3N 1Ut> CHEMICAL AND TOXICOLOGICAL PROPERTIES OF COAL FLY ASH John J. Suloway William R. Roy Thomas M. Skelly Donald R. Dickerson Rudolph M. Schuller Robert A. Griffin R L. LANGENHElM, OEPT. GEOL. UNIV. ILLINOIS 254 N.H.B., 1301 W. GREEN ST. URBANA, ILLINOIS 61S01 Illinois Department of Energy and Natural Resources STATE GEOLOGICAL SURVEY DIVISION STATE NATURAL HISTORY SURVEY DIVISION ENVIRONMENTAL GEOLOGY NOTES 105 1983 ACKNOWLEDGMENTS The authors thank Susan D. Kamp and Shirley A. Lowe for their assistance with the toxicity and bioaccumulation studies, Ivan G. Krapac for his assistance with the extract characterizations, R. R. Ruch and the Analytical Chemistry Section for the chemical data, Richard D. Harvey for the x-ray diffraction work, and Richard Larson, Institute for Environmental Studies, University of Illinois, for GC/Mass spectral analyses. Also acknowledged is the cooperation of the Illinois Power Company, Central Illinois Public Service Company, Commonwealth Edison Company, and Lou Cooper of Rockwell International in collecting fly ash samples. This project was partially supported by the Illinois Department of Energy and Natural Resources (DENR) under Contract No. 90.025. The authors greatly appreciate the support of W. Murphy and A. Burkard of DENR. John J. Suloway is now employed by Charles T. Main, Inc., Boston, Massachusetts 02199; Rudolph M. Schuller is employed by S.M.C. Martin, Valley Forge, Pennsylvania 19481. Cover design: William Roy Suloway, John J. Chemical and toxicological properties of coal fly ash /John J. Suloway and others. — Champaign, III. : State Geological Survey Division and State Natural History Survey Division, July 1983. 70 p. ; 28 cm. - (Illinois-Geological Survey. Environmental geology notes ; 105) I. Fly ash— analysis. 2. Fly ash— environmental aspects. I. Title. II. Series. Printed by authority of the State of Illinois/ 1983/2000 CHEMICAL AND TOXICOLOGICAL PROPERTIES OF COAL FLY ASH John J. Suloway Thomas M. Skelly ILLINOIS NATURAL HISTORY SURVEY Paul G. Risser, Chief Natural Resources Building 607 East Peabody Drive Champaign, Illinois 61820 William R. Roy Donald R. Dickerson Rudolph M. Schuller Robert A. Griffin ILLINOIS STATE GEOLOGICAL SURVEY Robert E. Bergstrom, Chief Natural Resources Building 615 East Peabody Drive Champaign, Illinois 61820 ENVIRONMENTAL GEOLOGY NOTES 105 1983 Digitized by the Internet Archive in 2012 with funding from University of Illinois Urbana-Champaign http://archive.org/details/chemicaltoxicolo105sulo INTRODUCTION 1 PURPOSE AND OBJECTIVES 2 SUMMARY OF STUDY FINDINGS 2 RECOMMENDATIONS 4 METHODS AND MATERIALS 5 Sample collection and preparation Analytical methods for inorganic, mineralogical, and physical properties Analytical methods for organic matter characterization Solvent extraction Pyrolysis study Extraction methods Methods for toxicity tests and bioaccumulation experiments PHYSICAL AND INORGANIC CHARACTERIZATION OF THE FLY ASH SAMPLES 12 Particle size and specific gravity Chemical and mineralogical composition Fly ash classifications ORGANIC MATTER CHARACTERIZATION OF SELECTED FLY ASH SAMPLES 18 Solvent extraction Pyrolysis studies CHARACTERIZATION OF THE FLY ASH EXTRACTS 32 U.S. EPA Extraction Procedure (EP) LONG-TERM EQUILIBRATION EXTRACTION 36 TOXICITY TESTS 46 BIOACCUMULATION EXPERIMENTS 52 REFERENCES 62 FIGURES 1. Areal extent of Pennsylvanian strata in which coal resources of the Illinois Basin are found and the approximate location of the parent coals of fly ashes 11 through 19. 7 2. HPLC of a known mixture of phenols and polyaromatic hydrocarbons referenced to toluene. 9 3. The particle size distribution in fly ashes, 12, 16, and 17. 12 4. The 1 2 fly ashes plotted on the Sialic-Ferric-Calcic diagram for classification. 1 7 5. The 12 fly ash samples and 27 other fly ash samples from the literature plotted on the Sialic-Ferric-Calcic diagram for classification. 19 6. Infrared spectrum of the benzene-extractable organic material in fly ash 18. 20 7. Infrared spectrum of the benzene-extractable organic material in fly ash W1. 21 8. Infrared spectrum of the LC-1 fraction from the benzene extract of fly ash W1. 22 9. HPLC chromatogram of the LC-2 fraction from the benzene extract of fly ash W1. 22 10. Infrared spectrum of the LC-3 fraction from the benzene-extractable organic matter in fly ash W1. 23 1 1. Gas chromatogram of the LC-3 fraction from the benzene-extractable organic matter in fly ash W1. 23 12. HPLC chromatogram of the LC-3 fraction from the benzene extract of fly ash W1. 24 13. Infrared spectrum of the LC-4 fraction from the benzene extract of fly ash W1. 24 14. HPLC chromatogram of the LC-4 fraction from the benzene extract of fly ash W1. 25 15. Infrared spectrum of the LC-5 fraction from the benzene extract of fly ash 18. 25 16. HPLC chromatogram of the LC-5 fraction from the benzene extract of fly ash W1. 26 17. Infrared spectrum of the LC-6 fraction from the benzene extract of fly ash W1. 26 18. HPLC chromatogram of the LC-6 fraction from the benzene extract of fly ash W1. 27 19. Gas chromatogram of the noncondensable hydrocarbons produced by pyrolysis at 450° C of fly ash 12. 30 20. Gas chromatogram of the noncondensable hydrocarbons produced by pyrolysis at 450°C of fly ash 13. 30 21. Gas chromatogram of the noncondensable hydrocarbons produced by pyrolysis at 450°C of fly ash W2. 31 22. Gas chromatogram of the noncondensable hydrocarbons produced by pyrolysis at 450°C of fly ash 15. 31 23. Gas chromatogram of the condensable organics produced by pyrolysis at 300° C of fly ash W1. 32 24. Changes in the concentrations of selected aqueous constituents in the LTE extract of fly ash 13 with time. 42 25. Changes in the concentrations of selected aqueous constituents in the LTE extract of fly ash 17 with time. 42 26. Changes in the concentrations of selected aqueous constituents in the LTE extract of fly ash W2 with time. 43 TABLES 1. Summary of the origin and general characteristics of the 12 fly ash samples. 6 2. Particle size data for the 12 fly ashes by pipet analysis and specific gravity. 13 3. Mineralogical composition of the 12 fly ash samples. 14 4. Chemical composition of the 12 fly ashes: major and minor constituents. 14 5. Sulfur species in the 12 fly ashes. 15 6. Trace constituent concentrations in the 12 fly ashes. 16 7. Fly ash sample classifications. 18 8. Carbon, sulfur, and benzene-extractable organic matter of selected fly ashes. 20 9. Liquid chromatographic fractionation of the benzene extracts of four fly ashes. 21 10. Hydrocarbons detected in the noncondensable pyrolysates. 28 1 1. Organic components detected in the condensable pyrolysates of the fly ashes. 29 12. Chemical constituent concentrations obtained by the proposed U.S. EPA Extraction Procedure (EP) performed on the 12 fly ashes. 34 13. Contaminant concentrations in EP extracts qualifying for hazardous waste classification. 35 14. Change in chemical composition as a function of time of fly ash 12 extract generated by long-term (142 days) equilibration. 37 15. Change in chemical composition as a function of time of fly ash 13 extract generated by long-term (141 days) equilibration. 38 16. Change in chemical composition as a function of time of fly ash 17 extract generated by long-term (106 days) equilibration. 39 17. Change in chemical composition as a function of time of fly ash 18 extract generated by long-term (140 days) equilibration. 40 18. Change in chemical composition as a function of time of fly ash W2 extract generated by long-term (140 days) equilibration. 41 19. Constituents in the long-term equilibrations exceeding EPA interim primary and secondary drinking water standards or irrigation water criteria as a function of time. 45 20. The percent mortality of a 1 -to-6-day old fathead minnow fry (Pimephales promelas) resulting from 96-hour exposures to full -strength extracts generated from five fly ashes. 46 21. The LC-50 values, amount of dilution necessary to eliminate mortality, and the initial pH values for extracts generated from five fly ashes. 47 22. The range of concentrations and recommended water quality levels for chemical constituents measured in test solutions of W2. 48 23. The range of concentrations and recommended water quality levels for chemical constituents measured in test solutions of 13. 49 24. The range of concentrations and recommended water quality levels for chemical constituents measured in test solutions of 17. 50 25. The range of concentrations and recommended water quality levels for chemical constituents measured in test solutions of 12. 51 26. The mean initial lengths and weights of adult fathead minnows used in the bioaccumulation experiments. 52 27. The mean initial lengths and weights of juvenile green sunfish used in the bioaccumulation experiments. 53 28. Initial mean total lengths and weights of adult fathead minnows exposed to extracts from five fly ashes and a control. 53 29. Initial mean total lengths and weights of juvenile green sunfish exposed to extracts from five fly ashes and a control. 54 30. Comparison of the mean initial lengths and weights between the control test organisms and the organisms exposed to fly ash extracts. 54 31. The mean final lengths and weights of juvenile green sunfish used in the bioaccumulation experiments. 54 32. The mean final lengths and weights of adult fathead minnows used in the bioaccumulation experiments. 55 33. Final mean total lengths and weights of adult fathead minnows exposed to extracts from five fly ashes and a control. 55 34. Final mean total lengths and weights of juvenile green sunfish exposed to extracts from five fly ashes and a control. 55 35. Comparison of the mean final lengths and weights between the control test organisms and the organisms exposed to fly ash extracts. 56 36. Differences between initial and final mean lengths and weights of adult fathead minnows exposed to extracts from five fly ashes and a control. 56 37. Differences between initial and final mean lengths and weights of juvenile green sunfish exposed to extracts from five fly ashes and a control. 56 38. The mean concentrations of various chemical constituents measured in adult fathead minnows exposed to extracts from five fly ashes and a control. 58 39. The mean concentrations of various chemical constituents measured in juvenile green sunfish exposed to extracts from five fly ashes and a control. 59 INTRODUCTION During the late 1970s shortages of natural gas, fuel oil, and gasoline dramatically demonstrated the need for the increased use of coal by electric utilities. Although predictions vary, the National Coal Association forecasts an increase in coal usage from 787 million metric tons in 1976 to approximately 1.5 billion metric tons by 1985. The combustion of coal produces solid wastes composed primarily of the noncombustible mineral matter (ash) present in the coal. Fly ash is that portion of ash that is small enough, in terms of particle size, to be entrained in the flue gases and carried away from the site of combustion. Of the 67.8 million tons of ash produced in the U.S. in 1977, approximately 48 million tons was fly ash (Faber, 1979). Ash production may reach 125 million tons by 1990 and may increase by a factor of four in the next 20 years (Faber, 1979). In Illinois, the three major electric utilities generated an estimated 1,867,000 tons of fly ash in 1979 (Roy et al., 1981). The implications of the Resource Conservation and Recovery Act (RCRA) of 1976 have focused attention on coal fly ash and its subsequent disposal problems. The prevalent method of fly ash disposal is by sluicing the ash slurries from the power plants into some type of natural or man-made basin where the ash settles. The resulting supernatant may contain potentially toxic trace constituents, leached from the fly ash, which could pose problems to the aquatic ecosystems into which they eventually flow. Several studies assessing the environmental impact of coal fly ash have dealt largely with fly ashes generated from coals from the Appalachian region (Chu et al., 1978; Furr et al., 1977; Klein et al., 1975; Plank et al., 1975) and from western bituminous, subbituminous, and lignite coals (Elseewi et al., 1980; Mann et al., 1978; Ondov et al., 1979; Swanson et al., 1976). Fly ashes produced by the combustion of coals from the Illinois coal basin have also been studied (Cox et al., 1978; Davison et al . , 1974; Griffin et al., 1980; Linton et al . , 1976; Natusch et al . , 1977; Theis and Wirth, 1977). However, as indicated in literature reviews by Adriano et al. (1980), Page et al. (1979), and Roy et al. (1981), the physicochemical properties of fly ash may vary from plant to plant and even from different boilers within a particular plant. Moreover, laboratory leaching and disposal pond studies of the aqueous chemical interactions with fly ashes generated from Illinois Basin coals have also produced varying results. Additional work with Illinois fly ashes is needed in order to assess the possible environmental impacts of coal fly ash disposal. Elevated pH levels of fly ash leachates have been shown to be toxic to aquatic organisms (Cairns et al . , 1972; Wasserman et al . , 1974). Other studies (Birge, 1978; Thompson, 1963) have examined the role of trace elements in the aquatic toxicology of leachates from coal and fly ash. Trace elements leached from fly ash can accumulate in the tissues of fish and fish forage (Cherry et al., 1976; Ryther et al., 1979). Contaminated fish from cooling lakes or other aquatic ecosystems exposed to fly ash effluent may pose potential health hazards to fishermen. PURPOSE AND OBJECTIVES The overall purpose of this investigation was to provide information that may be of assistance in predicting the environmental impacts of coal fly ash disposal. Data resulting from this investigation should be useful to utilities, consultants, and state, local, and federal agencies concerned with fly ash and its disposal. The objectives of the study were to: • Review the ecological and health literature concerning fly ash. • Assess the variability in terms of chemical composition and aqueous solubility of fly ashes derived from Illinois Basin coals, and compare these fly ashes to those generated from western U.S. coals. • Determine if the extracts generated from fly ash were acutely toxic to fishes. • Determine if the soluble trace metals in the fly ash extracts were accumulated by fishes under laboratory conditions. SUMMARY OF STUDY FINDINGS 1. Nine fly ash samples generated from Illinois Basin coals-- predominantly silts (USDA classif ication)--varied in color from very dark grayish brown (10YR Munsell soil colors) to gray (2.5Y - 5Y) . The average specific gravity of the nine samples was about 2.4. Two fly ashes generated by the combustion of western U.S. lignite coals were lighter in color (light gray) and had greater specific gravities (about 3.05), whereas a western subbituminous coal fly ash had a darker gray (10YR) color and a specific gravity of 2.2. 2. The general mineralogical composition of the Illinois Basin fly ashes was comparable to that of fly ashes generated from eastern U.S. bituminous coals, as reported elsewhere. They were essentially spherical particles composed of an amorphous alumino-si 1 icate glass, quartz, mullite (Al 5Si 2^13) » an d iron oxides. The subbituminous western ash was similar in mineralogical composition to the Illinois samples, except for the presence of calcite in the western ash. The two western lignite samples had higher concentrations of some alkaline metals and matrix sulfur, primarily in the form of anhydrite (CaS04) and periclase (MgO). 3. Most of the matrix sulfur in all 12 samples existed as sulfate compounds. The average ratio of sulfate S to sulfide S in the Illinois samples was about 5:1 . 4. The trace constituent concentrations in the samples were highly variable, but the Illinois fly ash samples generally had greater concentrations of (in decreasing order of concentration) Zn, Ni , Rb, Cs, Cr, Co, U, Ge, Mo, V, Li, Cd, Tl , Sm, Pb, Be, Eu, Tb, Ga, Ce, As, Cu, Lu, and Sc than did the three western fly ashes. Similar trends for certain transitional metals have been reported elsewhere for ashes from eastern and western coals. 5. Under laboratory conditions, the seven gray samples produced alkaline extracts, whereas the two reddish fly ashes generated acidic extracts. Color may be useful in predicting the initial pH of a fly ash slurry or leachate in the field. 6. The ratio of matrix CaO to SO3 may influence the pH of extracts during the initial stages. Short-term acidic extracts were associated with samples having a Ca0/S03 ratio of less than 2; alkaline solutions were produced from samples having matrix Ca0/S03 ratios exceeding 2. 7. The general trend of EP solubility for the Illinois Basin fly ashes was found to be SO4-S > Ca, B > Cd > Sb, Mn, Mg > Zn > Na, Mo > K, Ni, Cr, Cu > Be, Ba, Si, Al , Fe. The general pattern of solubility for the subbituminous fly ash was SO4-S > B > As > Ca > Se > Mg, Zn > Mn > Na > K, Ba, and for the two lignite fly ashes, SO4-S > B > K, Mo >> Se, Na > Ca > Zn, Mg > Be, Cr > Mn, Si, Ba. 8. Although all fly ashes are currently exempt from the list of hazardous wastes under RCRA, EP data indicated that one of the 12 samples would be classified as a hazardous waste by present criteria. One acidic fly ash contained enough soluble Cd to classify it as a hazardous waste if the status of fly ash as a nonhazardous waste were to be revised. 9. In long-term equilibrations (100-140 days) of five fly ash samples, the concentrations of several potential pollutants began to decrease almost immediately after the first day of extraction, and this decrease continued for 60 to 120 days until steady state conditions developed. The pH of the acidic extracts became neutral after about 3 to 5 weeks and consequently several potential pollutants were less soluble in the resulting nonacidic solution. In all five long-term equilibrations, several constituents reached a metastable equilibrium, persisting at invariant concentrations for the latter part of the extraction interval . 10. The specific concentrations of some of the inorganic constituents in the solutions (prior to equilibration and after steady state conditions developed) exceeded the EPA interim primary or secondary drinking water standards and irrigation water criteria. 11. Organic compounds identified in the fly ashes were only slightly soluble in the aqueous extracts. Although some of the organics present in the samples are on the priority pollutant list, they are present in such low concentrations that it is doubtful that they would pose any significant environmental problems during landfilling operations or ponding. 12. Fly ashes--particularly acidic types--are probably most toxic to aquatic ecosystems when initially slurried to disposal ponds; their toxicity may decrease with time. If the potential contaminants achieve steady state conditions in the disposal pond, they may have long residence times in the ash effluent, thus increasing the probability of bioaccumulation by aquatic organisms. 13. Of the 12 fly ash samples evaluated, five were selected for toxicity testing on the basis of the diversity of extract pH values observed. All five extracts were acutely toxic to fathead minnow fry. 14. Physicochemical components probably responsible for the acute toxicity of the fly ash extracts to fish were pH, Al , ionic strength, and Zn. Because of the complex composition of some extracts and the unknown synergistic and antagonistic effects of the chemical constituents of the extracts, it was not possible from these experiments to determine which chemical constituents specifically were responsible for the observed mortality. 15. The fly ash extracts were diluted to levels presumed subacutely toxic for use in bioaccumulation experiments. The growth of fathead minnows and green sunfish exposed to these diluted fly ash extracts was not significantly different from that of control test organisms exposed to filtered tap water under similar conditions. 16. The fathead minnows and green sunfish accumulated similar elements from the fly ash extracts; the six chemical constituents most commonly accumulated from fly ash extracts were Al, B, Cd, Mn, Mo, and Ni . Of these six chemical constituents, Cd appeared to be of greatest importance because of its highly toxic nature. RECOMMENDATIONS 1. An apparent relationship was observed between the initial pH character of a fly ash leachate and its color and the matrix Ca0/S03 ratio in the solid waste. Further study of the less commonly produced acidic high-iron fly ashes should be done. 2. The long-term equilibration (LTE) extraction procedure was designed to simulate equilibrated ash ponds. Although obtaining representative pond samples is difficult, such field work should be done to assess the accuracy of the LTE procedure. 3. Fly ash laboratory extracts often undergo complex changes in chemistry with time and should be studied to determine which mineral phases control the aqueous solubility of the components. The chemistry of slurry water and disposal ponds should also be studied and modeled to determine whether the same types of changes that occur in laboratory extracts occur in the field. 4. Grab samples were collected from only nine power plants, seven of which were in Illinois. To provide a more complete picture of fly ash composition and variability, samples from other Illinois power plants and from other states should be studied. 5. The scope of the ecological analyses of fly ash in this study consisted of acute static bioassays using fathead minnow fry and bioaccumulation experiments using fathead minnows and green sunfish. It is appropriate to expand the scope of ecological analysis to a multi-tier approach (Brown and Suloway, 1982; Lee et al., 1979) including bioaccumulation, bioconcentration, and biomagnif ication experiments. Several species of test organisms representing different trophic levels should be used in chronic or subchronic bioassays. A battery of health effects tests should be conducted to evaluate each fly ash and its extracts. The U.S. EPA has recommended (for a level 1 assessment) that solid wastes be tested for the presence of microbial mutagenicity, rodent acute toxicity, and cytotoxicity. The specific tests include the Ames Test, the Rabbit Alveolar Macrophage (RAM) assay, the Human Lung Fibroblast (WI-38) Assays, and acute toxicity bioassays with rats. With these tests it is possible to screen wastes, including fly ashes and their extracts, for possible carcinogenicity, cytotoxicity, and other detrimental health effects. METHODS AND MATERIALS Sample collection and preparation A summary of the origin and general characteristics of grab samples of 12 fly ashes collected for this study is given in Table 1. All of the samples were collected from the hoppers below the electrostatic precipitators at nine individual power plants. Two samples, each derived from different boilers, were collected at each of three of the facilities. Nine of the fly ash samples, identified as II through 19, were generated by the combustion of Illinois Basin coals (predominantly the Herrin No. 6 coal seam) in Illinois and Indiana. One fly ash (Wl) was produced by a power plant in Illinois using a low-sulfur subbituminous coal from Colorado (Fishcreek Seam), and the remaining two fly ashes (W2 and W3) were from plants outside Illinois using lignite from western North Dakota. Figure 1 shows the areal extent of the Illinois Basin and the approximate location of the parent coals of fly ashes II through 19 (coals from two mines were used to generate fly ash 15). All chemical and solubility studies were done with the bulk samples as taken from precipitator hoppers. The bulk samples were riffled to insure that representative samples were used for each experiment. Analytical methods for inorganic, mineralogical, and physical properties The 12 solid wastes were analyzed both chemically and mineralogical ly. Chemical analyses of the samples for Si, Al , Mg, Ca, K, Fe, Ti , and P were performed by x-ray fluorescence spectrometry. Arsenic, Ba, Br, Ce, Co, Cr, Cs, Eu, Ga, Hf, La, Lu, Ni , Rb, Sb, Sc, Se, Sm, Sr, Ta, Tb, Th, U, W, Yb, and Zn contents were determined by instrumental neutron activation analysis. Mercury determinations were carried out by neutron activation with radiochemical separation. Boron, Cu, Ge, Li, Mo, Pb, Sn, and V concentrations were measured by optical emission spectrochemical procedures. A detailed discussion of sample preparation, detection limits, and procedures for these techniques can be found in Gluskoter et al. (1977). The sulfur determinations were done by ASTM method D-2492, and total carbon determinations were carried out by ISO method 609-1975E. The mineralogy of the samples was determined by x-ray diffraction with a Philips Norelco x-ray diffractometer using CuKa radiation (Russell and Rimmer, 1979). Most of the chemical analyses of the supernatant solutions were determined by inductively coupled argon plasma spectrometry (ICAP) with a Jarrell-Ash Table 1. Summary of the origin and general characteristics of the 12 fly ash samples. Fly ash Color of sample 3 Location of coal source Location of power plant Boiler type 11 grayish brown 2.5Y 6/2 11 linois 11 1 inoi s b cyclone 12 very dark grayish brown 10YR 3/2 11 lino is 11 1 inoi s b pulverized 13 gray 5Y 5/1 Indiana 111 inoi s c pulverized 14 gray 5Y 5/1 Indiana 11 1 i noi s c pulverized 15 grayish brown 2.5Y 5.5/2 11 linois 11 linois pulverized 16 gray 2.5Y 5/0 11 linois 11 linois pulverized 17 very dark grayish brown 10YR 3/2 11 linois 11 linois cyclone 18 gray 2.5Y 5/0 11 linois 11 1 inoi s^ pulverized 19 gray 2.5Y 5/0 11 linois 11 1 inoi s^ pulverized Wl gray 10YR 6/1 Colorado 11 linois pulverized W2 light gray 2.5Y 7/2 N. Dakota Minnesota pulverized W3 gray - 1 ight gray 2.5Y 6.5/2 N. Dakota N. Dakota cyclone a Dry Munsell soil colors b » c » d Samples indicated were taken from same individual power plant but were derived from different boilers. ISGS 1963 Figure 1. Areal extent of Pennsylvanian strata in which coal resources of the Illinois Basin are found and the approxi- mate location of the parent coals of fly ashes 11 through 19. Model 975 Plasma AtomComp. The constituents determined by ICAP were Al , As, B, Ba, Be, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Ni , Pb, Sb, Se, Si, Sn, V, and Zn. The procedures and techniques of this specific instrument are discussed in a Fisher Scientific Company publication by the Jarrell-Ash Division (1978). Sulfate content was measured turbidimetrically (Standard Methods, 1975). Alkalinity was determined by titrations with dilute sulfuric acid, and oxidation-reduction potential (Eh), pH, and electrical conductance were measured by electrodes (U.S. EPA, 1974). Most of the samples were characterized in terms of particle size distribution by pipet and wet sieving methods (Soil Conservation Service, 1972). Specific gravity determinations were made by ASTM method CI 28. Analytical methods for organic matter characterization Solvent extraction. The organic material in the solid fly ash samples was extracted with benzene, using a large (70-mm x 300-mm body) Soxhlet apparatus. The sample size per Soxhlet varied from 350 to 500 g of fly ash, The volume of benzene used was 1 L and the extraction time was 24 hours. After extraction, the solvent volume was reduced on a rotary evaporator. Elemental sulfur, found to be co-extracted with the organics, was removed by passing the extract through a column of activated copper according to a method described by Blumer (1957). After removal of the sulfur, the final traces of solvent were removed with gentle heat (50°C) under a stream of dry nitrogen. The benzene-extractable materials, determined gravimetrical ly, were denoted as "total extractable organics." The extracts were separated into seven fractions according to the U.S. EPA Level 1 (Revised) Procedure for Organic Analysis (U.S. EPA, 1978). This separation was done by liquid chromatography (LC) on a silica gel column using a gradual gradient of solvents from nonpolar to polar. An infrared spectrum was run on each extract and on each LC fraction. Gas chromatography (GC), high pressure liquid chromatography (HPLC), and gas chromatography-mass spectroscopy (GC-MS) were used to further characterize the organic fractions. Pyrolysis study. A 5- to 10-gram sample of fly ash was placed in the bottom of a 300-mm x 13-mm-ID Pyrex tube, and a wad of organic-free quartz wool was positioned just above the fly ash to act as a retainer. The diameter of the tube was then constricted by heating with an oxygen-natural gas torch just above the quartz wool retainer. The top of the tube was then sealed with a skirted-septum stopper and the tube was evacuated for several minutes, using a vacuum pump linked to the tube via a hypodermic needle through the septum. Following the evacuation, the sample end of the tube was heated in a horizontal position at 450°C in a tube furnace while the upper end of the tube was cooled with powdered dry ice. After a 5-minute heating period the tube was immediately sealed and separated at the point of the constriction by melting the glass with an oxygen-natural gas torch. Thus, the volatile organics were condensed and trapped in the upper, cooled portion of the tube. The headspace gas (noncondensable at room temperature) was analyzed by GC, and the components were identified by comparison of retention times with known standards. The condensable portion was taken up in isooctane and analyzed by GC; one sample (derived from fly ash Wl ) was also analyzed by GC-MS. The major components in the samples were determined by comparison with the GC-MS analysis and with the retention times of reference standards. The infrared spectra were obtained with a Perkin-Elrner Model 283B Infrared Spectrophotometer. The samples were mounted as neat smears or thin films between sodium chloride prisms. Normally the spectra were obtained by using a 12-minute scan time with response setting 1 and slit program 6. Interpretation of the spectra was made with the help of the following references: Barnes et al. (1944), Bellamy (1958), Nakanishi (1962), Silverstein and Bassler (1963), and Szymanski (1967). A rough indication of the absorption intensities in the IR spectra obtained from the fly ash samples is reported in the Results Section; the absorption intensities are given as "strong," "medium," and "weak". "Strong" is defined as the strongest absorption in a given spectrum. "Medium" and "weak" designations relative to the strongest absorption within the same spectrum are then determined. A Perkin-Elmer Sigma 1 gas chromatographic system with a flame ionization detector was used for GC analysis. A 2-m x 3-mm stainless steel column packed with Chromosorb 102 was used for the noncondensable gas analyses. The carrier gas (helium) flow rate was 30 mL/min, the injection port temperature was 125°C, and the detector temperature was 200°C. The column oven temperature was programmed for an initial hold of 50°C for 1 minute, a temperature rise to 170°C at 10°/min, and a final hold at 170°C for 5 minutes. A 1.25-m X 3-mm stainless steel column packed with 3% SP-2100 on 100/120 mesh Supelcoport (Supelco Inc., Bellefonte, PA) was used for the analysis of the condensables from the pyrolysis study and for the extracts and subfractions of the extracts. The carrier gas (helium) flow rate was 35 mL/min, injection port temperature was 250°C, and the detector (FID) temperature was 315°C. The column oven temperature was programmed for an initial hold at 100°C for 2 minutes, a temperature rise rate of 4°/min to 260°C, with a final hold of 10 minutes. The latter column and conditions were also used for the Level 1 LC fractions. A Perkin-Elmer Series 3 Liquid Chromatograph with UV detection was used for HPLC determinations. An Altex Ultrasphere® 0DS, 5-um sphere size, 4.6 x 250-mm (Beckman Instruments, Inc., Berkeley, CA) HPLC column was used. A 5-cm guard column with LC-18 pellicular packing (Supelco, Inc., Bellefonte, PA) was placed between the sampling valve and the top of the analytical column. The elution solvent was methanol :water (80:20, v:v) with a 1 -mL/min flow rate under isocratic conditions. The order of elution under these parameters was shown to be phenols followed by toluene and then aromatic and polyaromatic hydrocarbons (PAHs) with ascending molecular weights (Fig. 2). Toluene was used as an internal reference standard. ISGS 1983 Figure 2. HPLC of a known mixture of phenols and polyaromatic hydrocarbons referenced to toluene. Peak identification: 1. phenol; 2. p-cresol;3. 2,3-dimethylphenol; 4. 2,4,5- trimethy phenol; 5. toluene; 6. phenan- threne; 7. pyrene; 8. chrysene; 9. benzo (a) pyrene. The GC-MS analyses were performed by the Institute for Environmental Studies at the University of Illinois, Urbana, using a Hewlett-Packard 5985A GC/MS/data system equipped with a capillary column coated with SP-2100. Extraction methods The proposed U.S. EPA Extraction Procedure (EP) (U.S. EPA, 1980) was used to study the solubility of the 12 fly ashes. The EP was intended to serve as a quick test for identifying wastes capable of posing potential pollution hazards when improperly disposed. The EP method calls for mixing 200 g of a solid waste with 3200 mL of deionized water and agitating the mixture by a shaking motion for 24 hours. During the 24-hour solubilization interval, the resulting mixture was acidified to a pH of 5.0 (+ 0.2) by periodic additions of 0.5N acetic acid if the pH of the aqueous phase was greater than 5. If the pH of the aqueous phase was less than 5, no additions of any kind were made. After the extraction interval, the solid and liquid phases were separated by filtration, and the filtrate was diluted to 4,000 mL with deionized water. In this study, the mixtures were filtered through a 0.45-ym-pore-size Millipore® filter membrane, and the filtrates (extracts) were acidified to a pH <1.5 with nitric acid (HNO3) prior to ICAP analysis. A long-term equilibration procedure was also used to assess the solubility of chemical constituents contained in some of the fly ash samples. This procedure involved mixing 3,400 g of fly ash with 17 liters of deionized water in a 19-liter reaction vessel made of Pyrex glass (the large volume was necessary for the bioassays and bioaccumulation studies). These mixtures were stirred for 30 minutes three times a week in order to (as a first approximation) simulate ash ponding environments according to a procedure designed by Griffin et al. (1980). However, this extraction procedure was more specifically oriented toward generating a solution at chemical equilibrium with the solid wastes. This procedure was used to produce a solution that might approximate the aqueous chemistry of pond effluent in settings where metastable chemical equilibrium conditions develop. Methods for toxicity tests and bioaccumulation experiments Using procedures outlined by the U.S. EPA (1975), 96-hour static bioassays of extracts generated from fly ash samples were conducted with l-to-6-day-old fathead minnow fry {Pimephales pvomelas) - The acute toxicity testing was divided into two phases: (1) the screening procedure and (2) the LC-50 determination. During the screening procedure the test organisms were exposed to the undiluted extracts; in the LC-50 determinations the organisms were exposed to "full-strength" extract diluted with filtered tap water. The LC-50 is the concentration of extract at which 50% mortality occurs during a bioassay. Ten 1- to 6-day-old fathead minnows were placed in 250-mL glass beakers containing 200 mL of undiluted or diluted extract. Each bioassay was replicated once. 10 The acute bioassays were conducted at a constant temperature (21° + 1°C) and photoperiod (16L-8D) in an environmental chamber. Test organisms were not fed, and the solutions were not aerated during the bioassay. During all bioassays, pH, dissolved oxygen, and temperature were monitored. Mortality data were collected at 24, 48, 72, and 96 hours after the bioassays had begun. Diluted and undiluted extracts were sampled at the conclusion of the bioassays for chemical analyses. The acute toxicity of the five undiluted LTE extracts was determined with the screening procedure. The LC-50 determinations demonstrated the relative acute toxicities of the solutions and were used to identify the most toxic extracts, to estimate the dilution necessary to eliminate mortality during a 96-hour static bioassay, and to establish extract concentrations for use in the bioaccumulation experiments. LC-50 values were calculated using graphic methods (Litchfield and Wilcoxon, 1949). In the bioaccumulation experiments for each fly ash extract, five adult fathead minnows were put into each of two 60-liter aquaria containing 40 liters of diluted extract. Control tanks contained aerated, filtered tap water. The five fish from each aquarium jointly constituted a single replicate for tissue analysis. This procedure was repeated using juvenile green sunfish {Lepomis oyanellus) . Bioaccumulation experiments were conducted at a constant temperature (23° + 3°C) and photoperiod (16L-8D) in a large environmental chamber. To insure the size similarity of test organisms used in each bioaccumulation experiment, each fish was weighed and measured before the test. At the conclusion of the experiment or at death if premature mortality occurred, the fish were weighed and measured again, frozen, and stored for chemical analysis. Water samples were analyzed weekly to monitor fluctuations in the chemical composition of the diluted leachates. Temperature was monitored daily and dissolved oxygen and pH were monitored twice per week. The fish were fed frozen brine shrimp daily and excess food was removed each day. Tests were conducted for 30 days. One-way analysis of variance (ANOVA) was used to determine if test organisms used in each replicate were significantly different in size. ANOVA was also used to compare final lengths and weights of fish with initial values to determine if the test organisms exposed to the extracts grew at different rates than those of the controls. The two replicate frozen green sunfish and fathead minnow groups for each fly ash extract and control were freeze-dried whole, using a Virtis Unitrap 10-100 Freeze Dryer with a Welch Duo-Seal Model 1402 Vacuum Pump, placed into polystyrene bottles with several glass beads, and homogenized using a Spex 8000-11 Mixer Mill. Polyethylene bottles were used to store the homogenized samples. Total digestion was required to analyze the fish samples for chemical constituents. A 5:1 mixture of HNO3 and redistilled perchloric (HCIO4) acid was added to 1-g subsamples of fish in 150-mL round bottom distillation flasks. Flasks were heated on a Kontes Rotary Kjeldahl Distillation Apparatus until HCIO4 fumes began to form. After cooling, the digested samples were transferred to 50-mL volumetric flasks and diluted to volume 11 with ultrapure water. The final HCIO4 concentration (5%) was within the range compatible with ICAP techniques. Diluted solutions were stored in 60-mL polyethylene bottles and refrigerated until analysis. PHYSICAL AND INORGANIC CHARACTERIZATION OF THE FLY ASH SAMPLES Particle size and specific gravity Results for the particle size determin Most of the samples fell within the si classification), predominantly in the sized component of the ashes (less tha particles) ranged from 83 to about 90 distribution of three of the fly ashes were selected for the illustration as and range of the textural distribution silt loam; 16 and 17 were both loams, ashes (Table 2) ranged from 2.2 to 3.1 averaged about 2.4. Comparable measur (EPRI, 1979). ations are presented in Table 2. It category (USDA soil 8- to 31-micron range. The silt- n 62-micron- to 2-micron-diameter percent (Table 2). The particle size is shown in Figure 3; these samples best demonstrating the variability s of the samples. Fly ash 12 was a The specific gravity of the fly g/cm3; the Illinois Basin samples ements have been reported elsewhere Chemical and mineralogical composition Chemical and mineralogical analyses of the fly ash samples indicated that the ashes generated from Illinois Basin coals (samples 11-19) consisted 30 25- 20- I 15- 10- l 1 1 1 1 >62 62-31 31-16 16-8 8-4 Diameter (/im) — T - 4-2 2-1 1-0.5 <0.5 ISGS 1961 Figure 3. The particle size distribution in fly ashes 12, 16, and 17. 12 essentially of Si, Al , and Fe as amorphous alumino-silicate glass, quartz (Si02), mullite ( Al 6Si 2^13) > and various iron oxide species such as magnetite ^304) and hematite (Fe203) (Table 3). Comparable results were reported by Natusch et al. (1977) and Griffin et al. (1980) for other Illinois Basin fly ashes. A small amount of lime (CaO) was also detected by x-ray diffractometry in four of the Illinois Basin samples. Silicon, reported as percent silica (Si02), ranged from about 43 to 52% (Table 4). Aluminum and Fe, reported in their oxide forms, represented approximately 20% of the material. The reddish-brown colors (10YR, dry Munsell soil colors) associated with 12 and 17 were probably due to the Fe levels, about 2 to 3% greater than the average levels of the seven other Illinois Basin fly ashes lacking the reddish-brown hues and having 2.5Y-5Y colors. The Ca, Mg, Na, Ti , K, and S together (as oxides) constituted about 10% of the samples. Other minor constituents (less than 0.01%) were Ba, Sr, P, and Mn. The total S content of the Illinois Basin samples ranged from 0.32 to 1.06% (Table 5). Most of the total S (62 - 92%) was present as sulfate compounds. The remaining S (8 - 38%) was in sulfide forms. The average ratio of sulfate-S to sulfide-S in the Illinois Basin samples was about 5:1. In contrast to the Illinois Basin fly ashes, the two lignite-base samples (W2 and W3) consisted of about 30% S i 2 , 25% CaO, and 8% MgO. The mineralogical composition of these samples was predominantly periclase (MgO), quartz (Si02), and anhydrite (CaSO/}). The lignite-base fly Table 2. Particle size data for the 12 fly ashes by pipet analysis (percent weight) and specific gravity. Particle size (y) Specific gravity Fly ash >62 31-62 16-31 8-16 4-8 2-4 1-2 0.5-1 <0.5 11 11 6 30 23 18 6 4 <1 2 2.4 12 19 23 17 22 11 4 2 <1 2 2.5 13 9 12 25 40 9 3 1 <1 <1 2.4 14 10 8 22 33 16 5 7 <1 <1 2.4 15 4 8 38 43 4 <1 3 <1 3 2.4 16 8 7 13 30 21 9 6 2 4 2.3 17 10 23 27 20 11 3 2 <1 5 .2.6 18 8 15 19 29 16 7 4 <1 3 2.4 19 7 17 21 27 15 9 3 <1 3 2.4 Ml 4 16 29 25 15 6 3 <1 2 2-2 W2 1 (99% <62y) a 3.0 W3 2 (99% <62y) a 3.1 a Sample chemistry incompatible with method, 13 Table 3. Mineralogical composition of the 12 fly ash samples. Fly Ash Mineral 11 12 13 14 15 16 17 18 19 Wl W2 W3 Quartz (Si02> X X X X X X X X X X X X Mullite (Al 6 Si 2°13) X X X X X X X X "Magnet ite-maghemite suite" (Fe304-Fe203) X X X X X X X X X Hematite (FezC^) X X X X X X X X X X Lime (CaO) X X X X X Calcite (CaC03) X Periclase (MgO) X X Anhydrite (CaSC^) X X Unidentified X X Table 4. Chemical composition of the 12 fly ashes: major and minor constituents (percent weight). Chemical constituent 11 12 13 14 15 Fly 16 ash 17 18 19 Wl W2 W3 Si0 2 52.07 48.99 48.71 49.42 48.97 48.11 43.39 52.16 50.85 58.06 35.15 22.98 Ti0 2 1.03 1.17 1.08 1.10 1.17 0.98 1.05 1.07 1.05 0.82 0.63 0.45 A1 2 3 18.93 18.44 22.79 21.92 22.43 18.95 17.16 19.99 19.37 24.34 11.28 13.32 Fe 2 3 17.06 17.86 16.14 16.37 17.40 16.01 18.49 14.23 14.18 3.29 4.66 7.56 CaO 5.25 3.30 2.52 2.35 2.94 5.11 4.13 4.37 4.10 7.21 23.66 25.38 MgO 0.41 0.20 0.40 0.61 0.60 0.56 0.51 0.75 0.35 1.14 7.91 7.50 MnO 0.04 0.08 0.03 0.05 0.05 0.04 0.05 0.02 0.03 0.02 0.08 0.03 Na 2 0.63 1.35 0.16 0.22 0.59 0.30 1.75 0.31 0.31 0.30 5.53 9.57 K 2 3.24 3.58 3.85 3.84 3.82 3.49 4.13 3.85 3.82 1.64 1.09 0.82 P2O5 0.09 0.16 0.27 0.18 0.34 0.07 0.39 0.09 0.09 1.05 0-12 0.23 S0 3 1.32 1.80 0.80 0.92 1.20 1.40 2.65 1.75 1.67 0.47 6.27 7.02 Total C 0.64 5.16 4.54 4.41 1.69 4.71 8.18 4.76 4.57 2.06 0.73 0.40 H 2 0" 0.30 0.31 0.31 0.33 0.27 0.39 0.28 0.38 0.33 0.40 0.20 0.20 14 Table 5. Sulfur species in the 12 fly ashes (percent weight). Fly ash Sulfate S Sulfide S Total S 11 0.43 0.10 0.53 12 0.66 0.06 0.72 13 0.26 0.06 0.32 14 0.23 0.14 0.37 15 0.42 0.06 0.48 16 0.50 0.06 0.56 17 0.97 0.09 1.06 18 0.62 0.08 0.70 19 0.57 0.10 0.67 Wl 0.09 0.10 0.19 W2 2.39 0.12 2.51 W3 2.68 0.13 2.81 ashes were also characterized by greater amounts of Na, Ba, and Sr, while Al and Fe were lower as compared with the amounts in the Illinois Basin samples. These findings are similar to those reported in the coal and fly ash literature, in which higher levels of Ba, Ca, Mg, Na, and Sr have been generally associated with western lignite coals (Abernathy, 1969; Furr et al., 1977; Gluskoter et al., 1977; and Natusch et al., 1977). The specific gravities reported in Table 2 for the Illinois Basin fly ashes are close to the specific gravity of pure quartz (Si02), which is 2.65. The higher specific gravities of the two lignite fly ashes W2 (3.0) and W3 (3.1) were probably due to the low carbon content (Table 4) and the dominant mineral s--periclase (MgO), with a density of 3.58 and anhydrite (CaS04), at about 2.92. The trace constituent concentrations in the fly ashes (Table 6) were extremely variable. Arsenic in the Illinois Basin samples (11-19) ranged from 21 to 360 mg/kg; Co varied from 38 to 88 mg/kg. Zinc was the most variable, ranging from 90 to 2,100 mg/kg. In spite of the variable nature of fly ash, the Illinois Basin samples can be broadly characterized as having greater trace constituent concentrations than the three western samples have. These trace constituents are (in order of decreasing average concentrations in the solid) Zn, Ni , Rb, Cs, Cr, Co, l), Ge, Mo, V, Li, Cd, Tl, Sm, Pb, Be, Eu, Tb, Ga, Ce, As, Cu, Lu, and Sc. Many of these elements have been cited in the literature as generally occurring in greater concentrations in eastern Paleozoic coals and their ashes than in western coals of Mesozoic and Tertiary-age (Abernathy, 1969; Gluskoter et al., 1977; Natusch et al., 1977; and Page et al., 1979). The average concentrations of Hf, Sb, Se, Ta, Th, W, and Yb in the fly ashes were not found to correlate with coal type in this study. 15 Table 6. Trace constituent concentrations (mg/kg) in the 12 fly ashes. Fly ash 17 18 19 Wl W2 Constituent 11 12 13 14 15 16 W3 Ag 0.2 0.5 0.2 0.1 0.4 0.2 1 0.4 0.4 0.1 0.5 0.1 As 21 59 150 200 360 23 60 44 45 8 27 89 B 1700 1600 940 920 1300 1500 870 910 890 800 5000 2300 Ba 580 660 840 900 780 480 2000 730 600 3000 6300 13800 Be 11 14 28 29 15 13 9 11 9 7 4 • 7 Br <5 <5 <5 <5 <5 <5 <5 4 4 <3 <7 <6 Cd 1.3 2.7 2.6 2.3 2.5 <1.0 37.8 5.1 4.7 <1.2 <1.1 <1.1 Ce 130 130 270 210 196 152 120 153 172 187 100 95 Co 38 47 88 82 63 42 41 45 46 11 10 13 Cr 222 284 172 172 172 176 310 232 225 43 45 47 Cs 12 15 13 13 14 13 17 14 14 5 3 2 Cu 79 126 125 115 97 70 189 78 73 47 96 50 Eu 2 3 3 4 3 2 2 2 2 2 <1 2 Ga 36 100 27 45 45 30 74 39 40 35 22 35 Ge 27 51 80 72 41 55 15 17 16 <9 <11 <11 Hf 6 7 7 7 6 6 6 6 6 14 8 7 Hg <0.02 0.06 0.15 0.11 <0.09 0.23 <0.02 0.24 0.22 0.03 0.36 0.10 La 41 84 65 91 95 66 43 64 70 85 30 30 Li 105 82 117 105 324 120 95 110 110 88 no 53 Lu 1 1 2 1 1 1 1 1 1 1 1 1 Mo 56 99 56 44 43 100 70 91 91 14 20 27 Ni 106 153 253 241 174 97 155 121 116 <15 <14 17 Pb 116 145 224 184 450 200 149 249 252 81 104 72 Rb 157 176 200 164 182 164 246 167 167 50 35 24 Sb 3 5 17 14 12 4 10 9 8 2 7 5 Sc 26 24 10 35 7 13 15 27 28 6 12 17 Se 19 24 10 8 7 13 15 12 15 6 19 10 Sm 11 20 14 20 14 13 12 13 13 13 4 5 Sr 430 <60 810 850 1140 390 510 470 420 1900 5500 7600 Ta 2 2 2 2 2 1 2 2 1 2 2 1 Tb 2 2 3 2 2 2 1 2 2 1 1 1 Th 22 26 31 27 25 22 23 25 24 33 24 21 Tl 16 19 11 12 16 11 42 18 19 <5 <7 <7 U 20 43 6 12 7 23 <6 26 31 4 <10 <10 w 2 7 1 2 3 3 <4 4 4 2 <5 <6 V 270 370 330 270 250 380 270 370 360 120 80 93 Yb 5 6 7 7 6 5 6 '6 6 5 4 5 Zn 630 90 720 760 870 340 2100 950 880 60 43 30 Zr 270 312 380 320 290 280 310 280 290 <15 460 350 Fly ash classifications The 12 fly ashes were classified by a system developed by Roy et al. (1981) and Roy and Griffin (1982). This system is based on the chemical composition of the solid waste and the pH of an ashidistilled water mixture (1:1). Seven of the nine Illinois Basin fly ashes were alkaline Modic silts (Fig. 4). Fly ashes fitting into the Modic field have a sialic component (% weight of SiOz + Al 2O3 + Ti02), which indicates that these elements consist of a combination of from >48% to 88% of the total mass. The ferric component (% weight of Fe203 + SO3) is from to 23%, and the Calcic component (CaO + MgO + Na?0 + K2O) is from to 29%. These seven 16 % Calcic Group Figure 4. The 12 fly ashes plotted on the Sialic-Ferric-Calcic diagram for classification. fly ashes produced alkaline leachates with pH values greater than 9.0 and had silt textures. The other two Illinois Basin samples differed in chemical composition: 12 was an acid C-Modic silt loam, and 17 was an acid C,Zn-Fersic silt. These two fly ashes produced acidic extracts. Both fly ashes had total C levels exceeding 5% and 12 was characterized by a high ferric component (Fig. 4) and Zn content (>0.2%). The two lignite-base fly ashes (W2 and W3) plotted more toward the Calcic end member than did the Illinois Basin samples. Fly ash W2 was an alkaline B,Ba,Sr-Calsialic, and W3 was classified as an alkaline B,Ba,Sr-Calcic. The subbituminous fly ash (Wl ) was an alkaline Ba-Modic silt. A summation of the classifications of all 12 fly ashes is given in Table 7. Figure 5 shows the positions of the fly ashes in this study and 27 other fly ashes on the sialic-ferric-calcic compositional field diagram. Twenty-one of the samples were fly ashes generated from eastern U.S. 17 Table 7. Fly ash sample classifications. Sample Type 11 alkaline Modic silt 12 acid C-Modic silt loam 13 alkal ine Modic silt 14 alkaline Modic si It 15 alkaline Modic silt 16 alkaline Modic silt 17 acid C, Zn-Fersic silt 18 alkaline Modic si It 19 alkaline Modic silt Wl alkaline Ba-Modic silt W2 alkaline B, Ba, Sr-Calsial ic a W3 alkaline B, Ba, Sr-Calcic a a Texture was not determined bituminous coals, one from a German bituminous coal and the other 17 samples were derived from subbituminous and lignite coals from the western U.S., India, and Australia. Fly ashes from eastern U.S. bituminous coals tended to fall on the left side of the diagram in the Modic and Fersic fields (Fig. 5): this pattern is reasonable, because the eastern U.S. coals generally have higher concentrations of Fe than do western coals (Gluskoter et al., 1977). Fly ashes from western U.S. lignite and subbituminous coals tended to plot on the right side of the diagram in the Modic, Calsialic, and Calcic fields. Western U.S. coals are generally associated with higher levels of Ca, Mg, and Na than are eastern coals (Abernathy, 1969; Furr et al., 1977; Gluskoter et al., 1977). Near the Sialic-Modic boundary are three fly ashes generated from lignite coals in India. Indian lignite coal is characteristically low in Ca (Chopra et al . , 1979); therefore, these fly ashes did not fit the general pattern for the U.S. ashes. Additional work with high-iron fly ashes is needed to provide a clearer indication of the distribution of Ferries and Fercalcics; few such fly ashes are completely characterized in the literature. However, the magnetic fractions of some Fersics and Modics can be classified as Ferries, as shown in Figure 5. ORGANIC MATTER CHARACTERIZATION OF SELECTED FLY ASH SAMPLES Solvent extraction Five fly ashes were extracted with benzene. An amount of elemental sulfur equivalent to about 10% of the total extractable material in each ash was co-extracted with the organic matter and interfered with the quantification 18 of the total extractable organics. The elemental sulfur was removed by passing the extract through activated copper powder following the first concentration step. The amount of the benzene-extractable organic matter in each fly ash sample is reported as mg/kg of fly ash and as a percent weight of the organic C contained in the sample (Table 8). The C and S values for each fly ash sample are also reported in Table 8. In two western fly ashes (Wl and W2), less than 1% of the total organic C was benzene-extractable; in two other fly ashes (16 and 18), less than 0.1% of the C was extracted into benzene. The unburned and partly burned coal particles in the fly ashes are presumed to be the source of most of the organic C. These coal particles would be only slightly soluble in benzene. • fly ashes from bituminous coals A fly ashes from subbituminous and lignite coals g magnetic fractions of bituminous fly ashes 1. Bobrowski and Pistilli (1979) 2. Chouetal. (1976) 3. Chopra et al. (1979) 4. Cooper (unpub. data) 5. Foster (unpub. data) 6. Griffin et al. (1980) 7. Harvey (unpub. data) 8. Hood (1976) 9. Hurst and Styron (1979) 10. Murtha and Burnet (1979) 11. Roseetal. (1979) 12. Ryanetal. (1976) 13. Santhanam and Ulrich (1979) 14. This investigation 15. Thornton et al. (1976) 16. van derSloot and Nieuwendijk 1981) 17. Wochoketal. (1976) % Calcic Group Figure 5. The 12 fly ash samples and 27 other fly ash samples from the literature plotted on the Sialic-Ferric-Calcic diagram for classification. 19 Table 8. Carbon, sulfur, and benzene-extractable organic matter of selected fly ashes. Total C (%) Inorganic C (%) Organic C (%) Total S (*) Benzene Extractable Fly Ash (mg/kg) Organic C (*) 15 1.69 <0.02 1.69 0.48 38.0 0.22 16 4.71 <0.02 4.71 0.56 17.1 0.04 18 4.76 <0.02 4.76 0.70 37.4 0-08 Wl 2.06 1.33 0.73 0.19 60.6 0.83 W2 0.73 <0.02 0.73 2.51 57.5 0.78 The infrared spectrum (Fig. 6, for example) of the benzene extracts was used for comparison with the infrared spectra of the corresponding LC fractions of the extracts. Absorption peaks due to aliphatic and aromatic structures and from hydroxyl, carbonyl, ether, and nitrogen containing groups were evident in all the extracts. The benzene extracts of four of the fly ashes were separated into seven LC fractions according to the Level 1 procedure. Only 1 1 mg of extract was obtained from fly ash 16; because the LC separation could not be done with this small amount of extract, the analysis of this sample was discontinued. The results from LC fractionation are expressed gravimetrically as milligrams of solvent-free LC fraction per kilogram of fly ash (Table 9). Except for the extract from Wl, the major portions of the organics in the extracts were found in fractions LC-1 and LC-6. The LC fractions of the Wl extract were more evenly distributed on a weight percent basis than were those of the other fly ashes. The IR spectrum indicated that the Wl extract had a somewhat different distribution of compounds (Fig. 7) than did the other fly ashes examined. 4000 3000 2000 1600 200 Wave number (cm ) Figure 6. Infrared spectrum of the benzene-extractable organic material in fly ash 18. 20 Table 9. Liquid chromatographic fractionation of the benzene extracts of four fly ashes. mg LC frac ti on per k 9 fly ash Fly Ash LC-1 LC-2 LC-3 LC-4 LC-5 LC-6 LC-7 15 16.0 0.1 1.3 1.8 2.3 9.3 1.2 18 16.0 0.1 1.8 2.1 1.8 8.7 1.6 Ml 13.0 1.3 8.2 3.9 2.6 6.0 1.9 W2 29.1 1.7 2.3 2.8 2.2 4.7 1.1 The infrared spectra of the LC-1 fractions of all the fly ash samples were very similar and were typical of aliphatic hydrocarbons showing strong -CH3 and -CH2 stretching absorptions, medium -CH2-C(CH3)2, and symmetrical -C-CH3 deformation absorptions (Fig. 8). Gas chromatograms of these fractions contained peaks for all n-paraffins from C]i through approximately C35, and numerous peaks due to much smaller concentrations of branched-chain aliphatics. The infrared spectra of the LC-2 fractions showed that the fractions were highly aliphatic, with yery weak aromatic absorptions, indicating alkyl- substituted and/or fused-ring aromatics. The gas chromatograms of these fractions indicated that the major constituents were n-paraffins. The HPLC chromatogram of the LC-2 fraction of fly ash Wl (Fig. 9) had nine major peaks including phenanthrene, pyrene, and chrysene. Phenanthrene and pyrene were also detected in coal ash in a study discussed in EPRI (1978). Numerous smaller peaks, most of which were eluted prior to chrysene, appeared in the HPLC chromatogram. This fact indicated that smaller quantities of polynuclear aromatic hydrocarbons other than chrysene (of lower molecular weight than chrysene and phenols) were possibly present in the fly ash. 4000 200 Wave number (cm ) Figure 7. Infrared spectrum of the benzene-extractable organic material in fly ash W1. ISGS 1M3 21 4000 200 ISGS 1983 3000 Wave number (cm ) Figure 8. Infrared spectrum of the LC-1 fraction from the benzene extract of fly ash W1. The infrared spectra of the LC-3 samples exhibited strong aliphatic absorption peaks and weak aromatic peaks except for the Wl LC-3 fraction (Fig. 10), which appeared to have more aromatic compounds than the remaining three LC-3 fractions- There were also strong absorptions in the carbonyl (1750-1700 cm - !) regions of the Wl LC-3 spectrum. Because these appeared in fraction LC-3, they were likely due to long-chain aliphatic esters or aryl esters. The aryl esters were first thought to be contaminants of plasticizers introduced during sample handling. Plastic bags were used as storage containers prior to organic analysis (both ethyl and diethyl phthalate were identified by GC-MS in the 450°C pyrolysate of fly ash Wl). However, aryl esters have been recently indicated in a char "X- u_ 6 V 7 8 ISGS 1983 Figure 9. HPLC chromatogram of the LC-2 fraction from the benzene extract of fly ash W1. See Figure 2 for identification of the numbered peaks. 22 4000 3000 2000 1600 1000 600 200 Wave number (cm ) ISGS 1983 Figure 10. Infrared spectrum of the LC-3 fraction from the benzene-extractable organic matter in fly ash W1. prepared by heating coal at 350°C in a fluidized bed (Fuller et al., 1982) Also, aryl esters were inexplicably found in the fly ash wash water from a power plant (F. Harrison, Lawrence Livermore National Laboratory, personal communication, 1982). The gas chromatograms of the LC-3 samples showed the presence of eight to ten dominant components, which are as yet unidentified (Fig. 11). The PAHs (phenanthrene, pyrene, and chrysene) were identified in the LC-3 samples using HPLC. Numerous other smaller peaks due to aromatics having molecular weights higher than chrysene were also detected. The HPLC chromatogram of Wl LC-3 is shown in Figure 12. ISGS 1983 Figure 11. Gas chromatogram of the LC-3 fraction from the benzene-extractable organic matter in fly ash W1. 23 Figure 12. HPLC chromatogram of the LC-3 fraction from the benzene extract of fly ash W1. See Figure 2 for identification of the numbered peaks. The infrared spectra of the LC-4 fractions showed t differences in the compositions of the organics der fly ashes. The LC-4 fraction of Wl (like the LC-3 aromatic compounds and was more complex in composit organics in the other fly ashes. The peaks due to resolved into at least two distinct peaks (Fig. 13) presence of both aliphatic and aryl esters or long- ketones. Phenanthrene and pyrene were again identi Other smaller peaks eluted earlier than pyrene; thi indicate that polar compounds were beginning to be major peaks later than that of pyrene. he beginning of major ived from the various fraction) contained more ion than were the carbonyl absorption were , indicating the chain aldehydes and fied by HPLC (Fig. 14). s was interpreted to eluted. There were no 4000 200 Wave number (cm ) Figure 13. Infrared spectrum of the LC-4 fraction from the benzene extract of fly ash W1. 24 ISGS 1963 Figure 14. HPLC chromatogram of the LC-4 fraction from the benzene extract of fly ash W1. See Figure 2 for identification of the numbered peaks. The infrared spectra of the LC-5 fractions were similar to the spectra of the LC-4 samples, except that the LC-5 fraction from 18 had anomalous and unassigned peaks at 2340 and 1690 cm"! (Fig. 15). The Wl sample had more carbonyl peaks than the other fly ash samples (such as the peak at 1630 cm -1 ) indicating the possible presence of additional aldehydes and ketones. The 1675 cm~l peak may be due to hydroxyl overtones. The HPLC chromatogram of the LC-5 fraction from the Wl fly ash extract (Fig. 16) showed numerous peaks with retention times in the same range as those of PAHs. According to the Level 1 scheme, this fraction contains aromatics with polar functional groups. The infrared spectra of the LC-6 fractions for 15, 18, and W2 were quite similar, with strong hydroxyl, carboxyl, and carbonyl absorptions. The infrared spectrum of the LC-6 fraction from Wl (Fig. 17) had well-resolved 4000 2000 1600 200 Wave number (cm ) Figure 15. Infrared spectrum of the LC-5 fraction from the benzene extract of fly ash 18. 25 ISGS 1983 Figure 16. HPLC chromatogram of the LC-5 fraction from the benzene extract of fly ash W1. Peak 5 is toluene, the internal standard. absorptions at 3190 and 3355 cm~l, overriding a broad hydroxyl peak and the peaks indicating aromatic character. These latter peaks were probably amino-nitrogen peaks. HPLC analysis showed that the sample probably contained a large number of phenolic compounds as well as other polar aromatics (Fig. 18). 4000 3000 2000 1600 1000 600 200 Wave number (cm ) Figure 17. Infrared spectrum of the LC-6 fraction from the benzene extract of fly ash W1. 26 ISGS 1963 Figure 18. HPLC chromatogram of the LC-6 fraction from the benzene extract of fly ash W1. Peak 5 is toluene, the internal standard. The LC-7 fractions were quite small and appeared to be contaminated with silica gel from the column. Infrared intensities were weak, but the absorptions were essentially comparable to the absorptions in the respective LC-6 fractions. The HPLC results showed only one major peak, which eluted earlier than toluene and was assumed to be a strongly polar compound. Some of the organics identified with these fly ashes are on the priority pollutant list; however, they are present in very small quantities (ppb levels at most), which are comparable to results reported elsewhere (EPRI, 1979). However, the organics associated with these fly ash samples do not appear to be present in concentrations that would pose any significant environmental hazard during landfilling operations or to the aquatic environment during ponding. Pyrolysis studies The noncondens tography. The detection of a appropriate co at the time of of the individ of low molecul hydrocarbons-- accounted for able gas in the headspace was analyzed by gas chroma- results of these analyses are given in Table 10. The particular component is indicated by an "x" in the lumn. Because the headspace was still at a reduced pressure analysis, no attempt was made to quantify the amount of any ual components. Only saturated and unsaturated hydrocarbons ar weight--typically found in the pyrolysates of higher were detected. In the Wl pyrolysate, carbon dioxide more than 50% of the total chroma tographable gases. 27 xxxxxxxxxxxxxxxxxx xxxxxxxxxxxxxxxxxx o o Ln «3- xxxxxxxxxxxx o o o «3- XXXXXXX XXX o o o IT) i/> o o CO CTi XX X X X X X X X X X oo X X X* X X X XX XX <£> X X X X X X X X xxxxxxxxxxxxxx •D 28 X X X X XXXXXX XX XX XXXXXX XX o S- OJ OJ c cd CD c c a; c c CD CD Q. a> a> -1-) 4-> o -•-> 4-> C C s- 3 cd a OJ CD CD Q. jz c _Q Q. a. cu c C i — C i— i — CD CD O) c CD CD ■(-> >1 c c >> c > > >> C C c CD o> r— c 13 sz ai .C -t-> x: -C ai CD 03 r— C >> T3 -O -t-J 4-> 4-> ■M Q. c -»-> C +j -t-> X X -C >> <0 Q. Q. 1 -C .c O O O E JQ -O E o Q. E Q. E E .c -C CD 4-> -*-> J- S- i/l i 1 1 i l/l 1 i 1 i i i 1 CD CD a_ -r- cm t— i CM -r- Table 11. Organic components in the condensable pyrolysates of the fly ashes: (x) detected; (xx) detected in larger quantity; (t) trace; (?) retention time does not match. Organic Fly Ash Component 12 13 14 15 16 17 18 19 Wl W2 W3 toluene X ethyl phthalate X XX X XX X XX X t n-Cm X X X X X t n-Cis X X X t X X t n-C 16 X X X t XX X X X XX t i-Ciy X t X X X X n-Ci7 X X X t X X X X X X t i-Cis X X t X X X X n-C 18 X X t X X X X X X t n-Cig X X X X X X X X X X t diethyl phthalate X XX XX XX XX XX XX X XX t n-C 2 o X X X X X X t i-Czi X n-C 2i X ? X X X X X ? X i-C 22 X X X n-C 2 2 X XX X X X X X t n-C 23 XX X t n-C 2 i» X X t XX X X X X X t n-C 25 X X t X X X n-C 26 XX XX X X n-C 27 C 2 8? X X XX X XX XX C 28 ? X X XX XX X XX The "GC-f ingerprints" of the noncondensable gas produced from the II, 12, 13, 14, and 17 samples were similar in the kind and quantity of any given component (Figs. 19, 20; Table 11). The 15, Wl, W2, and W3 condensates were also similar to each other (Figs. 21, 22); however, the two groups were quite dissimilar in that the non-condensables from the latter four ashes contained major components that were present in much lower quantities or did not appear in the former group. 29 ISGS 1963 Figure 19. Gas chromatogram of the noncondensable hydrocarbons produced by pyrolysis at 450°C of fly ash 12. Peak identification: 1. methane; 2. ethylene; 3. ethane; 4. C 3 's; 5. C^s; 6. C s 's. 1 AJ 2 J 5 ISGS 1983 Figure 20. Gas chromatogram of the noncondensable hydrocarbons produced by pyrolysis at 450°C of fly ash 13. See Figure 19 for identification of the numbered peaks. The condensable fraction from the pyrolysis of the Wl sample was analyzed by GC-MS. The major components detected were the n-paraffins with 13 to 28 carbon atoms per molecule. The compounds present in the largest quantities were n-C]j, n-Cig, n ~^2Q» n ~C22> n ~C24> and n ~C28 (Fi g- 23). In a study discussed in EPRI (1978;, n-C]7, n-Cig, n-C2i, n_c 22> and n_c 27-31 were tne dominant hydrocarbons in an ash sample, existing in the 516 to 816 ug/kg concentration range. This range is consistent with the semiquantitative analysis reported here. The results from this study are typical of results obtained when coal char is pyrolyzed under similar conditions. These results lead to the conclusion that a probable source of these hydrocarbons was the coal particles present in the ash. However, aryl esters, especially ethyl- and diethyl phthalate were detected in significant quantities. Diethyl phthalate appeared to be the major component in the condensates of the other fly ashes used in this study. The source of these phthalates in the condensates may have been the plastic bags used to store the samples. A 30 ISGS 1963 Figure 21. Gas chromatogram of the noncondensable hydrocarbons produced by pyrolysis at 450° C of fly ash W2. See Figure 19 for identification of the numbered peaks. ISGS 1983 Figure 22. Gas chromatogram of the noncondensable hydrocarbons produced by pyrolysis at 450°C of fly ash 15. See Figure 19 for identification of the numbered peaks. similar result was observed from benzene extracts of these ashes. However, others (Fuller et al . , 1982; Harrison, personal communication, 1982) have reported aryl esters in char prepared in a manner that would preclude aryl ester contamination and in fly ash wash water. 31 ISGS 1983 Figure 23. Gas chromatogram of the condensable organics produced by pyrolysis at 300 C of fly ash W1. Peak identification: 1. n-tridecane; 2. n-tetradecane; 3. n-pentadecane; 4. ethyl phthalate; 5. n-hexadecane; 6. n-heptadecane; 7. n-octadecane; 8. n-nondecane; 9. diethyl phthalate; 10. n-eicosane; 11. n-heneicosane; 12. n-docosane; 13. n-tetracosane; 14. n-octacosane. Identification of the major condensable components derived from the other fly ash samples was accomplished by making comparisons to the Wl GC-MS data and to the GC retention times of standards. Many other components were also detected; however, they were not sufficiently well-resolved nor present in large enough concentrations to permit identification. CHARACTERIZATION OF THE FLY ASH EXTRACTS Conventional chemical analysis of fly ash cannot presently be used to determine the mobility of potentially toxic trace constituents in aquatic ecosystems. Most fly ashes are composed primarily of aluminosilicate glass spheres that are only slightly soluble; however, the surfaces of the glassy spheres of the individual fly ash particles may contain adsorbed molecules of potentially toxic constituents that may be desorbed into water. The toxicity of leachates to aquatic organisms may be due partly to the release of some trace constituents that are absorbed on the surfaces of the particles rather than bound up in the insoluble glassy matrix. To evalua of fly as leaching The overa extracts The varia operating coals bei te the potent h, several la procedures an 11 indication from fly ashe ble nature of conditions o ng used, and ial for water and soil contamination from the leaching boratory extraction methods have been proposed. Several d solubility studies were reviewed by Roy et al . (1981). of these studies was that field leachates or laboratory s were extremely variable, as were the solid wastes. an ash and its leachate was directly related to the f the individual power plants, the composition of the the leaching or extraction procedures employed. The pH of fly ash leachate may range from 4 to more than 12; alkaline solutions were more commonly reported (Roy et al., 1981). Short-term extracts generated by the two reddish-brown samples (12 and 17, Table 1) were acic'~ (about pH 4.2), whereas the grayer samples (Table 1) were all alkali, e (pH >11). The color of fly ashes may be useful in predicting the initial pH of a leachate. The ratio of matrix CaO to SO3 may 32 influence the pH of the leachates. For the 12 samples in this study and the acid Fersic (an acidic high-iron fly ash) studied by Griffin et al. (1980), short-term (24-hour) extracts that were acidic were associated with samples having a Ca0/S03 ratio of less than two. Alkaline extracts were produced from samples having a matrix CaO/SCh ratio exceeding two. This observation may reinforce an observation by Swaine (1977) that H2SO4 exists on some fly ash particle surfaces. The presence of H2SO4 could result in acidic extracts from some ashes while the resulting pH is influenced by the dissolution of matrix lime in systems. U.S. EPA Extraction Procedure (EP) The results of the application of the proposed U.S. EPA Extraction Procedure (EP) are given in Table 12. The pH of all the extracts associated with the Illinois Basin samples was approximately 5.0, because the procedure calls for adjusting the pHs of the solutions to this value. However, the two lignite-base samples W2 and W3 still retained their alkaline character after the addition of the maximum allowable amount of acetic acid (800 ml_ of 0.5N). The extreme buffering capacity of these two samples could produce yery alkaline leachates in improper disposal schemes. Results (Table 12) indicated that, while the major constituents of the solid waste (Al, Si, and Fe) were only slightly soluble in this leaching environment, some trace and minor constituents were very soluble. Most of the S (90.0 _+ 16.6%) in the Illinois fly ashes was soluble, whereas about 18 to 75% of the matrix Ca went into solution. The amount of soluble B ranged from about 24 to 56% of the total, averaging about 44%, comparable to the amount of soluble B (about 50%) observed by Cox et al. (1978) in a short-term extraction procedure with an Illinois Basin fly ash. Calcium, S, and B were consistently the most soluble major constituents in the western ashes. Calcium was found to be among the most soluble constituents in lignite fly ashes by other investigators (Churey et al., 1979). The most soluble trace metal in the Illinois fly ashes was Zn; Ba was the most soluble trace metal in the subbituminous fly ash (Wl). The concentration of 0.16 mg/L As in the Wl solution indicated that about 40% of the available As was soluble. About 20% of the matrix Se in Wl was soluble, and Se concentrations were below detection limits in the Illinois fly ash extracts. Nearly 37% of the total Se in the W2 fly ash was solubilized, producing a solution with 0.35 mg Se/L. Churey et al. (1979) also found Se \/ery soluble in ashes from lignite coals. Chromium and Zn concentrations did not exhibit any discernible pattern; the amount of soluble Zn varied from 1.65 percent in 13 to nearly 29% in II. The EP test may not have been conducive to Zn extraction, or these results may indicate that most of the Zn in some samples was bound in the glassy matrix and did not exist as an adsorbed surface constituent or a soluble salt such as ZnSO/pHzO as proposed by Henry and Knapp (1980). In reporting on Teachability trends, Natusch et al. generalized that Fe, Si, Ba, Ca, and Mg were among the least soluble constituents. This study indicates that Ca and Mg may be more soluble when fly ash is subjected to the leaching conditions of the proposed EP procedure. Natusch et al. (1977) also concluded that Mn and Zn exhibited substantial extractabi 1 ity. In the present study, Mn and Zn were also among the more soluble 33 Q. X LLI < Q. Hi -a c _i 2 i C £ c ~S- CD 3 a> *-" .c V) IU re ;_: CJ a> o I- a \D CO O CM in ON o in o m CM in CN IT* CN in o r-- oo o o o — CN CN O O O CO O O O CN O ■* in m _ tf\ o o - m o oo *■ o •* rsi csi *r o _ v IO CO — o o o V V 3 o s o V CO — ITV >* o o vo CM O O CM CM O O 8 in o o V O CN v vo vO o o V V vO CM (O CO o o V (N o CM o o V o o ■* to o r- o — o o ■*■ in o O O — o ao tO *r co VO _ CN CM or> r- m co o vO O O — o CM r- — "9- O O CO ^- IT) «e Kl 03 fl OnCNOOOOvOOCN KlfiOOOOr^OOOOCJvOv O V CM fO V — "<*■ to + o o o V V o — o o v — v v 10 • .* « m >» F +- c () •— — *N c CO l/> — — n — (0 r- x • ID a. c E o c <0 s • • — +- C3 o .c • ■C h- Q. UJ LU cS cS 10 T? 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The amount of soluble Mn averaged 12.88 +_ 6.29% in the Illinois Basin samples. The general trend of EP solubility for the Illinois Basin fly ashes was: SO4-S > Ca, B > Cd > Sb, Mn, Mg > Zn, Na, Mo > K, Ni , Cr, Cu > Be, Ba, Si, Al, and Fe. The general pattern of EP solubility for the subbituminous fly ash Wl was: SO4-S > B, As > Ca > Se > Mg, Zn > Mn > Na > K, and Ba; SO4-S > B > K > Mo » Se, Na > Ca > Zn, Mg > Be, Cr > Mn, Si, and Ba was the order for the lignite fly ashes W2 and W3. However, these solubility trends apply only to EP extracts; in dissimilar leaching environments, different extractability trends may be observed. In solubility or leaching experiments in which extraction takes place in alkaline conditions (as typical with many fly ash leachates), different solubility regimes in the resulting alkaline solutions may take place, since the pH of the extract is often the dominant factor controlling the solubility of many inorganic constituents. The Cd level in the EP extract from 17 exceeded the recommended level outlined by the proposed U.S. EPA Resource Conservation and Recovery Act (RCRA) (Table 13). The concentrations listed are 100 times the EPA's National Interim Primary Drinking Water Standards (U.S. EPA, 1976). If the EP extract contains any constituent exceeding the maximum allowable level for that given contaminant in an EP aqueous extract, the parent waste may be classified as a hazardous waste. The classification of a waste as potentially hazardous may also be based on criteria other than the EP data (U.S. EPA, 1980). Fly ash was recently removed from the list of Subtitle C in Section 3001 of RCRA. Therefore, all fly ashes are classified as Table 13. Contaminant concentrations (mg/L) in EP extracts qualifying for hazardous waste classification (U.S. EPA, 1980). Constituent Concentration (mg/L) Arsenic 5.0 Barium 100 Cadmium 1.0 Chromium 5.0 Lead 5.0 Mercury 0.2 Selenium 1.0 Silver 5.0 Endrin 0.02 Lindane 0.40 Methoxychlor 10.0 Toxaphene 0.50 2,4-D 10.0 2,4,5-TP Si 1 vex 1.00 35 nonhazardous wastes under present criteria. However, these guidelines are still in a period of revision, and the status of fly ash as a nonhazardous waste may be modified. If the status of power plant by-products were to be revised, one fly ash (17) would fall into the hazardous waste classification. There was about 73.0% soluble Cd in this sample, releasing 1.38 mg Cd/L in solution; the maximum allowable extract level for Cd is 1.00 mg/L. On the basis of these data, the parent ashes of the other 11 EP extracts would not be classified as hazardous wastes under the present criteria. LONG-TERM EQUILIBRATION EXTRACTION Most aqueous systems of fly ash do not reach equilibrium in most short-term (24-hour) extraction tests (Elseewi et al., 1980). Short-term extraction procedures will leach out the more soluble salts, but other elements such as Sb, As, Ba, and Se (James et al., 1 977) ^ and Ca, Cu, Fe, and Zn (Natusch et al., 1977) may be continuously leached into solution for periods longer than 24 hours. Therefore, as a first approximation in predicting the water quality of ponded fly ash leachate, a long-term equilibration extraction procedure was designed to produce a solution potentially equilibrated with the solid waste. Fly ash ponds may reach metastable equilibrium conditions if the rates of the chemical reactions controlling the solubility of the particular mineral phases involved are slow in comparison with the retention times of the water in the ponds. Five of the 12 fly ash samples were chosen for solubility studies by this long-term equilibration (LTE) procedure to suggest the general chemical character of disposal ponds that may develop after these ashes have been slurried. In the LTE procedure (in contrast to the EP method), the pH of the solutions was not adjusted, and a greater solid-to-liquid ratio (a 20% slurry wt/vol) was used. These solutions were periodically sampled during the extraction period. Results for the two acidic fly ashes (12, 17), two alkaline samples (13, 18), and one of the western samples (W2) are presented in Tables 14, 15, 16, 17, and 18. It is difficult to make direct comparisons between the LTE data and those from the EP because of the different pHs of the extractants, the length of the solubilization period, the method of agitation, and the ratios of solid to liquid used in each procedure. After 24 hours (the duration of the EP method), the two LTE solutions generated from the Illinois Basin fly ashes (12 and 17) were acidic (pH 4.1), while the other two (13 and 18) were alkaline (about pH 11). The western fly ash extract, W2, was highly alkaline (pH 12.4). As suggested by the data in Tables 14-18, the solutions were probably not in chemical equilibrium with the solid phase after the first 24 hours of solubilization, because the concentrations of many aqueous species continued to change for several weeks. 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(0 CO r» r-~ tj • • • CM in CO in — vO o w— ^- IT\ •- r— in •* ■* CO IO (N CM + CM CM >> (0 tj VO o in >. ID tj to ON tO vO >» (0 tj n CO o CM 3 o in CM ■* O O — * — «- m--.-oaoocMOo — — !■■» O O CM — vO O tO o o p- o O O vO V V O O O O CM VO v cm v in CM 00 CM oo cm m — r» o vO tO CM r- CM CO CM oo • • o\ m o r— in CM + oo * *f oo o o — •— to CM O CM O O O CM O o o on o o o V V o o • o V CM o CM o oo CM to vo o to r^ O O CM m o • o V IO o o o — vo cm m cm o r» o cm o o CM • in ON on CM + -3- m o in o O CO O V o O V o V ON tO CM V o V CM vO CO CM o V o V o V o *3- o V o o VO o vO IO vO to vO *3- t CM to O o o CM o in CM CM O in O "3- m o o in CM o O in O in to o to o to vO T* CM CO to O !*■ CO CM vO vO CM + o in o vO in O o CO o V o O V o V to to CM V o V CM VO r» vO CM o V o V o V O CO o V o o ON to M- o CO *3- in o rO O o O <* o CO CM CM O in O m in o o vo CM o <* o in o in to ON fO o in vO in IO vO CO **■ rO CM in in CM VO >* CO CM + "3- O vo in o o CO o V O O V O V CO ■* CM V o CM r- CM o V o V o V o in o V o o ON VO to in • o 1- •«• V CM o — V o o CM V CM CM O O O fO V V CM oo in in o CM VO O o o — vo to 00 o — o o o O vo CM IO CM OOO CMOOOOCMOOOovOOOO — r» *r — to o vr~ o o\ *r — r-» CM — + OOO V V CM co m o o ^ 00 to o — o • • • • • • C-4 • — CM 00 ON ^~ o o OOO •— 0^ CM X CM V vO i — O . — 00 CM CM IT} • J* + n ID >~ F +- C U — •— s, c E E C • CJ • -Q > E c .c < en < CO cS $ cS — in io oo o — o o o o o o v v v vO o CM to to CM o o v v 00 o CM 00 o to OOO V V V tO vO CM o o — OOO V V o vO CMrOCMiOOOtOvO — OOOOtj-OO — OOO V V tO o o o V V 0> vO vO vO o to vO o m « tl L 3 « O)c0lD — -Q-OCD— c c3OOOU-N^sSS2ZQ.00tOcOt75 TJ- o CO T? o l_ o CD c en o l_ TJ o C IO in C5 CJ C^ +- a> _J > V ~ C7) +- E ID 10 SO4-S > B > Ca, Mg > Cu > Na, Be, Ni, K > Mn > Cr > Al > Ba, Si, Mo, Pb, and Fe. After 142 days, the relative solubilities were: SO4-S > B > Mg > Mo, Ca > Cd > Na > Se > Mn > Zn > Sb, K > Ni > Ba > Cu, Cr, Pb, and Si. The change in solubility 43 trends is a reflection of the shifts in equilibria controlling the solubility of the constituents during the extraction interval. In contrast, the pH of the two alkaline solutions (13 and 13) remained above pH 10 during the entire extraction interval (140 days), and slowly decreased thereafter. In both the acidic and alkaline solutions, Al was more soluble during the early phases of the procedure but significantly decreased in concentration with time. In contrast to the two alkaline solutions produced by the Illinois Basin fly ashes, the pH of the solution generated by the lignite fly ash (W2) was essentially invariant for the entire solubi 1 ization-equi 1 ibration interval (140 days). Moreover, the solubility of Al from the lignite sample steadily increased with time. Other studies dealing with fly ash extracts have also noted analogous changes in concentrations with time. Talbot et al. (1978) equilibrated a western U.S. fly ash for 6 months in an open system. The pH of the alkaline extract decreased from 11 to 8.8 after 1 month, having reached a steady state. Townsend and Hodgson (1973) equilibrated an alkaline fly ash generated from British coals in a closed system. They observed that the pH and the OH and Ca concentrations increased initially, and then became invariant, whereas the B and SOa concentrations decreased during the extraction interval. Helm et al. (1976) also noted that concentrations of SO4 and B decreased with time in solutions generated from shake tests with an alkaline fly ash produced from eastern bituminous coals. Page et al. (1979) equilibrated a 1:1 fly ash-water mixture for 30 days. In the resulting alkaline solution, Ca and OH concentrations steadily decreased, whereas the pH remained constant. The present study may have several implications concerning the water quality of ash disposal ponds in a chronological framework. The two fly ashes that formed acidic extracts initially contained potentially toxic trace metals, such as Cd. With time, these acidic solutions became neutral, and several such trace constituents were no longer soluble, although other potential pollutants persisted in solution for longer periods. The fly ashes that produced alkaline extracts generated solutions that remained alkaline, and similarly, several potential pollutants also persisted in solution. These results indicate that fly ash, particularly acidic samples, are most toxic to aquatic ecosystems when initially slurried to disposal ponds and that their toxicity may decrease with time. However, if potential pollutants are in metastable equilibrium in the pond, they may have long residence times in the ash effluent, increasing the probability of bioaccumulation by aquatic organisms. Excessive levels of Se have been detected in various species of fish inhabiting a cooling lake associated with a coal-fired power plant in Illinois (Larimore and Tranquilli, 1979). Intermittent overflow of a nearby ash pond into the cooling lake may have been the source of the Se. The specific concentrations of the constituents exceeding EPA interim primary or secondary drinking water standards or irrigation water criteria are listed in Table 19. Depending on the solid waste, As, Cd, Cr, and Se 44 ■o > w (O ■a c o o E-; a F b 'C c B C c O C o 0) C o u ~ ' X u 01 1- c n <+- O ro c .Q o u D c vT 3 a; E L. fl> ID CA to +- CD Ol •J| c D M i_ CD O C k. *-> D c 01 § *- r c 0) O 3 ♦_. 01 Ol C L. "~ CJ o O) TJ l_ 01 a> XI ,0 c m !0 r- yl in >. (M *t vO r— ID iri CM rO 00 r^ — CM XJ • o • O • O '*• • CM • vO • ro • CM O _ _ m vO ** m ro CM X L. 3 O in • o rO O • o vO *»■ m • CM O CM O vO • in >. CM (0 rO — 00 in XJ • • O • VO • 'St o o — — — • * vO •" — oo 1— 1 i_ 3 o rO • o CM • o CA r^ 00 ON • o CM • ro vo oo • Ov rO in • o m rr CM >> O O ro rO .c 10 • • • • 10 ■o o CM ro m O ID vO CO vO oo — >- o CM _ •~ Li. I~- 1— 1 1_ 1^ 00 VO ov __ 3 00 rO CM in ov CM _ m o o • • • • • • • • • • n o ro CM in ov vO vO vO IO 'd- oo in VO VO CM — io ~ «n vO ov in >» _ o — — p~ (0 • • • • • -o o o vO __ ^ , *r «*■ "" rO o si ro • o 00 O • o in • o O O O • ro • ro CM o • ro V) in Ov o> >■ o Ov ro vO (0 • • • • • T> o o to O ro CO co CM CM vO ** — •"" CM i—l l_ 3 • o o • to • VO • m vO • O • • CM • o o CM 00 CM CM *»■ f VO in -C — r^ Ov — OV vO ■— CM 1_ l_ CD cd +- ■r- (0 10 X in X • l_ in __ in Ol o in Ov CD in Ol o o o o c O ro o o -t- O o o O c • • • • • • • • 1 10 • • • • o o o o j* _ o O o in » o CM o CM jL c in in CM c CM • g L. in •l- 1_ T3 »^ c -o *— * ■t- E - CD m 10 3 3 >■ E p l_ m ■r- Ol E C +- L. o E 3 3 10 CD CO — 3 a> — 10 •— 3 •— — -o l_ c ■t- c \- C ■o — -1- i c — e c 5 CD W •— CD E o CD CL c O) ■4- o v-» — E o >• -* c l_ in -o i_ __ o Q. o c _ c 3 l_ — O o CL l_ 8 x: CD CD o l_ 10 3 X CO o *— o < o (/> to o s: CO M CL < s 2 45 were in concentrations exceeding the primary standards after 1 hour in the LTE solutions. After 106 to 140 days of extraction, the concentrations of these constituents changed, but the levels of some of the potential pollutants still remained above recommended levels. In each solution, other constituents exceeded the secondary standards and the recommended levels for irrigation water (U.S. EPA, 1976). As with the primary standards, certain potential pollutants remained in solution in excessive levels. Boron, Mo, and SO4 were constituents common to all five extracts that remained above recommended levels during the entire extraction interval . TOXICITY TESTS All five undiluted fly ash LTE extracts were acutely toxic to fathead minnows, causing total mortality (Table 20). Three of the extracts (W2, 13, and 18) were very alkaline (pH >10.0), and mortality due to ionic shock was expected. In a previous study (Suloway, et al., 1981), test solutions in which the pH was greater than 9.2 were acutely toxic to fathead minnow fry. However, two of the samples in the present study (12 and 17) were relatively neutral in pH and were not expected to cause total mortality. All extracts were then tested with LC-50 determinations. The concentration of dissolved oxygen in all the screening procedures was more than 60% of saturation. The pHs of the extracts remained relatively stable during the bioassays with the exception of 18, in which the pH decreased almost an entire pH unit. There was a 5% mortality in the controls. LC-50 determinations (Table 21) were made to measure the relative toxicities of the extracts and to determine the dilutions necessary to ensure survival during a 96-hour bioassay of the toxic extracts. An inverse relationship existed between toxicity and the LC-50 value for an extract. The LC-50 values for W2 and 13 were 2.8 and 63.0 (Table 21), respectively. Sixty-three mL of 13, diluted with 37.0 mL of dilution water, was just as toxic as only 2.8 mL of W2 diluted with 97.2 mL of dilution water. Therefore, with an increase in toxicity, there was a decrease in the LC-50 value. TABLE 20. The percentage of mortality of 1-to-6 day-old fathead minnow fry (Pimephales promelas) resulting from 96-hour exposures to full-strength extracts generated from five fly ashes. Initial and final pHs and concentrations of dissolved oxygen (mg/L) are listed. Sample pHi pHf D.O.-j D.O.f Mortality (%) W2 12.816 12.733 8.75 8.59 100.0 13 11.498 11.171 8.80 8.74 100.0 18 10.260 9.314 8.87 8.40 100.0 12 7.559 7.225 8.79 7.87 100.0 17 6.40 6.758 8.77 8.24 100.0 46 Table 21. The LC-50 values, amount of dilution necessary to eliminate mortality, and the initial pH values for extracts generated from five fly ashes. Fly ash s amp 1 e pHi LC-50 Confidence intervals 3 mL/lOOrnL mL/lOOriL Di lution for zero percent mortality W2 12.816 2.8 13 11.498 63.0 18 10.260 84.0 12 7.559 82.0 17 6.40 82.0 2.5 - 3.1 1:1000 58 - 68 1:2.5 80 - 88 1:1.4 78 - 86 1:2 79 - 85 >1:1.25 a There is a 95 percent probability that the LC-50 falls within the confidence interval listed. The results of the LC-50 determinations indicate that W2 was the fly ash extract most toxic to young fathead minnows; it required as much as a 1:1000 dilution to eliminate mortality. The 13 ash produced the second most toxic extract; the remaining three extracts had similar LC-50 values. The acute toxicity of a leachate should be partly a function of its chemical composition. Simple linear and multiple regression analyses were used to determine, for each extract, the relationship between the mortality data and the chemical data collected during the LC-50 determinations (Tables 22-25). The 18 test solutions were not chemically analyzed. The range of concentrations for each chemical constituent, the recommended water quality level for each chemical constituent, the change in r 2 for the multiple regression, and the r value for the simple linear regression are listed in each table. In statistical analysis, the values for r and r 2 will vary from <0.001 to 1.000. The closer the value is to 1.000, the stronger the relationship between mortality and a particular chemical constituent: for example, for the extract from W2 the strongest relationship detected by the multiple regression analysis (Table 22) was between mortality and initial pH (r 2 = 0.519). The concentrations of several chemical constituents (B, Mo, SO4, pH, and pHf) were highly correlated with mortality (r >0.70). When the results of these statistical analyses are considered with the levels of various chemical constituents present in the test solutions, the importance of various chemical constituents with respect to acute toxicity of a particular fly ash extract can be assessed. A strong relationship existed between the acute toxicity of the W2 leachate and its pH. Alkaline (pH > 9.2) solutions have been shown to be acutely toxic to young fathead minnows (Suloway et al., 1981). Cairns et al. (1972) described the effects of a fly ash pond spill on a small river and suggested that the principal lethal agent was the high pH level. Wasserman et al. (1974) reported that runoff from alkaline 'ash ponds was lethal to catfish because the increased pH caused the precipitation of ferric hydroxide, which might have clogged the gill apparatus, causing asphyxiation, 47 Table 22. The range of concentrations and recommended water quality levels for chemical constituents measured in test solutions of W2. Range of Recommended water Chemical concentr, ations quality levels r2 constituent (mg/Li ) a (mg/L) b Change rC Al <0.33 - 0.68 1.0 0.118 -0.20 As <0.07 0.05 - - B 1.23 - 5.72 25 0.003 0.89 Ba 0.049- 0.088 2.5 0.020 -0.82 Be <0.001- 0.009 0.055 0.019 0.23 Ca 6.69 - 17.4 16 - - Cd <0.04 0.001 - - Co <0.01 0.25 <0.001 -0.12 Cr <0.01 - 0.02 0.25 0.140 0.69 Cu <0.004- 0.014 0.05 0.001 -0.21 Fe <0.04 0.25 - - Mg 5.57 - 17.2 87 0.010 -0.88 Mn <0.008 0.1 <0.001 0.04 Mo 0.03 - 0.19 7 <0.001 0.89 Ni <0.03 0.01 - - Pb <0.05 0.05 - - Sb <0.04 0.2 <0-001 0.05 Se <0.07 0.25 0.040 0.26 Si 4.34 - 5.54 - 0.053 0.35 Sn <0.03 - 0.17 - S0 4 74 328 250 0.006 0-89 V <0.08 ; 0.008 0.24 Zn <0.005- 0.147 0.1 0.004 0.05 pHi 8.4 - 10.4 6.5-9. 0d 0.519 0.72 pHf 8.4 - 8.9 6.5-9. Qd 0.003 0.84 a Al 1 values in mg/L except pH. b Values are MATES cited from Cleland and Kingsbury (1977) unless another source is indicated. c Values of r2 and r represent the results from multiple and simple linear regression analyses of the relationship between mortality observed in the test solutions of the extract and the concentrations of each chemical constituent measured in those test solutions. d From Quality Criteria for Water 1976 (U.S. EPA, 1976). The extract of 13, like that generated from W2, was very alkaline and relatively toxic. The regression analyses indicated strong relationships between the final and initial pH and fish mortality (Table 23). Although the range of values for the final pH regression was rather narrow, there were 16 data points between the minimum and maximum pH values. The initial pH values were also elevated enough to cause mortality. Aluminum, As, and Ca were present in concentrations that exceeded recommended values; however, probably only Al was present at sufficient levels to be acutely toxic. The extract generated from 17 was slightly acidic (pH < 6.7) when the LC-50 determinations were calculated (Table 24). The extract was much less toxic than those of W2 and 13; therefore, test solutions used to determine the LC-50 value did not require large dilutions. The high percentage of extract in the test solutions (75 to 100%) and the lower pH resulted in 48 Table 23. The range of concentrations and recommended water quality levels for chemical constituents measured in test solutions of 13. Range of Recommended water Chemical concentrations quality levels r2 (d) constituent (mg/L) a (mg/L) b Change rC Al 0.27 - 1.94 1.0 <0.001 0.31 As <0.07 - 0.14 0.05 0.034 0.16 B 3.99 - 12.7 25 0.011 0.31 Ba 0.075- 0.1 2.5 <0.001 -0.66 Be <0.009 0.055 0.002 -0.27 Ca 18.1 - 21.1 16 - - Cd <0.01 0.001 - - Co <0.004 0.25 - - Cr <0.01 - 0.03 0.25 0.008 0.12 Cu <0.006 0.05 0-019 -0.30 Fe <0.04 0.25 - - Mg 7.64 - 18.7 87 0.033 -0.66 Mn <0.009 0.1 Mo 0.01 - 4.18 7 0.007 0.31 Na <2.73 - - - Ni <0.03 0.01 - - Pb <0.05 0.05 - - Sb <0.03 - 0.05 0.2 0.005 0.30 Se <0.07 - 0.08 0.25 0.023 -0.08 Si 4.74 - 10.3 - <0.001 0.03 Sn <0.04 - 0.002 -0.26 S0 4 50 -161 250 <.001 0.16 V <0.08 - 0.46 - 0.031 0.35 Zn <0.02 0.1 0.016 -0.02 pHi 8.3 - 10.3 6.5-9.0 d 0.246 0.50 pH f 8.3 - 8.5 6.5-9.0 d 0.469 0.84 a Al 1 values in mg/L except pH. b Values are MATES cited from Cleland and Kingsbury (1977) unless another source is indicated. c Values of r2 and r represent the results from multiple and simple linear regression analyses of the relationship between mortality observed in the test solutions of the extract and the concentrations of each chemical constituent measured in those test solutions. d From Quality Criteria for Water 1976 (U.S. EPA, 1976). higher concentrations of various chemical constituents in the test solutions of 17 than were found for 13 or W2. The concentrations of B, Cd, Mn, Ni , SO4, and Zn exceeded recommended levels in the test solutions (Table 24). However, B, Cd, Mn, Ni , and SO4 were probably not present in sufficient concentrations by themselves to cause mortality according to toxicity data available in the literature (Cardwell, 1976; Cleland and Kingsbury, 1977; Pickering and Gast, 1972; Pickering, 1974; Pickering and Henderson, 1966). Zinc concentrations ranged from 0.21 mg/L to 0.63 mg/L in the 17 test solutions (Table 24). Toxic effects of Zn on fathead minnows having mean 96- hour LC-50 values of 0.6 mg/L Zn in duplicate flow-through acute bioassays included mortality at concentrations as low as 0.294 mg/L of Zn (Benoit and Holcombe, 1978). However, 8-week-old fathead minnows and soft water (46 mg/L as CaC03) were used in their experiments. Chapman (1978) reported that 49 Table 24. The range of concentrations and recommended water quality levels for chemical constituents measured in test solutions of 17. Chemical constituent Range of concentrations (rag/Lja Recommended water ity levels r2 ig/L) b Change rC 1.0 _ _ 0.05 - - 25 0.025 0.78 2.5 - - 0.055 - - 16 - - .0.001 0.012 0.68 0.25 0.092 0.58 0.25 - - 0.05 - - 0.25 - - 87 0.047 0.79 0.1 0.084 0.78 7 - - - - - 0.01 0.019 0.82 0.05 0.2 <0.001 0.59 0.25 0.002 0.67 - 0.003 0.78 Al As B Ba Be Ca Cd Co Cr Cu Fe Mg Mn Mo Na Ni Pb Sb Se Si Sn S0 4 V Zn pHi pH f 41 3 <0.08 - 0.30 <0.07 66.5 - 90.1 0.31 - 0.078 <0.001- 0.012 <0.004 <0.01 - 0.04 <0.004- 0.05 <0.02 <0.004- 0.016 <0.05 13.1 - <0.008- <0.01 - <2.73 <0.03 - 0.22 <0.05 - 0.06 0.03 - 0.06 <0.07 - 0.18 3.44 - 6.89 <0.04 -1786 <0.08 0.21 - 0.63 6.6 - 8.0 6.8 - 8.2 7 88 2.37 250 0.050 0.74 0.1 0.002 0-74 6.5-9.0 d 0.645 -0.80 6.5-9.0 d 0.018 -0.79 a Al 1 values in mg/L except pH . b Va1ues are MATES cited from Cleland and Kingsbury (1977) unless another source is indicated. c Values of r2 and r represent the results from multiple and simple linear regression analyses of the relationship between mortality observed in the test solutions of the extract and the concentrations of each chemical constituent measured in those test solutions. d From Quality Criteria for Water 1976 (U.S. EPA, 1976). 96-hour LC-50s for Zn for steel head trout varied, depending on which life stage was exposed. Mount (1966) found an inverse relationship between Zn toxicity and water hardness for fathead minnows. Mount tested the acute toxicity of Zn under various pH and hardness conditions, making direct correlations of Zn and toxicity difficult. Using hard (200 mg/L as CaC03) and alkaline (nominal pH = 8.0) dilution water, the LC-50 was approximately 8.2 mg/L of Zn. These data suggest that Zn might be partly responsible for the mortality caused by 17 test solutions. Sulfate and other ions were present in relatively high concentrations, contributing to the electrical conductivity (EC), which varied between 4.1 and 5.29 mmhos/cm (Table 16) in the undiluted extract of 17. Significant mortality of fathead minnow fry has been observed in reconstituted water in 50 Table 25. The range of concentrations and recommended water quality levels for chemical constituents measured in test solutions of 12. Range of Recommended water Chemical concentr ations quality levels r2 constituent (mg/L) a (mg/L)b Change re Al <0.07 - 0.33 1.0 0.075 0.61 As <0.07 0.05 - - B 72.8 - 91.7 25 <0.001 0.70 Ba 0.021- 0.049 2.5 0.286 -0.67 Be <0.001- .008 0.055 0.083 -0-29 Ca <0.004 16 Cd <0.04 0.001 0.022 0.48 Co <0.004 0.25 <0.001 -0.24 Cr <0.01 0.25 0.002 -0.39 Cu <0.004- 0.014 0.05 - - Fe <0.04 0.25 - - Mg <0.001 87 - - Mn 1.54 - 2.01 0.1 0.020 0.70 Mo 7.45 - 9.96 7 0.011 0.71 Na <2. 73 - - - Ni 0.04 - 0.07 0.01 0.020 0.57 Pb <0.05 - 0.07 0.05 - - Sb 0.09 - 0.11 0.2 0.003 0.50 Se 0.07 0.25 - - Si 3.74 - 5.17 - 0.145 0.28 Sn <0.04 - - - S0 4 33 -3036 250 0.026 0.75 V <0.08 - - - Zn 0.09 - 0.27 0.1 0.019 0.33 pHi 7.6 - 7.6 6.5-9. d 0.246 -0.49 pHf 7.6 - 7.7 6.5-9. 0d 0.016 -0.72 a Al 1 values in mg/L except pH. b Values are MATES cited from Cleland and Kingsbury (1977) unless another source is indicated. c Values of r? and r represent the results from multiple and simple linear regression analyses of the relationship between mortality observed in the test solutions of the extract and the concentrations of each chemical constituent measured in those test solutions. d From Quality Criteria for Water 1976 (U.S. EPA, 1976). which the EC exceeded 4.0 mmhos/cm (Suloway et al., 1981). Thus, the total ionic strength of the test solutions of 17 also probably contributed to the acute toxicity of this fly ash extract. The extract generated from 12 was nearly neutral in pH when the LC-50 determinations were made (Table 24). This extract was much less toxic than were the W2 and 13 extracts (Table 21); therefore, test solutions used to determine the LC-50 value were comprised of 50 to 100% extract. Because of the high percentage of extract used in the test solutions, concentrations of various chemical constituents were higher in the test solutions of 12 than in 13 and W2. The concentrations of B, Mn, Mo, Ni , SO4, and Zn in test solutions of 12 exceeded recommended water quality levels and correlated well with mortality data based on the simple linear regressions. 51 Boron concentrations were high, but extremely high concentrations of B are required to produce toxic effects in aquatic life (Becker and Thatcher, 1973). For example, the minimum lethal dose for minnows exposed to boric acid at 20° C for 6 hours was reported to be 18,000 to 19,000 mg/L in distilled water and 19,000 to 19,500 mg/L in hard water (Le Clerc and Devlaminck, 1955; Le Clerc, 1960). According to toxicity data available in the literature (Cardwell, 1976; Cleland and Kingsbury, 1977; Mount, 1966; Pickering, 1974; Pickering and Gast, 1972; Pickering and Henderson, 1966). The individual concentrations of Mn, Mo, Ni, SO4, and Zn were probably not high enough to cause the mortality observed in the test solutions of 12, The total ionic strength of the 12 extract as measured by EC was less than that of the 17 extract (Tables 14 and 16). The EC of the undiluted 12 extract ranged from 2.74 to 3.80. Insignificant mortality was observed in reconstituted water in which the EC was less than 3.0 (Suloway et al . , 1981). Because of the complex chemical composition of the 12 fly ash extract and the unknown synergistic and antagonistic effects of the chemical constituents composing the extract, it is not possible from these experiments to determine specifically which chemical constituents were directly responsible for the observed mortality. BIOACCUMULATION EXPERIMENTS Analyses of variance of fish lengths and weights (Tables 26 and 27) showed that only the fathead minnows were different in weight for sample 13, and so all duplicates were combined for each organism for each sample. The mean initial length and weight of fathead minnows used in the bioaccumulation experiments were approximately 50 mm and 1 g, respectively (Table 28). The mean initial length and weight of the green sunfish used Table 26. The mean initial lengths and weights of adult fathead minnows used in the bioaccumulation experiments. Sample N Mean length (mm) F value 3 Mean weight (g) F value 3 W2-A W2-B 5 5 50.4 49.2 0.176 1.106 1.164 0.008 I3-A I3-B 5 5 53.4 50.6 1.252 1.334 1.012 4.207 I8-A I8-B 5 5 49.2 49.4 0.004 1.102 1.118 0.003 I7-A I7-B 5 5 49.0 49.4 0.069 1.064 1.204 0.350 I2-A I2-B 5 5 46.8 48.8 0.361 1.008 1.256 0.724 Control' ControT -A -B 5 5 47.8 48.2 0.060 0.994 1.002 0-002 a Results of the analysis of variance indicate that if Fn 8) ^ s greater than 3.46, the replicates are significantly different. 52 Table 27. The mean initial lengths and weights of juvenile green sunf ish used in the bioaccumulation experiments. Sample N Mean len (mm) gth F value a Mean weight (g) F value 3 W2-A W2-B 5 5 50.2 46.0 0.859 1.376 1.012 1.709 I3-A I3-B 5 5 48.6 49.2 0.292 1.304 1.344 0.030 I8-A I8-B 5 5 49.0 48.6 0.020 1.278 1.202 0.083 I7-A I7-B 5 5 51.4 50.8 0.044 1.498 1.484 0.002 I2-A I2-B 5 5 51.0 50.8 0.098 1.578 1.568 0.012 Control-A Control-B 5 5 47.8 48.6 0.133 1.356 1.326 0.013 a Results of the analysis of variance indicate that if F( i s 8) "• s greater than 3.46, replicates are significantly different. were 50 mm and 1.3 g, respectively (Table 29). Fathead minnows and green sunf ish in the control solutions were essentially the same size as those exposed to the fly ash extracts (Table 30). At the conclusion of the experiments, all the duplicates that could be analyzed proved to be homogeneous (Tables 31 and 32). The mean final lengths and weights of the fathead minnows and green sunfish between replicates were not significantly different from each other (Tables 33 and 34). Although the concentrations of the extracts to which the organisms were exposed should not have caused mortality, it was hypothesized that the toxic components may have been of sufficient concentration to cause sublethal, physiological perturbations resulting in decreased growth. The results of the AN0VA demonstrated that at the termination of the bioaccumulation experiments the green sunfish and fathead minnows in the Table 28. Initial mean total lengths and weights of adult fathead minnows exposed to extracts from five fly ashes and a control. Mean Standard Mean Standard Sample N length (mm) deviation weight (g) deviation Control 10 47.9 3.33 0.998 0.230 W2 10 49.8 4.09 1.135 0.300 13 10 52.0 3.66 1.160 0.252 18 10 49.3 4.76 1.110 0.389 17 10 49.4 4.34 1.134 0.334 12 10 47.8 4.81 1.132 0.432 53 Table 29. Initial mean total lengths and weights of juvenile green sunfish exposed to extracts from five fly ashes and a control. Mean St andard Mean Standard Sample N length (mm) deviation weight (g) deviation Control 10 48.2 3.1 1.341 0.379 W2 10 48.1 5.1 1.194 0.433 13 10 48.9 3.0 1.324 0.328 18 10 48.8 4.0 1.240 0.374 17 10 51.1 4.0 1.491 0.431 12 10 50.9 3.9 1.573 0.366 Table 30. Comparison of the mean initial lengths and weights between the control test organisms and the organisms exposed to fly ash extracts. Green length sunfish 3 weight Fathead length minnow 3 weight Control vs W2 b 0.002 0.585 1.167 1.178 Control vs 13 0.229 0.010 2.618 0.748 Control vs 18 0.124 0.322 0.242 0.551 Control vs 17 0.613 2.883 0.677 1.001 Control vs 12 2.619 1.738 0.003 0.673 3 The values listed are Fm \q\ values generated by one-way analysis of variance. If'the F value is greater than 3.01, the means are significantly different. b N = 10 for each test and control group. Table 31. The mean final lengths and weights of juvenile green sunfish used in the bioaccumulation experiments. Sample Mean length (mm) Mean weight F value 3 (g) F value 3 2.912 2.362 0.529 2.700 2.478 0.167 2.711 2.614 0.027 3.594 3.798 0.049 3.280 3.480 0.055 2.933 3.068 0.021 W2-A W2-B 5 5 56.2 52.4 I3-A I3-B 5 5 54.4 54.4 I8-A I8-B 5 5 55.6 54.6 I7-A I7-B 5 5 59.2 60.6 I2-A I2-B 5 5 58.2 58.8 Control-A Control-B 5 5 54.0 56.8 0.789 0.000 0.058 0.177 0.020 0.119 3 Results of the analysis of variance indicate that if F^g) is greater than 3.46, the replicates are significantly different. 54 Table 32. The mean final lengths and weights of adult fathead minnows used in the bioaccumulation experiments. Sample Mean len (mm) gth F value 3 Mean weight (g) F value 3 W2-A W2-B 53.2 50.1 0.829 1.500 1.530 0.009 I3-A I3-B 54.5 50.2 b 1.710 1.322 b I8-A I8-B 52.4 50.0 0.486 1.554 1.242 0.825 I7-A I7-B 43.0 53.4 b 0.900 1.646 b I2-A I2-B 47.2 48.6 0.190 0.958 1.312 1.435 Control Control -A -B 50.2 49.6 0.045 1.392 1.218 0.459 a Results of the analysis of variance indicate that if F(i s 8) i s greater than 3.46, the replicates are significantly different. ^Insufficient data for statistical analysis. Table 33. Final mean total lengths and weights of adult fathead minnows exposed to extracts from five fly ashes and a control. Mean Standard Mean Standard Sample N length (mm) deviation weight (g) deviation Control 10 49.9 4.0 1.305 0.373 W2 10 52.1 3.6 1.515 0.456 13 7 51.4 3.5 1.433 0.123 18 10 51.2 5.0 1.398 0.510 17 6 51.7 8. 2 1.522 0.563 12 10 47.9 4.6 1.135 0.453 Table 34. Final mean total lengths and weights of juvenile green sunfish exposed to extracts from five fly ashes and a control. Sample N Mean length (mm) Standard deviation Mean weight (g) Standard deviation Control 10 56.0 6.6 2.997 1.155 W2 10 54.3 6.3 2.637 1.104 13 10 54.4 4.4 2.589 0.777 18 10 55.1 6.1 2.661 0.815 17 10 59.9 7.1 3.696 1.305 12 10 58.5 6.3 3.380 1.213 55 controls were essentially the same length and weight as those exposed to the extracts (Table 35). Furthermore, when the differences between initial and final mean lengths and weights for fathead minnows (Table 36) and green sunfish (Table 37) were compared, the growth of the control and experimental animals was approximately the same. Only the fathead minnows exposed to 13 and 12 extracts grew appreciably less than the controls, but the differences were not significant. Table 35. Comparison of the mean final lengths and weights between the control test organisms and the organisms exposed to fly ash extracts. Green sunfish a Fathead minnow 3 length weight length weight Control vs W2 b 0.313 0.457 Control vs 13 0.368 0.773 Control vs 18 0.091 0.508 Control vs 17 1.467 1.447 Control vs 12 2.676 0.470 1.503 0.585 0.369 0.291 0.968 1.141 0.446 0.195 0.516 0.753 a The values listed are Fn 13) values generated by one-way analysis of variance. If the F vatue is greater then 3.01, the means are significantly different. b N = 10 for each test and control group, except for 13 fathead minnows, N = 7, and for 17 fathead minnows, N = 6. Table 36. Differences between initial and final mean lengths and weights of adult fathead minnows exposed to extracts from five fly ashes and a control. Difference in Difference in mean lengt h Percent increase mean weight Peri :ent increase (mm) in mean length (g) in mean weight Control + 2.0 4.2 +0.307 30.8 W2 +2.3 4.6 +0.380 33.5 13 +0.6 1.2 +0.273 23.5 18 +1.9 3.9 +0.288 25.9 17 +2.3 4.7 +0.388 34.2 12 +0.1 0.2 +0.003 0.3 Table 37. Differences between initial and final mean lengths and weights of juvenile green sunfish exposed to extracts from five fly ashes and a control. Differences in mean length (mm) Percent in mean increase length Differences in mean weight (g) ' Percent increase in mean weight Control + 7.8 16.2 +1.656 123.5 W2 +6.2 12.9 +1.443 120.9 13 +5.5 11.2 +1.265 95.6 18 +6.3 12.9 +1.421 114.6 17 +8.8 17.2 +2.205 147.9 12 +7.6 14.9 +1.807 114.9 56 Several of the extracts generated from the fly ash samples contained relatively elevated concentrations of trace elements. The bioaccumulation experiments were designed to determine if fathead minnows or green sunfish would concentrate these chemical constituents directly from the diluted leachates. Ryther et al . (1979) demonstrated in laboratory experiments that many elements, including As, Co, I, Se, V, and Zn were concentrated from fly ash by sandworms (Nereis vivens) and three species of marine bivalves (My a arenavia, Mevoenavia mevaenavia, and Crassostvea virginiaa) . Depending on the organism and the constituent, these elements were concentrated by factors ranging from 1.2 to nearly 14. Typical enrichment was in the range of 1.2 to 1.6. Cherry et al. (1976) noted that Se, Br, Zn, CI, and Ca were concentrated in mosquito fish, Gambusia af finis . The constituent most concentrated was Se (9.4 mg/kg in mosquito fish muscle). Excessive levels of Se were found in fish in an Illinois cooling lake (Larimore and Tranquilli, 1981). Magnuson et al. (1980) found that crayfish accumulated Ba, Cr, Fe, Se, and Zn from a fly ash pit effluent. Concentrations of 24 elements (mg/kg) were measured in the fish tissues from the bioaccumulation experiments of the present study (Tables 38 and 39). Fathead minnows exposed to diluted W2 extract contained at least twice as much Al, As, and Ni as the controls. The level of Ni (0.944 mg/kg) was more than five times that found in the control fish. Similar accumulations were found in the green sunfish. The concentrations of Al, As, and Ni in green sunfish exposed to W2 were 1.5, 1.3, and 4.6 times, respectively, those found in the controls. Concentration factor is defined by Phillips and Russo (1978) as the ratio of the concentration (wt/wt) of a substance in an organism (or a particular tissue or organ) to the concentration (wt/vol) of that substance in the water in which that organism had been living. For example, an organism containing 10 yg Cu/g tissue taken from a lake containing 1 yg Cu/L has concentrated Cu 10,000 times; thus, by definition, the concentration factor is 10,000. The mean final concentrations of Al , As, and Ni in the diluted W2 extract in which the fathead minnows were placed were 0.39, <0.05, and <0.02 ppm, respectively. The concentration factors for As and Ni cannot be calculated, but they would be high (>20). The concentration factor for Al in W2 by fathead minnows was 37.2. The concentration factor for Al in W2 by green sunfish was 40.8. The concentration factors for As and Ni in W2 by green sunfish were both greater than 15. Both green sunfish and fathead minnows concentrated Mo from 13 extract. The concentration of Mo present in the 13 extract did not exceed primary or secondary drinking water standards (Table 19), nor did it exceed the level recommended by the EPA to protect aquatic life (Table 23). Yet the green sunfish exposed to the 13 extract had 10 times more Mo than did the control fish. The difference between the levels of Mo in fathead minnows exposed to the control solution and to the 13 extract was almost a factor of 6. The concentration factors of Mo for green sunfish and fathead minnows exposed to 13 fly ash extract were 1.4 and 1.6, respectively. Fathead minnows accumulated Al from the 13 extract. The concentration factor for Al from 13 by fathead minnows was 253.6; the level of Al present 57 Table 38. The mean concentrations of various chemical constituents measured in adult fathead minnows exposed to extracts from five fly ashes and a control. Fly ash Control W2 13 18 17 12 Al 6.34 14.5 27.9 7.66 13.0 3.62 As <0.498 0.939 0.562 0.689 <.498 <0.498 B 0.994 1.16 1.27 2.42 4.15 3.99 Ba 10.3 11.4 11.9 8.84 10.1 8.32 Be <0.012 <0.012 <0.012 <0.012 <0.012 0.012 Ca 7000 10700 8380 9080 8310 7930 Cd 0.051 0.062 0.033 0.044 0.422 0.125 Co 0.555 0.477 0.653 0.487 1.00 0.473 Cr 0.983 1.16 0.597 1.76 0.887 0.691 Cu 1.78 1.46 1.36 1.26 0.849 0.809 Fe 21.5 21.6 26.9 21.1 26.1 18.2 K 11700 13400 14400 12200 14300 13200 Mg 282 371 295 322 293 291 Mn 1.55 2.00 1.70 2.67 25.2 638 Mo <0.050 0.062 0.290 1.06 0.315 0.324 Na 845 1120 1090 950 945 876 Ni 0.161 0.944 0.162 0.268 0.969 0.442 P 2092 2870 2340 2560 2380 2350 Pb 2.99 2.26 2.26 1.70 1.16 0.796 Sb 0.207 0.348 0.251 0.220 0.201 0.324 Se 0.397 0.609 0.330 0.422 0.328 0.566 Si 0.677 0.857 1.80 0.778 0.749 0.641 Sn 0.651 0.299 <0. 187 0.315 0.371 <0.187 Zn 47.0 51.7 41.0 43.2 38.3 36.0 % Extr •act 0.0 1.0 10.0 15.0 15.0 15.0 in the fathead minnows exposed to the 13 extract was four times greater than the level measured in the control fish (Table 38). Green sunfish did not accumulate Al from 13, but they did accumulate Pb. The concentration of Pb in the tissues of green sunfish exposed to the 13 extract was twice that present in the controls. The concentration factor for Pb was greater than 25. Neither the concentration of Al nor of Pb exceeded primary or secondary drinking water standards in the 13 extract (Table 19). The results of the LC-50 determinations gave some indications of a problem with Al in the 13 extract, because the level of Al exceeded the recommended level for the protection of aquatic life (Table 23). As occurred with the extract from 13, Mo was accumulated from the 18 extract by both the fathead minnows and the green sunfish. Molybdenum levels in the green sunfish tissue exposed to the 18 extract were almost 40 times greater than those in the control fish. The level of Mo accumulated in fathead minnows exposed to 18 extract was more than 20 times that found 58 Table 39. The mean concentrations of various chemical constituents measured in juvenile green sunfish exposed to extracts from five fly ashes and a control. Fly ash Control W2 13 18 17 12 Al 6.96 10.6 4.56 2.00 11.3 10.2 As 0.587 0.784 <0.498 0.478 0.543 0.499 B 1.62 1.89 1.08 1.56 4.16 4.62 Ba 1.28 1.52 1.20 0.894 0.949 0.867 Be <0.012 <0.012 <0.012 0.012 <0.012 <0.012 Ca 10400 14400 11100 11300 10600 9780 Cd 0.038 0.043 0.045 0.042 0.056 0.049 Co 0.520 0.530 0.381 0.364 0.600 0.504 Cr 1.04 1.42 1.01 1.32 0.944 0.841 Cu 0.325 0.335 0.464 0.304 0.344 0.336 Fe 20.8 25.7 15.2 15.0 23.2 19.6 K 12600 10600 14300 12700 13500 12300 Mg 350 434 363 378 344 326 Mn 3.55 4.13 3.18 3.44 4.61 2.78 Mo <0.064 0.080 0.628 2.38 0.435 1.04 Na 986 1020 1060 981 1040 9720 Ni 0.146 0.668 0.263 0.370 0.308 0.228 P 2780 3310 2920 2980 2600 2630 Pb 0.511 0.457 1.03 0.510 0.748 0.367 Sb 0.289 0.342 0.243 0.381 0.233 0.252 Se 0.351 0.425 0.538 0.370 0.435 0.480 Si 0.892 1.73 0.716 0.625 0.855 0.759 Sn 0.190 0.357 0.261 0.213 0.279 0.246 Zn 32.1 43.5 34.5 39.4 34.2 28.6 % Extract 0.0 1.0 10.0 15.0 15.0 15.0 in the controls. The concentration factors of Mo for green sunfish and fathead minnows exposed to 18 extract were 1.1 and 0.50, respectively. These relatively low concentration factors indicate that there were high levels of Mo in the 18 extract and that the level of Mo in the fish tissue might increase further with longer exposure. Fathead minnows exposed to extract generated from 17 accumulated Al, B, Cd, Mn, and Ni . The level of Cd in the 17 extract exceeded the primary drinking water standard, and the level of Mn exceeded the secondary drinking water standard (Table 19). The bioconcentration factors of Al , B, Cd, Mn, Mo, and Ni by fathead minnows exposed to the 17 extract were >162, 0.3, 21.1, 68.8, 0.8, and 38.8, respectively. The levels of these elements in the fathead minnows exposed to the 17 extract were at least twice those found in the control fathead minnows. In fact, the levels of five of these six elements (all but Al ) were 5 times those found in the controls. 59 The green sunfish exposed to the 17 extract accumulated the same elements as the fathead minnows although some of these constituents accumulated to a lesser degree. The levels of B, Mo, and Ni present in the green sunfish exposed to the 17 extract were at least twice those measured in the controls- The concentration factors for B, Mo, and Ni in green sunfish exposed to the 17 extract were 0.29, 1.1, and 12.3, respectively. Finally, the composition of the extracts generated from samples 17 and 12 were similar. The accumulation of elements from the 12 extract by the test organisms also was similar to that observed in test organisms exposed to 17. The chemical constituents accumulated to the greatest degree by the fathead minnows were B, Cd, Mn, Mo, and Ni (Table 38). The concentration factors for B, Cd, Mn, Mo, and Ni in fathead minnows exposed to the 12 extract were 0.3, >6.3, 81.8, 0.2, and >22.1, respectively. The green sunfish exposed to the 12 extract accumulated the same chemical constituents as did the fathead minnows, although some of these elements were accumulated to a lesser degree. The levels of B and Mo in the green sunfish exposed to the 12 extract were almost 2.9 and 17.0 times, respectively, those measured in the controls. The concentration factors for B and Mo in green sunfish exposed to the 12 leachate were 0.3 and 0.5. The six most frequently accumulated chemical constituents from the fly ash extracts were Al , B, Cd, Mn, Mo, and Ni . Other chemical constituents were accumulated, but these elements were accumulated to the greatest extent. In most situations, the results of the chemical analyses of the extracts and the LC-50 determinations did not indicate which chemical constituents would be accumulated. The United States Food and Drug Administration (FDA) currently lists Hg, Pb, Cd, As, Se, and Zn at the top of the priority list in its program concerning toxic elements in food (Jelinek and Corneliussen, 1977). Of these, only Hg has an FDA-specified regulatory limit for fish and shellfish (Anonymous, 1974); FDA guidelines for other metals in foods have not been established (Phillips and Russo, 1978). Aluminum is an element which is relatively inert on biological processes, and it rarely presents a human health hazard (Schroeder and Darrow, 1973). Aluminum has a relatively high bioaccumulative tendency in freshwater fish muscle. Consumption of seafoods containing Al presents little risk due to the low toxicity of Al to human beings (Phillips and Russo, 1978). Boron is used in a process for bleaching pulverized wood by the pulp and paper industry (Thompson et al., 1976), as a hardener for other metals (Phillips and Russo, 1978), and as a neutron absorber in nuclear installations (National Academy of Science, 1973). It becomes enriched in fly ash from fossil fuels. Boron generally has a low bioaccumulative tendency in freshwater fish and a low toxicity to aquatic organisms and to humans (Phillips and Russo, 1978). Cadmium is rare in nature, but is highly toxic (National Academy of Science, 1973). Inhalation or ingestion of Cd produces both acute and chronic health effects. Cadmium poisonings in humans resulting from oral consumption or inhalation are well documented (Fassett, 1975; Flick et al., 1971; Voors and Shuman, 1977; American Conference of Governmental and Industrial Hygientists, 1974; Stokinger, 1963; World Health Organization, 60 1972). Cadmium is a dangerous cumulative poison. A concentration factor of up to 1,000 has been reported (National Academy of Science, 1973). Several authors have measured Cd uptake by freshwater organisms. The accumulation of Cd by freshwater fish has been studied in white catfish, Iotaluvus aatus (Rowe and Massaro, 1974); goldfish, Cavaseiue auvatus (Marafante, 1976); bluegill, Lepomis maevoehivus (Mount and Stephan, 1967; Eaton, 1974); zebra fish, Bvaohydanio vevio (Rehwolt and Karimian-Teherani , 1976); stickleback, Gastevosteue aculeatus (Pascoe and Mattey, 1977); guppy, Poedlia reticulata (Kinkade and Erdman, 1975); brook trout, Salvelinis fontinalis (Benoit et al., 1976); rainbow trout, Salmo gaivdmvi (Kumada et al., 1973); and largemouth bass, Miavopterus ealmoides (Cearley and Coleman, 1974). \lery little Cd is accumulated in the edible portions of fishes; it is usually concentrated in the gills, liver, and kidneys. Cadmium in fishes, therefore, does not appear to represent a hazard to human consumers. However, oysters, abalone, and mussels are capable of accumulating extremely high levels of Cd in edible portions (Phillips and Russo, 1978). Manganese has a relatively low tendency for bioaccumulation in freshwater fishes. Manganese has a low toxicity to humans, but poisonings have occurred from excessive exposures to Mn in plants (Berry et al., 1974). Chronic poisoning may result from the inhalation of Mn compounds (Sullivan, 1969). Manganese has been detected in marine and freshwater fishes and has been shown to be accumulated via the food chain in marine and freshwater invertebrates. However, Mn appears to be a relatively nonhazardous element in most waters due to the low toxicity of Mn to humans and aquatic life (Phillips and Russo, 1978). Molybdenum has a low bioaccumulative tendency in fish. Bioaccumulation of Mo by lake trout, Salvelinus mmaycush, was studied by Tong et al. (1974). Molybdenum compounds exhibit a low order of toxicity for exposed workers (American Conference of Governmental and Industrial Hygienists, 1974). Molybdenum does not tend to accumulate in the edible portions of fish and has a relatively low toxicity to humans (Phillips and Russo, 1978). Although Ni is present in considerable amounts in plant and animal tissues, dietary intake of Ni is not harmful to humans. Workers exposed to Ni may develop a sensitivity to it and even dermatitis. Because of Ni's low toxicity to humans, almost no information is available on the accumulation of Ni by aquatic organisms (Phillips and Russo, 1978). In industrial situations Ni dust has been shown to cause lung and nasal cancers in exposed workers (Doll, 1958), and Ni metal can cause eczema in sensitized workers (Browning, 1969). Nickel carbonyl, an intermediate in the nickel refining process (also found in cigarette smoke and a possible product of the incomplete combustion of coal), can cause cancer in rats and humans and represents the primary nickel related hazard to human health (Sunderman and Donnelly, 1965; Schroeder, 1970). The low toxicity of nickel when orally ingested has been demonstrated for several animals (Underwood, 1971). Nickel constantly occurs in food, many waters, and all forms of life, both marine and terrestrial (Bowen, 1966). The results of this study demonstrated that fly ash extracts were acutely toxic to fathead minnows and that various trace elements are accumlated in both 61 fathead minnows and green sunfish. Of the six chemical constituents most commonly accumulated in the fish, Cd appears to be the most toxic. 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