech- niques, bioavailability, and chemical characterization can be considered. In light of the understanding that complex mixtures can vary widely from combustion and distillation products of fossil or synthetic fuels, to pyrolysis products of tobacco or synthetic materials in buildings, to components leaking from waste-dump sites some criteria must be identified for the mixture, re- 65

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66 COMPLEX MIXTURES gardless of origin. The first criterion, physical state, must be determined. One can encounter such complexity as a mixed-state situation, a slurp of particu- late matter with a liquid or a gas or vapors and gases, which differs substan- tially from each fraction and is not toxicologically comparable with the "mix." The second, chemical-class diversity and component multiplicity, will have to be evaluated; this is difficult, in that a continuum of complexity can be encoun- tered, and whether the components are known or unknown will influence the predictability of the composition and the biohazard. The third criterion, stabil- ity of the mixture, will be important, because chemical instability (i.e., the potential for chemical interactions) will seriously affect the reliability of the sample and the reproducibility of the toxicologic experiment to evaluate the mixture. Complex mixtures can be divided according to whether they are derived from combustion or distillation products or from noncombusted materials. Ex- amples of the first case are fossil and synthetic fuels and vegetable and syn- thetic materials. Examples of the second are food, water, and drugs; hazardous waste; municipal and sewage waste. If one knows the origin of a sample, one can deduce qualitative and quantitative information about the mixture in ques- tion, even if physical characterization and chemical characterization are mini- mal. Extensive information on chemical characterization of a series of fossil- fuel-related materials has been published (e.g., Wright and Dauble, 19861. That information makes it possible to predict chemical classes to be found in mixtures derived from these sources. A detailed discussion of the various ori- gins of complex mixtures is found in Appendix A. SAMPLING Consideration of bioavailability (relevant to human exposure) and of ulti- mate sample use must be incorporated into the sampling strategy, if it is to be effective in producing materials for assay that will provide data relevant to human health. It is important also to consider the preservation of sample integ- rity; sample alterations must be minimized to ensure that the substance assayed is the substance presented to the human environment. COLLECTION STRATEGY Exposure In designing a sampling protocol, input from several kinds of specialists is necessary. Toxicologists, industrial hygienists, or other experts in human health effects should be consulted regarding the most likely routes of exposure to the mixture in question. Exposure of humans via inhalation or ingestion of water or food is most common. In occupational settings, absorption through

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SAMPLING AND CHEMICAL CHARACTERIZATION 67 the skin can also be important. Exposure to a mixture via a combination of routes is not unusual. For example, particles might be inhaled and later swal- lowed after being cleared from the lungs by mucocilia~y action. It is usually practical to consider only the presumed primary route of exposure in designing a sampling protocol. Meteorology Seasonal or meteorologic considerations are particularly germane to the de- sign of protocols for sampling environmental mixtures. Increases in air tem- perature can result in loss of benzoLa~pyrene (BaP), a carcinogenic polycyclic aromatic hydrocarbon (PAH), from particles collected during high-volume at- mospheric sampling (De Wiest and Rondia, 19761. Seasonal variation can also affect surface areas and density of atmospheric particles (Corn et al., 1971; Flessel et al., 19841. Wastewater, soil, and waste-dump sample composition can be expected to vain seasonally. Changes in temperature, freezing condi- tions, and rainfall can all modify the water table and influence environmental sample composition. Temporal Factors Industrial hygienists and process engineers should be consulted as to tempo- ral considerations of sampling. For industrial samples, the time course of pro- duction is important. One must consider whether to sample only at the end of a particular batch process, at the middle of a run, or throughout the production of the material in question. For example, it has been shown that the composition of coal-liquefaction recycle oils changes markedly during the first few days after startup of a process, but is relatively stable after that (Burke et al., 19841. In the case of air sampling at a manufacturing site, both the time of day and the point in the workweek are important. The variability of samples during a work- week has been illustrated in the monitoring of oncology nurses handling cyto- static drugs; the mutagenicity of material extracted from their urine increased toward the end of the week and decreased during the weekend (Nguyen et al., 1982). The duration of sampling is important, particularly for emission materials. If the substances of interest are in low concentration, the sampling period must be long enough to collect material required for the assays proposed. This state- ment of the obvious must be balanced by two other considerations. First, it can take some preliminary investigation to ascertain the likely concentration and to determine whether the concentration of the material is relatively stable or likely to fluctuate. Second, the nature of the collected material might change as the capacity ofthe collection device is approached. Gorse et al. (1982) showed that the biologic activity of diesel exhaust particles changed as the collecting filter

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68 COMPLEX MIXTURES became loaded: the percentage of extractable material, the fluorescence of high-pressure liquid chromatography (HPLC) fractions, and the mutagenicity with respect to Salmonella typhimurium all increased linearly, presumably be- cause the loaded filter became a more efficient collector of mutagenic vapors. Spatial Considerations Inclusion of spatial considerations in the sampling design requires the advice of experts, including industrial hygienists, engineers, and biostatisticians. The primary consideration should be the relevance of the sample site to potential human exposure. If the material is from a manufacturing or refining process, the design should ignore materials in closed systems in favor of open points of maintenance, ingredient addition, product removal, and so forth. Waste sites should be studied as to the availability of deposited materials. Personnel access to the site and the potential for materials to enter water supplies, soil, and food chains are important. In the case of emission, the nature of the research or regulatory questions asked will define whether sampling should focus on the point of discharge, some distant site, or both. A testing program will probably require consideration of multiple testing sites for comparative studies. Whether sampling is to be purposive or of a random statistical design will be determined largely by the nature of the poten- tial for human exposure. Purposive sampling requires selection of a set of sites for generating samples of a particular type. In a study of coal-liquefaction biohazard potential, sam- pling sites would be at various process points: the coal-slur~ying step, the reac- tion vessel, points of refining and separation, discharge of wastewater, final products, recycle materials, and waste. Similarly, sampling could be done in a waste-dump site with a history of material escape or near an emission source and at designated distances from it. Random statistical designs seek to provide an overall picture of an area by sampling at a statistically determined number of places within that area. In a series of publications prepared for the Department of Energy, Gilbert (1983, 1984) described a number of sampling designs, generally termed "probability sampling" (see Table 4-1~. In simple random sampling (see Figure 4-1), eveIy unit of a target sample population (or geographic area) has an equal probability of being collected for assay. The units are numbered from 1 to N. and samples are chosen by drawing n numbers (n < N) from a random-number table or by use of a computer. The units designated by the selected numbers are sampled. This mode of sampling is best applied to a homogeneous population with no dominant spatial or temporal trends. Gilbert noted that most statistical inferen- tial procedures assume that data were collected through simple random sam- pling. Sites of likely sampling of complex mixtures might not be homogeneous with regard to composition or bioavailability of components (e.g., waste

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SAMPLING AND CHEMICAL CHARACTERIZATION TABLE 4-1 Summary of Sampling Designs and When They Are Most Useful 69 Sampling Design Haphazard sampling Most Useful When Population homogeneous over time and space essential; method not recommended, because of difficulty in verifying assumption of homogeneity Target population well defined and homogeneous, so sample-selection bias is not a problem; or specific environmental samples selected for unique value and interest, rather than for making inferences to wider population Judgment sampling Probability sampling Simple random sampling Stratified random sampling Systematic sampling Multistage sampling Cluster sampling Double sampling Homogeneous, i.e., no dominant trends or patterns Homogeneous within strata (subregions); might want to consider strata as domains of study Trends over time or space must be quantified or strictly random methods are impractical Target population large and homogeneous; simple random sampling used to select contiguous groups of population units Population units cluster (schools of fish, clumps of plants, etc.); ideally, cluster means are similar in value, but concentrations within clusters should vary widely Must be strong linear relation between variable of interest and less expensive or more easily measured variable dumps). In addition, practical considerations in the collection of field samples can limit the use of simple random samples. Another type of random sampling is stratified sampling. This assumes a number of nonoverlapping populations that differ from each other, but are internally homogeneous. The population or study site is divided into as many strata as appropriate, and simple random sampling is applied to each stratum. Another technique is multistage subsampling, which involves division of the site or population into primary units (Cochran, 19771. A set of primary units is chosen by simple random sampling, and samples are collected within each of these, under the direction of simple random sampling. This type of design is particularly applicable to geographic areas with variations in terrain, habitat, or other factors that require comparison. It is also useful for a relatively homo- geneous, but large, study site, if the number of samples that can be collected is limited. In cluster sampling, which is related, population units are grouped into clusters, a number of clusters are randomly selected, and all units within the selected clusters are sampled. Distinct from the random designs are the methods of systematic sampling. Gilbert (1984) indicated that these methods often find use in environmental monitoring, because they are generally easier to implement under field condi- tions. In addition, data from statistical investigations have indicated that sys-

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70 SIMPLE RANDOM (a) (c) (e) (g) COMPLEX MIXTURES STRATIFIED RANDOM ~ - (b) ~ - /- ~ TWO-STAGE SAMPLING I A. I . I . | . . PRIMARY UNITS (d) | | | \m -- 1 1 _ . . _ SYSTEMATIC GRID RANDOM WITHIN BLOCKS .. 1 . .. ... . I 1. 1- (flu .~.~.~-e 1. 1.1- .-- . A. SYSTEMATIC UNALIGNED _ AI B I C I D E I F |.G |.H _~1 J it ; (h) SYSTEMATIC RADII CLUSTER SAMPLING 6~9 CLUSTERS FIGURE 4-1 Some probability field sampling designs. Reprinted with permission from Gilbert (1983). tematic sampling can be superior to simple or stratified random sampling for some types of environmental variables. In general, systematic sampling begins with random selection of one unit of the study population. This serves as the starting point of a sampling pattern according to some established spatial or temporal frequency. A problem common to systematic designs is that, if the variable being measured is subject to periodicity or cycles, misleading results

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SAMPLING AND CHEMICAL CHARACTERIZATION 71 will be obtained. Gilbert cited another difficulty: the accuracy of estimates of sampling errors and other statistics depends on the study population's being random. In the aligned-square grid design, a location (or other unit) is chosen at random. The location of each sample is then chosen by applying a grid of fixed dimensions over the chosen area, and two random coordinate numbers are drawn to fix the location of the original point. Each sample site is then fixed in relation to this original point. Variations include the use of a triangular grid and the unaligned-grid-pattern design. In the latter (Figure 4-2), a point A is chosen randomly, and X and Y coordinates are established. To set points B. C, and D, one uses the X coordinate of A and three new randomly chosen Y coordinates. To set points E through I, the point A coordinate Y and random X coordinates are used. One can also design systematic sampling methods based on lines. Figure 4-1 illustrates periodic sampling of radii from a central point, such as a known discharge source. Aligned Square Grid I ~ I I J I -HA my- ~ -- T.-- (a) (c) Central Aligned Square Grid _ _ - - 1_ - - I1 1 1 2- it- 1~- r. (b) : l 1 , 1 1 1 1 - . - 1 _ - _ _ 1 1 t_~- _ ~ ~ ~ I , 1 1 1 Unaligned Grid ~ .BI I .D| ~Hi Hi'- '~1 E | I G I H 1 (d) ) \\ >/ \ A\ ,~ \ I ~ I ~ K .~ | ~ / \|\ / ~ / ~ / \ Triangular Grid FIGURE 4-2 Some systematic designs for sampling in space. Reprinted with permission from Gilbert (1984).

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72 COMPLEX MIXTURES COLLECTION PROCEDURE Designing the collection process requires the input of a toxicologist to pro- vide information on the nature of the assays and of a chemist and an engineer to produce a protocol that will efficiently provide a relevant sample material. One type of information to be supplied by a toxicologist is the amount of material that needs to be collected. Testing protocols geared to chemical analysis gener- ally require smaller samples than more biologically oriented approaches. In vitro tests are more sparing of sample than are whole-animal studies. The collection procedure depends largely on the source of the material and its physical state. Environmental samples are likely to be mixtures of materials in various physical states. They might include mixtures of gases, aerosolized liquids, and suspended particles; combinations of liquid and solid waste; bio- logic tissues, which are largely water; and so forth. We present here examples of sample types and methods deemed appropriate for their collection. Many of these were described at greater length in a recent EPA document (U. S. EPA, 1985), and some useful techniques were also reviewed by Alfheim et al. (19841. Gases and Aerosols Vapor-phase organic chemicals have been collected from ambient air, com- bustion exhaust gases, cigarette smoke, and indoor spaces for chemical charac- terization and bioassay (Hanson et al., 1981 , 1984; Griest et al., 1982; Higgins et al., 1983; Pellizzari et al., 1976; Pellizzari, 1982; Hughes et al., 1980; Krost et al., 1982~. Chemical transformations and perturbations of the original chemical mixture can occur during the sampling step (Berkley and Pellizzari, 1978; Pellizzari et al., 1984; Pellizzari and Krost, 19841. Air particles are a common source of mixtures that have environmental or health significance. Alfheim et al. (1984) recommended that particle-size frac- tionation be included in the collection scheme to increase the biologic rele- vance of a particulate sample. The International Standards Organization (ISO, 1983) and the American Conference of Governmental Industrial Hygienists (Lippmann, 1985) have established cut sizes appropriate to fractionation. They depend on the toxicity at deposition sites in the airways or at sites along the clearance pathways or storage sites. Inspirable particles are those which can be aspirated by the nose or mouth. Thoracic particles are those which can enter the thorax. Respirable particles are those which penetrate the lung's conductive airways. Another reason for size separation is that the chemical composition and biologic activities are related to particle size. Among urban air particles, small size is associated with the presence of acidic compounds, and larger sizes with basic groups (Miller et al., 19791. In comparative assays, most mutagenic activity has been associated with smaller

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SAMPLING AND CHEMICAL CHARACTERIZATION 73 particles, less than 2.5,um in diameter (Talcott and Harger, 1980; Preidecker, 1980; Chrisp and Fisher, 19801. Most of the total PAH content of air particles is found in particles less than 5 ,um in diameter. It has been recommended, however, that results of assays of particles collected with size fractionation be compared with results of assays of particles collected without fractionation. Artifacts of size separation reportedly have reduced activity in mutagenicity assays (Alfl~eim et al., 1983), whereas other chemical transformations report- edly have increased mutagenicity (Clark et al., 19811. Point-source sampling for air particles includes use of impactors (Cheng and Yeh, 1979), cyclones, electrostatic precipitators, and filters (U.S. EPA, 1985~. Sampling methods have been described by Brusick and Young (1982) and Lentzen et al. (19781. Collection of particles from ambient air generally uses high-volume samplers (U.S. EPA, 1971), so-called massive-volume samplers (Henry et al., 1978; Cheng et al., 1984), and medium-, low-, or ultrahigh- volume samplers (Fitz et al., 19831. It has been recommended (U.S. EPA, 1985) that preparation of particulate samples for bacterial-mutagenicity moni- toring begin with collection of standard high-volume samples with inert filter- collection media. For collection of larger amounts of material or when circum- stances dictate a shorter collection period, use of an ultrahigh-volume sampler would be appropriate (U.S. EPA, 19851. If gaseous emission is collected at high temperature, there will be less oppor- tunity for condensation of materials on particles. To collect a gaseous mixture that adequately reflects the material being produced or emitted to the human environment, the possible presence of volatile materials must be considered in the collection scheme. When it is feasible, a gas can be cooled before introduc- tion to an adsorbent material. Alfheim et al. (1984) indicated that XAD-2 resin was most commonly used for this purpose. Gaseous samples can thus be re- duced to collected particles, extracts from absorbents, and condensates. The testing of volatile materials not captured that way is a subject for research and is not generally applicable to routine environmental monitoring or widely used in bioassays. Aqueous Materials Aqueous samples may be collected in a relatively homogeneous state or may contain suspended solids. The most common method of sampling water is manual-grab collection of the required volume. Water generally has low con- centrations of biologically active materials, which must be concentrated for application in most tests. Concentration protocols are therefore identified as the major part of the collection procedure. Methods for concentration of water with less than 5 % associated solids, particularly drinking water, have been well described (Kopfler, 1980; Jolley, 1981; NRC, 19821. Aqueous solutions can be concentrated by removing the water via freeze concentration, lyophiliza-

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74 COMPLEX MIXTURES lion, vacuum evaporation, and reverse osmosis (Shapiro, 1961; Baker, 1970; Dawson and Mopper, 1978; Crathorne et al., 1979; Jolley et al., 1975; Kopfler et al., 19771. These methods concentrate organic and inorganic materials to- gether, a procedure that Kopfler (1980) claimed was a disadvantage if the bio- assay system to be used could not tolerate high concentrations of inorganic materials. Another scheme involves selective concentration of organic materials from drinking water by adsorption of the contaminants on activated carbon or XAD resin columns (Middleton et al., 1956; Kopfler, 1980; McGuire and Suffet, 1983; U.S. EPA, 1985~. A variety of solvents can be used for elusion of or- ganic substances from the activated-carbon columns. Supercritical liquid car- bon dioxide is an efficient elusion solvent (Modell et al., 1978~. This method can be used for large-scale processing of water samples and results in the re- cove~y of gram quantities of contaminants. The limitations of these techniques include the nonextraction or nonrecove~y of inorganic materials and highly polar materials, ionic organic species, or volatile low-molecular-weight or- ganic compounds. Methods that might be suitable for collection of these sub- stances were cited by EPA (19851. Kopfler (1980) noted that organic acids and bases might be amenable to collection on resin columns after adjustment of the water pH to suppress ionization. Altering the pH of a mixture of materials, however, also results in changing its chemical composition or biologic activity. Aqueous samples with large amounts of suspended solids are generally best prepared by separation ofthe phases. Gravity partitioning is done by storing the sample at 4C for 24 hours. The solid phase can then be removed and pro- cessed separately for assay. Alternatively, high-pressure filtration or high- speed centrifugation can be used for phase separation. The liquid portion can be separated into aqueous and nonaqueous components, concentrated if neces- saty, and assayed. Some samples with suspended solids are amenable to pro- cessing by liquid-liquid extraction methods. Details of some of these protocols were described by EPA (19851. Nonaqueous Materials Many environmental and indust~y-related samples are nonaqueous liquids, including organic liquids, light and heavy oils, and some tars. Samples can contain mixtures of volatile (b.p., 36-100C), moderately volatile (b.p., 100- 300C), and nonvolatile (b.p., over 300C) materials, and there might be associated solids. Generally, the composition of such materials is poorly char- acterized and subject to variation after sampling. Much of the information on samples of this sort has been derived from research on fossil-fuel materials (Wright and Dauble, 19861. Sampling itself is usually not difficult; grab sam- pling often suffices. The samples are generally concentrated enough for assay of undiluted or unprocessed material. The preparatory issue with these materi-

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SAMPLING AND CHEMICAL CHARACTERIZATION 75 als therefore is not sampling, but rasher treatment to make the sampled material compatible with the bioassay in question. Some of these issues are discussed later. Solids and Sediments Solid materials appear to be amenable to simple sampling techniques. How- ever, the entire mass of material collected might not constitute the sample of interest. Soils and sediments are examples of materials wherein an unknown or small concentration of a substance of biologic interest is associated with a large quantity of matrix. The protocol for these materials must therefore include extraction and concentration. Specific recommendations for treatment of soils were made by EPA (19851. Efforts should first be made to provide a homogeneous sample. Aggregates can be broken by crushing or cutting. To avoid a particle-size bias, the material can be quartered. This is done by spreading out the material on a clean surface and mechanically dividing the sample into four parts; three parts are returned to the storage vessel, and the remainder is quartered until the desired amount is obtained. Sediments might contain water, which can be removed as described previ- ously. The next step should be extraction in a Soxhlet apparatus with highly pure organic solvents. The nature of material to be recovered will depend largely on the solvents used. Solvents used for extracting materials from soil matrices for chemical analysis have included the following: benzene, ethyl acetate, and benzene-methanol-acetone (2: 1: 1) for humic substances (Ogner and Schnitzer, 1970; Cifrulak, 19691; n-pentane, carbon tetrachloride, and methylene chloride for oil (Jobson et al., 1974; Jensen, 1975; McGill and Rowell, 1980~; and hexane-isopropanol (3:1) for polychlorinated biphenyls (Carey and Gowen, 19781. Other extracting solvents have been used specifically to produce samples that would be amenable to biologic testing. Mutagenic materials were obtained from agricultural soils extracted with hexane-acetone (2:1) and dichloro- methane (Goggelmann and Spitzauer, 1982; Brown et al., 19851. Likewise, mutagenic sediment extracts have been obtained through sequential extraction with diethyl ether and methanol (Kinae et al., 198 11. Ether has also been used on sediments (Sato et al., 19831. The choice of solvents can likely be dictated solely by the nature of the material to be recovered, if the solvent can be evapo- rated or otherwise removed before bioassay. EPA (1985) has recommended rotary evaporation. The pH of the soil or sediment will be a major influence on the types of compounds extracted. For most other types of solid samples, the primary preparative consideration will be to constitute a material compatible with the bioassay selected. The sample must be representative of the environmental or human exposure poten-

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88 COMPLEX MIXTURES TABLE 4-4 Conventional Instrumental Techniques for Chemical Analysis Instrumental Technique Ultraviolet and visible spectroscopy Vibrational spectroscopy (infrared and Raman) Information Content Conjugation Selected References Brown, 1980; Silverstein and Bassler, 1963 Borwn, 1980; Strommen and Nakamoto, 1984; Gans, 1980; Case and Fately, 1980; Clerc et al., 1981 Penzer, 1980 Chemical functionalities and assembly of atoms Molecular emission spectroscopy Mass spectrometer Nuclear magnetic resonance spectrometer Atomic absorption spectroscopy and inductively coupled argon . . . plasma emission Electron paramagnetic spin resonance Selective detection Molecular weight, chemical functionalities, overall structure, and assembly of atoms Anangement of atoms in molecule Elements Free-radical formation Brown, 1980 Watson and Throck, 1985; Wilson et al., 1981; Smith and Udseth, 1983 Jones, 1980; Jackrnan and Sternhell, 1969 Wood, 1980; Cantle, 1982 used to identify the chemicals responsible for toxicity. Extreme caution should be exercised when one is comparing chemical data bases derived from different complex mixtures, because the separation techniques introduce uncertainty as to whether structural elucidation is unequivocal or merely postulative or tentative. For structural analysis, these modern methods are used most efficiently if they are combined, because they can provide complementary information that increases their overall effectiveness. Guidelines for the combined application of spectroscopic methods are available (Clerc et al., 1981; Silverstein and Bassler, 19631. The most generally applied methods for the characterization of organic substances are ultraviolet spectroscopy, infrared spectroscopy, proton and carbon-13 nuclear magnetic resonance, and mass spectrometer (Clerc et al., 19811. Specialized techniques such as magnetic resonance of other nu- clei, Raman spectroscopy, and optical rotary dispersion are used less often. Gas chromatography/Fourier-transform infrared (GC/FT-IR) spectroscopy is now being developed for routine use in identifying analyses in complex mix- tures with the aid of software programs for the automatic interpretation of spectra (Growths, 1980; Gurka, 1985~. Infrared, Raman, visible, ultraviolet, electron-spin resonance, and magnetic circular dichroism spectroscopies have all been used in conjunction with matrix isolation (Barnes and Orville-Thomas, 19801. Matrix isolation traps isolated molecules of the species to be studied in a

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SAMPLING AND CHEMICAL CHARACTERIZATION 89 large excess of an inert material by rapid condensation at a low temperature, so that the diluent forms a rigid cage or matrix (Barnes and Orville-Thomas, 1980~. The noble gases (primarily argon) and nitrogen are most widely used for matrix materials. More recent uses of matrix isolation have been in combina- tion with GC effluents in which high-resolution gas chromatography (HRGC) has been coupled with FT-IR spectroscopy. Several HPLC/FT-IR systems have been described (Growths, 19801. The exquisite sensitivity of GC/FT-IR with matrix isolation rivals that of mass spectrometer; these two methods can also be combined to provide simultaneous and complementary information during chromatography of a complex mixture. The gas chromatograph is the most commonly used inlet system for analysis of complex mixtures with mass spectrometry (Watson and Throck, 19851. It is rarely possible to isolate in pure form each of the hundreds of individual sub- stances present. However, HRGC combined with mass spectrometer (GC/ MS) can often serve as the final purification step by resolving the various components and presenting them one at a time to the mass spectrometer. The mass spectrometer can also serve as a universal detector for SFC and HPLC (Smith and Udseth, 19831. Several types of devices are under develop- ment (e.g., moving wire or moving belt, direct inlet, and thermospray) to introduce relatively nonvolatile materials after separation into the ion source of the mass spectrometer. A fast-atom-bombardment (FAB) ionization technique combined with a moving belt exploits the attributes of FAB ionization of non- volatile analyses and allows analysis in a manner very similar to that of GC/MS (Smith and Udseth, 19831. An alternative to resolving components chromatographically is separating them by mass spectrometric methods the so-called MS/MS methods (Watson and Throck, 1985; Smith and Udseth, 1983; Henderson et al., 1982, 1983, 19841. The complex mixture is ionized, usually gently, to produce charactens- tic ions from each component. The ions suspected to arise from the component of interest are selected by mass analysis in the first stage of a double mass spectrometer, and their identity is confirmed by mass analysis in the second stage on the basis of the fragment ions arising from collision-induced associa- tion of the selected ions. REFERENCES Ahuja, S. 1984. Overview: Multiple pathways to ultrahigh resolution chromatography, pp. 1-8. In S. Ahuja (ed.). Ultrahigh Resolution Chromatography. ACS Symposium Series 250. American Chemical Society, Washington, D.C. Alfheim, I., G. Lofroth, and M. Molter. 1983. Bioassay of extracts of ambient particulate matter. Environ. Health Perspect. 47:227-238. Alfheim, I., A. Bjorseth, and M. Molter. 1984. Charactenzation of microbial mutagens in complex samplesmethodology and application. CRC Crit. Rev. Environ. Control 14:91-150.

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SAMPLING AND CHEMICAL CHARACTERIZATION 91 Cheng, Y.-S., and H.-C. Yeh. 1979. Particle bounce in cascade impactors. Environ. Sci. Technol. 13: 1392-1396. Cheng, Y.-S., R. L. Hanson, R. L. Carpenter, C. H. Hobbs. 1984. Use of a massive volume air sampler to collect fly ash for biological characterization. J. Air Pollut. Control Assoc. 34:671-674. Chess, E. K., and R. D. Smith. 1984. Development and Evaluation of Supercritical Fluid Chromatog- raphy/Mass Spectrometry for Polar and High Molecular Weight Coal Components. PNL-SA-12298. CONF-840694-9. Battelle Pacific Northwest Labs, Richland, Wash. (Available from NTIS as DE850008271XAB.) (8 pp.) Chrisp, C. E., and G. L. Fisher. 1980. Mutagenicity of airborne particles. Mutat. Res. 76: 143-164. Chrisp, C. E., G. L. Fisher, and J. E. Lammert. 1978. Mutagenicity of filtrates from respirable coal fly ash. Science 199:73-75. Chriswell, C. D., B. A. Glatz, J. S. Fritz, and H. J. Svec. 1978. Mutagenic analysis of drinking water, pp. 477-494. In M. D. Waters, S. Nesnow, J. F. Huisingh, S. S. Sandhu, and L. Claxton (eds.). Application of Short-Term Bioassays in the Fractionation and Analysis of Complex Environmental Mixtures. Plenum, New York. Cifrulak, S. D. 1969. Spectroscopic evidence of phthalates in soil organic matter. Soil Sci. 107:63-69. Clark, C. R., T. J. Truex, F. S. C. Lee, and I. T. Salmeen. 1981. Influence of sampling filter type on the mutagenicity of diesel exhaust particulate extracts. Atmos. Environ. 15:397-402. Claxton, L. D. 1982. Review of fractionation and bioassay characterization techniques for the evalua- tion of organics associated with ambient air particles, pp. 19-34. In R. R. Tice, D. L. Costa, and K. M. Schaich (eds.). Genotoxic Effects of Airborne Agents. Environmental Science Research. Vol. 25. Plenum, New York. Clerc, J. T., E. Pretsch, and J. Seibl. 1981. Structural Analysis of Organic Compounds by Combined Application of Spectroscopic Methods. Elsevier, New York. (288 pp.) Cochran, W. G. 1977. Sampling Techniques, 3rd ed. John Wiley & Sons, New York. (274 pp.) Corn, M., T. L. Montgomery, and N. A. Esmen. 1971. Suspended particulate matter: Seasonal vari- ation in specific surface areas and densities. Environ. Sci. Technol. 5: 155-158. Crathorne, B., C. D. Watts, and M. Fielding. 1979. Analysis of non-volatile organic compounds in water by high-performance liquid chromatography. J. Chromatography 185:571 -690. Daisey, J. M., T. J. Kneip, I. Hawryluk, and F. Mukai. 1980. Seasonal variations in the bacterial mutagenicity of airborne particulate organic matter in New York City. Environ. Sci. Technol. 14: 1487-1490. Dawson, R., and K. Mopper. 1978. A note on the losses of monosaccharides, amino sugars, and amino acids from extracts during concentration procedures. Anal. Biochem. 84: 186-190. Dehnen, W., N. Pitz, and R. Tomingas. 1977. The mutagenicity of airborne particulate pollutants. Cancer Lett. 4:5-12. Demirgian, J. 1984. Computerized rapid analysis of complex mixtures by gas chromatography. J. Chromatogr. Sci. 22:153-160. De Wiest, F., and D. Rondia. 1976. Sur la validite des determinations du Benzo (a) pyrene atmosphe- rique pendant les mods d~ete. Atmos. Environ. 10:487~89. (English abstract.) Eckert, C. A., J. G. Van Alsten, and T. Stoicos. 1986. Supercritical fluid processing. Environ. Sci. Technol. 20:319-325. Edstrom, T., and B. A. Petrol 1968. Gel permeation chromatographic studies of polynuclear aromatic hydrocarbon materials. J. Polym. Sci. Part C (21): 171-182. Eisenberg, W. C. 1978. Fractionation of organic material extracted from suspended air particulate matter using high pressure liquid chromatography. J. Chromatogr. Sci. 16: 145- 151. Epler, J. L. 1980. The use of short-term tests in the isolation and identification of chemical mutagens in complex mixtures, pp. 239-270. In P. J. de Serres and A. Hollaender (eds.). Chemical Mutagens: Principles and Methods for Their Detection, Vol. 6. Plenum, New York. Epler, J. L., B. R. Clark, C.-H. Ho, M. R. Guerin, and T. K. Rao. 1978. Short-term bioassay of complex organic mixtures: Part II, mutagenicity testing, pp. 269-289. In M. D. Waters, S. Nesnow,

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92 COMPLEX MIXTURES J. L. Huisingh, S. S. San&u, and L. Claxton (eds.). Application of Short-Term Bioassays in the Fractionation and Analysis of Complex Environmental Mixtures. Plenum, New York. Fitz, D. R., G. J. Doyle, and J. N. Pitts, Jr. 1983. An ultrahigh volume sampler for the multiple filter collection of respirable particulate matter. J. Air Pollut. Control Assoc. 33: 877-879. Flessel, P., G. Guirguis, J. Cheng, K. Chang, and E. Hahn. 1984. Monitoring of Mutagens and Carcinogens in Community Air. ARB-R-84/223. California State Air Resources Board, Sacramento, Calif. (Available from NTIS as PB85-173763/XAB.) (134 pp.) Florin, I., L. Rutberg, M. Curvall, and C. R. Enzell. 1980. Screening of tobacco smoke constituents for mutagenicity using the Ames' test. Toxicology 15:219-232. Flotard, R. D. 1980. Sampling and Analysis of Trace-Organic Constituents in Ambient and Workplace Air at Coal-Conversion Facilities. Argonne National Laboratory, Argonne, Ill. (Available from NTIS as ANL/PAG-3.) (51 pp.) Gans, P. 1980. Vibrational spectroscopy, pp. 115-147. In S. B. Brown (ed.). An Introduction to Spectroscopy for Biochemists. Academic Press, New York. Gilbert, R. O. 1983. Field sampling designs, simple random and stratified random sampling. TRANS- STAT Statistics for Environmental Studies, No. 24. PNL-SA-11551. Battelle Pacific Northwest Labs, Richland, Wash. (Available from NTIS as DE83016826.) (38 pp.) Gilbert, R. O. 1984. Field sampling designs: Systematic sampling. TRANS-STAT Statistics for Environmental Studies. No. 26. PNL-SA-12180. Battelle Pacific Northwest Labs, Richland, Wash. (32 pp ) Goggelmann, W., and P. Spitzauer. 1982. Mutagenic activity, content of polycyclic aromatic hydro- cargons (PAM) and humus in agricultural soils. Abstract No. 50. Mutat. Res. 97: 189-190. Gorse, R. A., Jr., I. T. Salmeen, and C. R. Clark. 1982. Effects of filter loading and filter type on the mutagenicity and composition of diesel exhaust particulate extracts. Atmos. Environ. 16: 1523- 1528. Gouw, T. H., R. E. Jentoft, and E. J. Gallegos. 1979. Some recent advances in supercritical fluid chromatography, pp. 583-592. In K. D. Timmerhaus and M. S. Barber (eds.). High-Pressure Sci- ence and Technology, Vol. 1: Physical Properties and Material Synthesis. Plenum, New York. (583 pp.) Griest, W. H., C. E. Higgins, R. W. Holmberg, J. H. Moneyhun, J. E. Caton, J. S. Wike, and R. R. Reagen. 1982. Characterization of vapor- and particulate-phase organics from ambient air sampling at the Kosovo gasifier, pp. 395-410. In L. H. Keith (ed.). Energy and Environmental Chemistry, Vol. 1. Ann Arbor Science, Ann Arbor, Mich. Griff~ths, P. R. 1980. Chromatography and PT-IR spectrometry, pp. 149-155. In J. R. Durig (ed.). Analytical Applications of FT-IR to Molecular and Biological Systems. D. Reidal, Dordrecht, Hol- land. (607 pp.) Guerin, M. R. 1981. The integrated approach to chemical-biological analysis, pp. 1-16. In J. C. Harris, P. L. Levins, and K. D. Drewitz (eds.). Proceedings, 2nd Symposium on Process Measure- ments for environmental Assessment, February 25-27, Atlanta, Gal, 1980. Industrial Environmen- tal Research Lab., Research Triangle Park, N.C. (Available from NTIS as PB82-211574.) Guerin, M. R., B. R. Clark, C.-H. Ho, J. L. Epler, and T. K. Rao. 1978. Short-term bioassay of complex organic mixtures: Part I, chemistIy, pp. 247-268. In M. D. Waters, S. Nesnow, J. L. Huisingh, S. S. San&u, and L. Claxton (eds.). Application of Short-Term Bioassays in the Fraction- ation and Analysis of Complex Environmental Mixtures. Plenum, New York. Guerin, M. R., C.-H. Ho, T. K. Rao, B. R. Clark, and J. L. Epler. 1980. Separation and identification of mutagenic constituents of petroleum substitutes. Int. J. Environ. Anal. Chem. 8:217-225. Guerin, M. R., J. Dutcher, E. S. Olson, E. J. Peterson, V. C. Stamoudis, D. H. Stuermer, and B. W. Wilson. 1983. Summary of chemical characterization methodologies with future directives, pp. 263-266. In C. W. Wright, W. C. Weimer, and W. D. Felix (eds.). Advanced Techniques in Syn- thetic Fuels Analysis. PNL-SA-11552. CONF-811160. U.S. Department of Energy, Technical In- formation Center, Oak Ridge, Tenn. (Available from NTIS as DE83015528.)

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SAMPLING AND CHEMICAL CHARACTERIZATION 93 Gurka, D. F. 1985. Interim protocol for the automated analysis of semivolatile organic compounds by gas chromatography/Fourier transform infrared (GC/FT-IR) spectrometry. Appl. Spectrosc. 39:827-833. Hackett, P. L., R. L. Music, D. D. Mahlum, and M. R. Sikov. 1983. Developmental effects of oral administration of solvent refined coal materials to rats. (Abstract.) Teratology 27:47A. Hanson, R. L., R. L. Carpenter, and G. J. Newton. 1980. Chemical characterization of polynuclear aromatic hydrocarbons in airborne effluents from an experimental fluidized bed combustor, pp. 599- 616. In A. Bjorseth and A. J. Dennis (eds.). Polynuclear Aromatic Hydrocarbons: Chemistry and Biological Effects. Battelle Press, Columbus, Ohio. Hanson, R. L., C. R. Clark, R. L. Carpenter, and C. H. Hobbs. 1981. Evaluation of Tenax-GC and XAD-2 as polymer absorbents for sampling fossil fuel combustion products containing nitrogen oxides. Environ. Sci. Technol. 15:701-705. Hanson, R. L., R. E. Royer, J. M. Benson, R. L. Carpenter, G. J. Newton and R. F. Henderson. 1982. Chemical fractionation and analysis of organic compounds in process streams of low Btu gasifies effluents, pp. 205-223. In E. L. Fuller, Jr. (ed.). Coal and Coal Products: Analytical Characteriza- tion Techniques. Polynuclear Aromatic Hydrocarbons. ACS Symposium Series 205. American Chemical Society, Washington, D.C. Hanson, R. L., C. R. Clark, R. L. Carpenter, and C. H. Hobbs. 1984. Comparison of Tenax-GC and XAD-2 as polymer absorbents for sampling combustion exhaust gases, pp. 79-93. In L. H. Keith (ed.). Identification and Analysis of Organic Pollutants in Air. Butterworth, Boston, Mass. Hanson, R. L., A. R. Dahl, S. J. Rothenberg, J. M. Benson, A. L. Brooks, and J. S. Dutcher. 1985. Chemical and biological characterization of volatile components of environmental samples after fractionation by vacuum line cryogenic distillation. Arch. Environ. Contam. Toxicol. 14:289-297. Haugen, D. A., and V. C. Stamoudis. 1986. Isolation and identification of mutagenic polycyclic aromatic hydrocarbons from a coal gasifies condensate. Environ. Res. 41 :400-419. Henderson, T. R., R. E. Royer, C. R. Clark, T. M. Harvey, and D. F. Hunt. 1982. MS/MS of diesel emissions and fuels treated with NO2. J. Appl. Toxicol. 2:231-237. Henderson, T. R., J. D. Sun, R. E. Royer, C. R. Clark, A. P. Li, T. M. Harvey, D. H. Hunt, J. E. Fulford, A. M. Lovette, and W. R. Davidson. 1983. Triple quadrupole mass spectrometry studies of nitroaromatic emissions from different diesel engines. Environ. Sci. Technol. 17:443-449. Henderson, T. R., J. D. Sun, A. P. Li, R. L. Hanson, W. E. Bechtold, T. M. Harvey, J. Shabanowitz, and D. F. Hunt. 1984. GC/MS and MS/MS studies of diesel exhaust mutagenecity and emissions from chemically defined fuels. Environ. Sci. Technol. 18:428-434. Henry, W. M., R. I. Mitchell, and R. J. Thompson. 1978. Development of a Large Sampler Collector of Respirable Particulate Matter. EPA-600/4-78/009. Battelle Columbus Labs, Columbus, Ohio. (Available from NTIS as PB-281 528/0.) (54 pp.) Higgins, C. E., W. H. Griest, and G. Olerich. 1983. Application of Tenax trapping to analysis of gas phase organic compounds in ultra-low tar cigarette smoke. J. Assoc. Off. Anal. Chem. 66: 1074- 1083. Higgins, C. E., W. H. Griest, and M. R. Guerin. 1984. Sampling and Analysis of Cigarette Smoke Using the Solid Adsorbent Tenax. ORNL/TM-9167. Oak Ridge National Lab, Oak Ridge, Tenn. (Available from NTIS as DE 84012025.) (25 pp.) Hite, M., and H. Skeggs. 1979. Mutagenic evaluation of nitroparaffins in Salmonella typhimurium/ mammalian-microsome test and the micronucleus test. Environ. Mutagen. 1 :383-389. Ho, C.-H., C. Y. Ma, B. R. Clark, M. R. Guerin, T. K. Rao, and J. L. Epler. 1980. Separation of neutral nitrogen compounds from synthetic crude oils for biological testing. Environ. Res. 22: 412-422. Hoffmann, D., K. No~poth, R. H. Wickramasinghe, and G. Muller. 1980. The detection of mutagenic air pollutants from filter samples by the salmonella/mammalian S-9 mutagenicity test^ (Ames test) with S. typhimurium TA98 (Part 1). Zentralbl. Bakteriol. Mikrobiol. Hyg. 1 Abt., Orig. B 171: 388-407.

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