Envlron. Sci. Technol. 1985, 19, 924-928
lated Processes"; Brinckman, F. E.; Fish, R. H., Eds.; National Bureau of Standards: Washington, DC, 1981; NBS Spec. Publ. No. 618, pp 21-38. Saar, R. A,; Weber, J. H. Environ. Sci. Technol. 1982,16,
Aqueous Solution";International Union of Pure and Applied Chemistry, Butterworth: London, 1965. (21) Yoe, Y. H.; Jones, A. L. Ind. Eng. Chem. Analy. Ed. 1944, 16, 111-115.
510A-516A.
Jorgensen, A. D.; Stetter, J. R. Anal. Chem.
1982, 54,
381-385.
Stetter, J. R.; Stamoudis, V. C.; Jorgensen, A. D. Environ. Sci. Technol., following paper in this issue. Perrin, D. D. "Dissociation Constants of Organic Bases in
Received for review September 27, 1983. Revised manuscript received January 1,1985. Accepted April 17,1985. This work was supported by the US.Department of Energy under Contract W-31-109-Eng-38.
Interactions of Aqueous Metal Ions with Organic Compounds Found in Coal Gasification: Process Condensates Joseph R. Stetter" and Vassiiis C. Stamoudls Energy and Environmental Systems Dlvision, Argonne National Laboratory, Argonne, Illinois 60439
Andrew D. Jorgensent University of Southern Indiana, Evansville, Indiana 477 12
The acidic, basic, and neutral fractions of a coal gasification tar were analyzed by capillary column gas chromatography and gas chromatography/mass spectroscopy. Studies were performed to characterize the interactions between basic and neutral fraction components of the tar and aqueous solutions containing Fe3+. Basic organic constituents, especially pyridines and anilines, were affected by the presence of aqueous iron ions, while the neutral constituents were not.
Introduction In the preceding paper (I),a model system was used to elucidate the chemical interactions between aqueous metal ions and certain organic chemicals that are present in coal gasification condensates. However, no measurements have been made that would indicate the effect of exposing an authentic coal conversion material to the environment. In this paper, results are reported of a detailed analysis of (1) the basic and neutral components of a tar obtained from a condensate of a high-Btu coal gasification pilot plant and (2) the interactions of aqueous iron ions with the complex basic and neutral fractions of these samples. Because the basic and neutral fractions of coal gasification tars are known to contain a wide variety of chemicals, including several potent mutagens (2-14))the analysis, fate, and toxicology of these compounds are of great concern. Environmental and health consequences depend on the particular species present and the extent to which trace aqueous metal ions can influence the partitioning of real materials between aqueous and organic solutions.
Experimental Section Sample Description. The tar sample was taken from the HYGAS coal gasification pilot plant in Chicago. Operated by the Institute of Gas Technology, the plant is designed to produce 1.5 million ft3 of substitute natural gas equivalent per day from approximately 80 tons of coal. The plant was operating with a feed of bituminous coal (Kentucky no. 9 and no. 11)during run 84 when the ma+Present address: Allegheny College, Meadville, PA 16335. 924
Environ. Sci. Technol., Vol. 19, No. 10, 1985
terials studied in this investigation were collected. The HYGAS plant uses a three-stage fluidized-bed hydrogasification system; details of the facility and its operation have been published (25). The feed coal is pulverized, pretreated, and mixed with a recycling oil (initially toluene) to create a slurry. The coal slurry, which is fed into the top of the gasifier, is subsequently stripped of light oil and gasified in three stages at progressively higher temperatures. A sample was taken from the upper part of the gasifier, called the low-temperature reactor (LTR),where the first stage of gasification takes place. The LTR sample is representative of the chemicals formed during the gasification process and, in principle, provides information on the less-volatile materials formed (2). The basic and neutral fractions used in this study were obtained from the LTR condensate. Phase Separation and Distillation. The original LTR sample consisted of an aqueous layer and an oil layer. These layers were separated, and the oil was concentrated by rotary evaporation to a nonvolatile organic residue (NVO). The NVO residue (tar) was held a t 50 "C and 1 mmHg for 2 h after the solvents were removed. Acid-Base-Neutral pH Fractionation. The NVO sample was partitioned between 1.0 N HC1 and methylene chloride (dichloromethane) to give an aqueous layer containing the alkaline chemicals as salts and a methylene chloride layer containing the acidic and neutral chemicals. The latter were then partitioned between methylene chloride and 1.0 N NaOH to give an aqueous layer containing the acids as salts and a methylene chloride layer containing the neutral chemicals. The aqueous layers were each neutralized and back-extracted with methylene chloride to obtain separate methylene chloride extracts of the acidic, basic, and neutral chemicals. Analysis of Basic and Neutral Fractions. The organic compounds in the basic and neutral fractions were analyzed by capillary column gas chromatography (GC) to quantify individual compounds and by gas chromatography/mass spectrometry (GC/MS) to identify compounds. A Hewlett-Packard (HP) Model 5880A equipped with H P level 4 computer control and reporting capability was used for gas chromatographic analyses. Flexible, fused
0013-936X/85/0919-0924$01.50/0
0 1985 American Chemical Society
Table I. Organic Compounds Identified in Basic Fraction of HYGAS Low-Temperature Reactor Tar retention time,’ min
compound
concn, mg/g
10.5 13.1 14.9 16.2 18.0 18.9 19.8 20.2 20.9 21.2 23.0 24.0 24.3 24.6 25.4 27.5 28.2 28.9 29.3 30.0 30.6 31.2 33.2 34.0 34.5 35.0 35.2 36.2 36.2 37.1 37.7 37.9 39.2 39.8 40.6 41.4 43.0 43.5 44.1 45.6 46.0 46.8 47.5 48.4 48.7 49.5
methylpyridine methylpyridine methylpyridine C2-pyridine C2-pyridine C2-pyridine Cz-pyridine Cz-pyridine (&-pyridine C2-pyridine C3-pyridine C3-pyridine C3-pyridine aniline C3-pyridine C4-pyridine C4-pyridine C,-pyridine C4-pyridine methylaniline methylaniline methylaniline C4-pyridine C4-pyridine C4-pyridine C4-pyridine C,-pyridine (&pyridine (&-pyridine C,-pyridine (&-pyridine C2-aniline C,-pyridine (&-pyridine azanaphthalene azanaphthalene C3-aniline C3-aniline C3-aniline methylazanaphthalene methylazanaphthalene methylazanaphthalene methylazanaphthalene methylazanaphthalene methylazanaphthalene methylazanaphthalene
9.1 12.4 5.5 2.3 22.4 4.6 1.9 1.9 3.5 3.1 17.6 5.8 8.3 5.4 3.4 3.5 5.8 3.9 3.5 14.8 19.6 46.3 1.9 6.8 4.3 1.6 2.4 3.2 5.7 8.1 5.6 19.8 9.1 3.4 120.4 29.6 2.3 3.5 7.1 44.6 14.0 12.7 17.6 31.6 15.3 6.5
retention time,’ min
compound
49.9 50.2 50.8 51.2 51.8 53.0 53.3 54.3 54.7 55.2 56.2 57.2 58.5 59.0 59.4 60.0 60.6 61.1 61.6 62.4 62.8 63.7 64.9 65.6 65.9 66.6 68.4 68.7 69.8 70.5 70.8 72.3 73.8 74.5 75.2 75.7
Cz-azanaphthalene methylazanaphthalene Cz-azanaphthalene Cz-azanaphthalene C,-azanaphthalene Cz-azanaphthalene Cz-azanaphthalene C2-azanaphthalene azabiphenyl Cz-azanaphthalene azafluorene C3-azanaphthalene C3-azanaphthalene methylazabiphenyl C3-azanaphthalene C3-azanaphthalene C3-azanaphthalene C3-azanaphthalene 1-naphthylamine methylazaacenaphthene 2-naphthylamine C2-azabiphenyl Cz-azabiphenyl azafluorene azafluorene methylazafluorene methylnaphthylamine methylnaphthylamine methylnaphthylamine azaacenaphthene azaacenaphthene azaphenanthrene azaphenanthrene azaphenanthrene Cz-azafluorene azaanthracene methylazaanthracene and/or methylphenanthrene methylazaphenanthrene methyl-azaphenanthrene and/or methylazaanthracene azapyrene aminoanthracene and/or aminophenanthrene aminoanthracene and/or aminophenanthrene
78.0 77.3 79.4 80.8 91.4 93.9 94.9
t
concn, mg/g 18.1 14.0 3.5 6.0 5.9 21.6 5.9 22.5 18.9 16.1 11.0 12.5 5.8 9.4 6.1 5.4 1.3 8.0
8.5 4.0 43.6 4.8 3.8 8.5 11.0 7.0 10.3 12.2
14.4 4.4 5.3 5.6 15.3 26.8 4.4 28.9 9.6 9.5 5.0 5.3 5.9 1.6 5.6
Temperature program is described in the text.
silica, wall-coated, open tubular capillary columns obtained from H P were used for chromatographic separation of the samples. The columns were 50 m long, were coated with SP 2100 (methyl silicone), and had inside diameters of 0.21 or 0.31 mm. The temperature was programmed to increase from 20 to 270 OC a t a rate of 2 OC/min, with a 2-min hold a t 20 OC after injection. The gas chromatograph was equipped with a H P Model 1883B Grob-type split/splitless capillary inlet system operated in the splitless mode, which allowed continuous septum purge except during the first 0.6 min after injection. The carrier gas was ultra high purity helium, and a flame ionization detector (FID) was used for all gas chromtographic analyses. Acceptable precision in component concentration measurements was obtained by using a trace impurity in the solvent as an internal standard, and peaks of interest were reproduced to a precision of 5 % An H P Model 5984A GC/MS instrument, equipped with an H P Model 5840A GC and an H P Model 5934A data system, was used to identify compounds. Representative standards were used to obtain both retention times and mass spectra for direct comparisons. Identifi-
.
cation of compound classes was emphasized rather than differentiation among specific isomers. Therefore, isomers are reported as Cz, C3, ...,C, homologues, where n refers to the total number of carbon atoms in the saturated alkyl substitutions attached to the parent organic compound. Compound classes (such as pyridines and anilines, azanaphthalenes and aminonaphthalenes, and biphenyls and acenaphthenes) that give somewhat similar spectra can be distinguished by observing their characteristic chromatographic retention times. Interaction Experiments. The iron solution was prepared by dissolving reagent-grade iron(II1) chloride hexahydrate in water to yield a concentration of 200 ppm of Fe3+by weight (pH -2.5). A diluted solution of 20 ppm of Fe3+ (pH -2.9) also was used. The experiments to study the interaction of aqueous iron ions and organic compounds consisted of placing approximately 100 pL of the appropriate fraction (basic or neutral) dissolved in methylene chloride a t a concentration of 40 mg/g into a microvial and adding 200 pL of the appropriate aqueous iron solution. Thorough contact of the phases was achieved by shaking and repeated syringe injection of one Environ. Sci. Technol., Vol. 19, No. 10, 1985
925
Table 11. Organic Compounds Identified in the Neutral Fraction of HYGAS Low-Temperature Reactor Tar retention time," min 42.3 44.5 44.9 46.2 46.5 47.2 47.5 49.7 50.2 50.7 52.0 53.0 53.2 53.9 53.9 54.4 54.7 55.2 56.7 57.7 58.6 59.2 59.6 60.4 61.5 61.8 62.7 63.4 65.0 65.5 66.0 66.9 67.5 68.2 68.6 69.4 69.7 70.5 71.6 72.0 72.4 72.9 a
concn, retention time: min mg/g methylindene 0.8 73.8 naphthalene 22.9 74.7 benzothiophene 5.0 75.1 Cz-indan 0.5 75.6 Cz-indan 0.7 76.9 C2-indan 1.7 78.2 Cz-indan 2.1 78.6 Cz-indan 0.3 79.0 C2-indene 2.4 80.7 (&-indene 2.5 80.9 methylbenzothiophene 5.7 81.5 2-methylnaphthalene 62.6 82.7 methylbenzothiophene 6.7 83.2 1-methylnaphthalene 29.6 84.7 1-methylnaphthalene 29.6 85.2 C3-indan 1.0 86.1 CJndan 1.0 87.34 C3-indan 8.6 88.7 indole 2.3 89.34 C3-indan 1.0 89.92 biphenyl 23.0 92.18 C,-benzothiophene 3.8 94.50 C2-naphthalene 12.1 95.4 C2-naphthalene 26.5 Cz-naphthalene 36.6 96.6 C2-naphthalene and methylbiphenyl 5.6 98.9 C2-naphthalene 3.6 99.4 (&naphthalene 3.6 100.1 acenaphthene 9.0 101.9 methylbiphenyl 13.3 methylbiphenyl and C3-benzothiophene 102.8 6.0 C3-naphthalene 103.3 7.8 dibenzofuran 103.4 38.5 C3-naphthalene 104.2 4.3 C3-naphthalene 7.6 C3-naphthalene 108.6 4.9 4.3 C3-naphthalene 113.5 C3-naphthalene 8.0 125.6 methylfluorene 42.0 126.6 6.3 C3-naphthalene and C4-benzothiophene 8.5 C4-benzothiophene and C2-biphenyl and methylacenaphthene 8.0 compound
concn, mg/g xanthene 13.8 methyldibenzofuran 20.6 Cz-oacenaphthene 6.5 C4-naphthalene 3.1 C4-naphthalene 1.5 Cz-fluorene 17.4 Cz-fluorene 8.4 C3-biphenyl and C2-acenaphthene 8.7 C3-biphenyl 8.0 dibenzothiophene 7.7 C3-biphenyl 7.2 phenanthrene 51.4 anthracene 22.7 C4-biphenyl and azaphenanthrene 4.2 C4-biphenyl and and C3-acenaphthene 3.2 C4-biphenyl and C3-acenaphthene 5.1 methyldibenzothiophene 3.8 methylphenanthrene 10.8 methylphenanthrene 9.2 methylanthracene 9.8 phenylnaphthalene 14.2 C2-phenanthrene 4.4 C2-anthracene and/or 6.6 C2-phenanthrene fluoranthrene 11.2 pyrene 10.0 methylphenylnaphthalene 5.3 methylphenylnaphthalene 4.6 methylphenylnaphthalene and 4.9 alkane (Cz2) methylphenylnaphthalene 4.8 methylfluoranthene 4.7 1.1 methylpyrene methylfluoranthene and/or 6.7 methylpyrene Cz-fluoranthene and/or 5.6 Cz-pyrene chrysene 10.2 2.2 benzopyrene benzopyrene 1.0 compound
Temperature program is described in the text.
phase into the other. Phase separation was assisted by centrifugation when necessary. A sample of the organic layer was withdrawn periodically via a 10-pL syringe and analyzed by gas chromatography. The concentrations of organic compounds in the various samples were measured for up to 4 days by using techniques described previously ( 1 , 16).
Results and Discussion Composition of the Acidic, Basic, and Neutral Fractions. Tables I and I1 list the specific organic compounds found in the basic and neutral fractions and their concentrations. These species represent the broad spectrum of basic and neutral compounds produced in coal conversion processes. The acidic fraction contained primarily hydroxy aromatic compounds, with phenols and cresols by far the major components. Because these compounds are rather water soluble, the acid fraction was not used in our aqueous experiments. However, they are known to readily partition to the aqueous phase, as confirmed by the relative abundance of phenolic compounds in coal conversion wastewaters (2,17).The main classes of chemicals were Co-to C6-phenols,Co- to C2-hydroxyindansand hydroxyindenes, Co- to C,-naphthols, Co- to C3-hydroxybiphenyls, Co- to C1-hydroxyacenaphthenes and hydroxyfluorenes, and hy926
Envlron. Scl. Technol., Vol. 19, No. IO, 1985
droxyphenanthrene and hydroxyanthracene. Over 150 constituents were identified in the basic fraction. The major components were one- to four-ring azaarenes and one- to three-ring aromatic amines. Both parent and alkylated species were present. The concentrations of five-ring azaarenes and four-ring amines were relatively low, which is typical of coal gasification materials. The severe environment of a gasifier is not conducive to production of high concentrations of high molecular weight basic compounds. The neutral fraction contained one- to five-ring aromatic hydrocarbons; naphthalenes were the predominant species. However, significant amounts of dibenzofurans and thiophenes were present, along with small quantities of the neutral nitrogen heterocycle indole. Carbazoles were not present in significant concentration in this gasification tar. Interaction of Aqueous Fe3+and Organic Compounds. The basic and neutral fractions were chosen for study for three primary reasons. First, they contain most of the known sample bioactivity (2-6). The basic fraction contains over 50% of the mutagenicity, as measured by the Ames assay, with only 4 % of the mass. The neutral fraction contains the remaining mutagenicity and possesses about 60% of the mass (2). Second, little is known about the environmental mobility of the specific chemical species in the basic and neutral fractions. Third, because prior
Table 111. Effect of Water and Aqueous Fea+on Components of Basic Fraction of HYGAS Low-Temperature Reactor Tar % decrease in concn after contact with
retention time, mina 29.5 30.3 32.4 33.8 33.9 34.1 34.7 37.6 38.2 38.6 39.1 39.4 39.8 42.6 44.9 45.1 46.1 47.7 48.7 49.6 51.3 53.3 53.6 54.1 54.6 55.3 55.8 56.6 57.5 57.9 58.1 59.7 60.8 62.2 62.4 63.0 65.9 67.0 67.3 68.1 68.6 70.7 71.7 72.3 73.1 75.6 84.1 85.9
compound Cz-pyridine Cz-pyridine C3-pyridine C3-pyridine C3-pyridine C3-pyridine C3-pyridine C4-pyridine C4-pyridine C4-pyridine methylaniline methylaniline methylaniline C4-pyridine (&-aniline (&pyridine C5-pyridine azanaphthalene (quinoline) azanaphthalene (isoquinoline) C3-aniline Cl-azanaphthalene Cl-azanaphthalene C1-azanaphthalene C2-azanaphthalene Cz-azanaphthalene Cz-azanaphthalene Cz-azanaphthalene C2-azanaphthalene Cz-azanaphthalene azabiphenyl Cz-azanaphthalene C3-azanaphthalene C3-azanaphthalene and methylazabiphenyl 1-naphthylamine Cz-azabiphenyl 2-naphthylamine azafluorene C1-naphthylamine C1-naphthylamine C1-naphthylamine C3-azabiphenyl %ringb aza 3-ring aza 3-ring aza 3-ring aza methyl-3-ring aza azapyrene 3-ring amino
orig concn, mg/g 22.4 4.6 3.5 17.6 5.8 8.3 3.4 3.5 5.8 3.9 14.8 19.6 46.3 6.8 19.8 9.1 3.4 120.4 29.6 3.5 44.6 17.6 31.6 3.5 6.0 5.9 21.6 5.9 22.5 18.9 16.1 12.5 15.2
pure HzO
20 ppm of Fe3+ for 4 h
200 ppm of Fe3+ for 18 h
1 1 1 2 0
88 100 55 96 81
0 0 6 5 2 2 2 7 1 3 6 1 2 0 1 1 4 0 4 0 1 0 0 2 2 4 6
91 74 86 80 27 13 14 71 7 7
100 100 100 100 100 100 100 100 100 100 78 91 84 78 60 63 79 70 87 55 87 55 50 80 60 57 89 80 85 80 40 58 33
8.5 4.0 43.6 11.0 10.3
7 5 0
10 11 0
0
6
12.2
14.4 4.4 5.6 15.6 26.8 28.9 9.6 5.9 5.6
1 4 6
18 6 1 0 3 5 0 20 3 8 5 4 5 7
12 0
10 0
6 19 35 2 0 0
5 10 2
65 72 25 25 25 20 30 20 3 25 5 30 10 20
‘Temperature program: 12-min hold at 20 “C, 3 ‘C/min up to maximum of 270 O C . This program differs from that used in the analysis summarized in Table IV. The term “3-ring” refers to phenanthrene or anthracene.
studies on model solutions were performed with basic and neutral compounds ( I ) , a comparison with this prior work is possible. Figure 1is a partial chromatogram obtained before and after exposure of the basic fraction to the aqueous solution. A marked difference in behavior is evident between comparably sized and substituted pyridines and anilines. The pyridines were almost totally extracted to the aqueous layer, while the anilines were less so. These data suggest that organic mixtures containing basic molecules, after contact with an aqueous solution containing Fe3+,will have a concentration distribution of individual species much different than that which existed before such contact. Table I11 summarizes the results for exposure of the basic compounds dissolved in methylene chloride to a 20-ppm Fe3+solution after 4 h and a 200-ppm Fe3+solution after 18 h. Although none of the constituents of the fraction has an appreciable solubility in water under these
conditions (Table 111,column 4),the concentration of many species was greatly changed in the presence of aqueous Fe3+ (Table 111, columns 5 and 6). An analysis of five samples over time at different Fe3+solution concentrations confirmed that both time of contact and metal ion concentration significantly affect the amounts of organic species transported from the organic phase. In the preceding study ( l )Fe3+ , and quinoline were reported to form a four-ligand complex in the aqueous phase. The transport of the basic materials from the organic to the aqueous phase can occur by protonation and by complex formation ( I ) . However, the rate of extraction by complex formation for model compounds is much slower (1). Since the time of contact is a significant factor in the amount of the basic material transported to the aqueous phase, complex formation by the aqueous iron must be a strong influence in the organic compound transport, and these observations cannot be totally exEnviron. Sci. Technol., Vol. 19, No. 10, 1985
927
ture work will address speciation and the quantitation of these observations for complex mixtures for use in environmental modeling studies. Registry No. Fe3+,20074-52-6;quinoline, 91-22-5; isoquinoline, 119-65-3; 1-naphthylamine, 134-32-7; azabiphenyl, 52642-16-7; methylaniline, 26915-12-8;2-naphthylamine, 91-59-8; azafluorene, 97485-90-0; methylnaphthylamine, 1321-96-6;azapyrene, 8912646-5; benzonitrile, 100-47-0; acetophenone, 98-86-2; dihydronaphthalene, 29828-28-2; naphthalene, 91-20-3;benzothiophene, 11095-43-5; methyltetrahydronaphthalene, 31291-71-1; 2methylnaphthalene, 91-57-6; 1-methylnaphthalene, 90-12-0; biphenyl, 92-52-4; acenaphthene, 83-32-9; methylbiphenyl, 2865272-4; methylacenaphthene, 36541-21-6.
PURE
BASE
Literature Cited
30
40
50
MINUTES
Figure 1. Section of gas chromatograph for base fraction, before and after contact with aqueous 20-ppm Fe3+solution for 2 days. Only the early peaks are displayed. See Table 111 for identification and quantitation.
Table IV. Neutral Fraction Compounds Not Extracted by Aqueous Fe3+ benzonitrile acetophenone dihydronaphthalene naphthalene benzothiophene C2-indan (four isomers) C2-indene C1-tetrahydronaphthalene 2-methylnaphthalene C1-benzothiophene
1-methylnaphthalene biphenyl C2-naphthalene (five isomers) acenaphthalene C1-biphenyl C,-benzothlophene C6-indan (&naphthalene (four isomers) C1-acenaphthene
plained by the low pH of the aqueous phase. An examination of the variation of results for the basic fraction as a function of elution time showed that the order of elution relates approximately to size and polarity of the chemical. Also, as the elution time increases,the transport from the organic to the water layer generally becomes smaller. This trend, observed in prior experiments (1,16) appears to offer some potential for developing a general relationship for estimating chemical partitioning in complex mixtures. To study the effect of Fe3+ ions on the components of the neutral fraction, several experiments parallel to those described above were conducted. Aqueous layers included pure water (97 h of contact), an aqueous 20-ppm Fe3+ solution (72 h of contact), and an aqueous 200-ppm Fe3+ solution (93 h of contact). The results showed that virtually no substances in the neutral fraction were affected by the aqueous Fe3+ ions. Table IV lists the chemical species analyzed in each solution. Summary and Conclusions Coal gasification condensates contain acidic, basic, and neutral constituents of environmental importance. Contact with aqueous Fe3+significantly affects the mobility of basic chemicals, especially pyridines. However, neutral components-aromatic hydrocarbons and oxygen- and sulfur-containing aromatic compounds-are essentially unaffected under the experimental conditions studied. This study as well as prior work ( I , 16) indicate that the environmental fate of these materials is related to several factors, including the pH of the solution as well as the specific metal ions present and their concentrations. Fu928
Environ. Sci. Technol., Vol. 19, No. IO, 1985
(1) Jorgensen, A. D.; Stetter, J. R.; Stamoudis, V. C. Environ. Sci. Technol., preceding paper in this issue. (2) Stamoudis, V. C.; Bourne, S.; Haugen, D. A.; Peak, M. J.; Reilly, C. A.; Jr.; Stetter, J. R.; Wilzbach, K. In “Coal Conversion and the Environment: Chemical Biological, and Ecological Considerations”; Mahlum, D. D.; Gray, R. H.; Felix, W. D., Eds.; U.S. Department of Energy: 1981; CONF-80-1039, NTIS (DE82000105), pp 67-95. (3) Haugen, D. A.; Peak, M. J.; Suhrbier, K. M.; Stamoudis, V. C. Anal. Chem. 1982,54,32-37. (4) Haugen, D. A.; Stamoudis, V. C.; Peak, M. J.; Boparai, A. S. Polynucl. Aromat. Hydrocarbons: Int. Symp., 6th 1982, 347-356. (5) Haugen, D. A.; Stamoudis, V. C.; Peak, M. J.; Boparai, A. S. Polynucl. Aromat. Hydrocarbons: Int. Symp., 7th 1983, 607-620. (6) Stamoudis, V. C.; Haugen, D. A.; Peak, M. J.; Wilzbach, K. E. In “Advanced Techniques in Synthetic Fuels Analysis”;Wright, C. W.; Weimer, W. C.; Felix, W. D., Eds.; U S . Department of Energy: 1983, CONF-81-1160 (also available as PNL/SA-11552), NTIS (DE83015528), pp 201-214. (7) “Coal Conversion and the Environment: Chemical, Biological and Ecological Considerations”; Mahlum, D. D.; Gray, R. H.; Felix, W. D., Eds.; U.S. Department of Energy: 1981; CONF-80-1039, NTIS (DE82000105). (8) Tomkins, B. A.; Ho, C. Anal. Chem. 1982, 54, 91-96. (9) Ho, C.; Clark, B. R.; Guerin, M. R. J. Environ. Sci. Health, Part A 1976, A l l (7), 481-489. (10) Hill, J. 0.;Royer, R. E.; Mitchell, C. E. Environ. Res. 1983, 31, 483-492. (11) Hansen, L. D.; Phillips, L. R.; Mangelson, N. F.; Lee, M. L. Fuel 1980,59,323-330. (12) Guerin, M. R.; Rubin, I. B.; Rao, T. K.; Clark, B. R.; Epler, J. L. Fuel 1981,60, 282-288. (13) Ghassemi, M.; Iyer, R.; Scofield, R.; McSorley, J. Environ. Sci. Technol. 1981, 15, 866-873. (14) Benson, f . M.; Mitchell, C. E.; Royer, R. E.; Clark, C. R.; Carpenter, R. L.; Newton, G. J. Arch. Environ. Contam. Toxicol. 1982, 11, 547-551. (15) Jonardi, R. J.; Anastasia, L.; Massey, M.; Karst, R. “Environmental Assessment of the HYGAS Process”; Institute of Gas Technology, Chicago, IL, 1979, U.S.Department of Energy Report FE-2433-25, NTIS. (16) Jorgensen, A. D.; Stetter, J. R. Anal. Chem. 1981, 54, 381-385. (17) Stamoudis, V. C.; Stetter, J. R.; Flotard, R. D.; Boparai, A.; Haugen, D. A.; Peak, M. J.; Reily, C. A., Jr. Proc. Bienn. Synfuel Wastewater Workshop,3rd; compiled by King, C. J.; US.Department of Energy: 1984; DOE/METC/84-5, NTIS (DE84009294), pp 186-194.
Received for review September 27, 1983. Revised manuscript received January 1,1985, Accepted April 17, 1985. This work was supported by the U S . Department of Energy under Contract W-31-109-Eng-38. Work by A.D.J. was performed at Argonne National Laboratory while he was a Faculty Research Participant, under a program administered by the Argonne Division of Educational Programs.
