Chemical and toxicological properties of coal fly ash - University of ...

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The authors thank Susan D. Kamp and Shirley A. Lowe for their assistancewith the toxicity and bioaccurnulation studies, Ivan G. Krapac for hisassistance with the extract characteri ations, Re R. Ruch and theAnalytical Chemistry Section for the chemical data, Richard D. Harvey forthe x-ray diffraction work, and Richard Larson, Institute for EnvironmentalStudies, University of Illinois, for GC/Mass spectral analyses.A1 so acknowledged i s the cooperat ion of the I1 1 inoi s Power Company, CentralI1 1 inois Public Service Company, Commonwealth Edison Company, and LouCooper of Rockwell International in collecting fly ash samples.Thi s project was partial ly supported by the I1 1 inoi s Department of Energyand Natural Resources (DENR) under Contract No. 90.025. The authorsgreatly appreciate the support of W. Murphy and A. Burkard of DENR.John J. Suloway is now employ by Charles T.Massachusetts 02199; Rudol ph Schul ler is empValley Forge, Pennsylvania 19481.Cover design: William RoySuloway, John J.Chemical and toxicological properties of coal fly ash /John J.Suloway and others. - Champaign, ill. : State Geological SurveyDivision and State Natural History Survey Division, July 1983.70 p. ; 28 cm. - (Illinois-Geological Survey. Environmentalgeology notes ; 105)1. Fly ash-analysis. 2. Fly ash-environmental aspects. I. Title.1 I. Series.Printed by authoity of the State of //linois /l983/2UOU

V SURVEYatural Resources Building607 East Peabody DriveChampaign, Illinois 61820STATE GEOLOGICAL SUobert E. Bergslrom, ChiefNatural Resources Building615 East PeabodyChampaign, Illinois 61820TAL GEOLOGY NOTES 1051983

PURPOSE AND OBJECTIVES 2SUMMARY OF STUDY FIND!RECOMMENDATIONS 4METHODS AND MATERIALS 5Sample collection and preparationAnalytical methods for inorganic, mineralogical, and physical propertiesAnalytical methods for organic matter characterizationSolvent extractionPyrolysis studyExtraction methodsMethods for toxicity tests and bioaccumulation experimentsPHYSICAL AND INORGANIC CHARACTERIZATION OF THE FLY ASH SAMPLES 12Particle size and specific gravityChemical and mineralogical compositionFly ash classificationsSolvent extractionPyrolysis studieslZATBON OF SELECTED FLY ASH SAMPLES 18CHARACTERlZATlONl OFU.S. EPA Extraction ProLONG-TERM EQUlLlBTOXICITY TESTS 46BIOACCUMULATION EXPEREFERENCES 62FIGURESAreal extent of Pennsylvanian strata in which coal resources of the Illinois Basin are foundand the approximate location of the parent coals of fly ashes I1 through 19. 7HPLC of a known mixture of phenols and polyaromatic hydrocarbons referenced to toluene. 9The particle size distribution in fly ashes, I2,16, and 17. 12The 12 fly ashes plotted on the Sialic-Ferric-Calcic diagram for classification. 17The 12 fly ash samples and 27 other fly ash samples from the literature plottedon the Sialic- Ferric-Calcic diagram for classification. 19Infrared spectrum of the benzene-extractable organic material in fly ash 18. 20Infrared spectrum of the benzene-extractable organic material in fly ash W1. 21lnfrared spectrum of the LC-1 fraction from the benzene extract of fly ash W1. 22HPLC chromatogram of the LC-2 fraction from the benzene extract of fly ash W1. 22lnfrared spectrum of the LC-3 fraction from the benzene-extractable organic matter in fly ash W1. 23Gas chromatogram of the LC-3 fraction from the benzene-extractable organic matter in fly ash W1. 23HPLC chromatogram of the LC-3 fraction from the benzene extract of fly ash W1. 24lnfrared spectrum of the LC-4 fraction from the benzene extract of fly ash W1. 24HPLC chromatogram of the LC-4 fraction from the benzene extract of fly ash W1. 25l nfrared spectrum of the LC-5 fraction from the benzene extract of fly ash 18. 25HPLC chromatogram of the LC-5 fraction from the benzene extract of fly ash W1. 26lnfrared spectrum of the LC-6 fraction from the benzene extract of fly ash W1. 26HPLC chromatogram of the LC-6 fraction from the benzene extract of fly ash W1. 27Gas chromatogram of the noncondensable hydrocarbons produced by pyrolysis at 450°C of fly ash 12. 30Gas chromatogram of the noncondensable hydrocarbons produced by pyrolysis at 450°C of fly ash 13. 30Gas chromatogram of the noncondensable hydrocarbons produced by pyrolysis at 450°C of fly ash W2. 31Gas chromatogram of the noncondensable hydrocarbons produced by pyrolysis at 450°C of fly ash 15. 31Gas chromatogram of the condensable organics produced by pyrolysis at 300°C of fly ash W1. 32Changes in the concentrations of selected aqueous constituents in the LTE extract of fly ash I3 with time. 42Changes in the concentrations of selected aqueous constituents in the LTE extract of fly ash I7 with time. 42Changes in the concentrations of selected aqueous constituents in the LTE extract of fly ash W2 with time. 43

TABLESSummary of the origin and general characteristics of the 12 fly ash samples. 6iParticle size data for the 12 fly ashes by pipet analysis and specific gravity. 13Mineralogical composition of the 12 fiy ash samples. 14Chemical composition of the 12 fly ashes: major and minor constituents. 14Sulfur species in the 12 fly ashes. 15brace constituent concentrations in the 12 fly ashes. 26Fly ash sample classifications. 48Carbon, sulfur, and benzene-extractable organic matter of selected fly ashes. 20Liquid chromatographic fractionation of the benzene extracts of four fly ashes. 21Hydrocarbons detected in the noncondensable pyrolysates. 28Organic components detected in the condensable pyrolysates of the fly ashes. 29Chemical constituent concentrations obtained by the proposed U.S. EPA Extraction Procedure (EP)performed on the 12 fly ashes. 34Contaminant concentrations in EP extracts qualifying for hazardous waste classification. 35Change in chemical composition as a function of time of fly ash I2 extract generated by long-term(142 days) equilibration. 37Change in chemical composition as a function of time of fly ash I3 extract generated by long-term(141 days) equilibration. 38Change in chemical composition as a function of time of fly ash I7 extract generated by long-term(1 06 days) equilibration. 39Change in chemical composition as a function of time of fly ash I8 extract generated by long-term(140 days) equilibration. 40Change in chemical composition as a function of time of fly ash W2 extract generated by long-term(140 days) equilibration. 49Constituents in the long-term equilibrations exceeding EPA interim primary and secondary drinkingwater standards or irrigation water criteria as a function of time. 45The percent mortality of a 1 -to-6-day old fathead minnow fry (Pimephaiespromelas) resulting from96-hour exposures to full -strength extracts generated from five fly ashes. 46The LC-50 values, amount of dilution necessary to eliminate mortality, and the initial pH values for extractsgenerated from five fly ashes. 47The range of concentrations and recommended water quality levels for chemical constituents measured in testsolutions of W2. 48The range of concentrations and recommended water quality levels for chemical constituents measured in testsolutions of 13. 49The range of concentrations and recommended water quality levels for chemical constituents measured in testsolutions of I?. 50The range of concentrations and recommended water quality levels for chemical constituents measured in testsolutions of 12. 56The mean initial lengths and weights of adult fathead minnows used in the bioaccumulation experiments. 52The mean initial lengths and weights of juvenile green sunfish used in the bioaccumulation experiments. 53Initial mean total lengths and weights of adult fathead minnows exposed to extracts from five fly ashesand a control. 53initial mean total lengths and weights of juvenile green sunfish exposed to extracts from five fly ashesand a control. 54Comparison of the mean initial lengths and weights between the control test organisms and the organismsexposed to fly ash extracts. 54The mean final lengths and weights of juvenile green sunfish used in the bioaccurnulation experiments. 54The mean final lengths and weights of adult fathead minnows used in the bioaccumulation experiments. 55Final mean total lengths and weights of adult fathead minnows exposed to extracts from five fly ashes anda control. 55Final mean total lengths and weights of juvenile green sunfish exposed to extracts from five fly ashes anda control. 55Comparison of the mean final lengths and weights between the control test organisms and the organismsexposed to fly ash ex tracts. 56Differences between initial and final mean lengths and weights of adult fathead minnows exposed to extractsfrom five fly ashes and a control., 56Differences between initial and final mean lengths and weights of juvenile green sunfish exposed to extractsfrom five fly ashes and a control. 56The mean concentrations of various chemical constituents measured in adult fathead minnows exposed toextracts from five fly ashes and a control. 58The mean concentrations of various chemical constituents measured in juvenile green sunfish exposed to extractsfrom five fly ashes and a control. 59

During the late 1970s shortages of natural gas, fuel oil, and gas01 inedramatically demonstrated the need for t e increased use of coal byelectric utilities. Although predictions vary, the National CoalAssociation forecasts an increase in coal usage from 787 million metrictons in 1976 to approximately 1.5 billion metric tons by 1985. Thecombustion of coal produces solid wastes composed primarily of thenoncombustible mineral matter (ash) present in the coal. Fly ash is thatportion of ash that is small enough, in terms of particle size, to beentrained in the flue gases and carried away from the site of combustion.Of the 67.8 million tons of ash produced in the 1J.S. in 1977, approximately48 million tons was fly ash (Faber, 1979). Ash production may reach 125million tons by 1990 and may increase by a factor of four in the next 20years (Faber, 1979). In Illinois, the three major electric utilitiesgenerated an estimated l,867,OO0 tons of fly ash in 1979 (Roy et al.,1981).The imp1 icat ions of the Resource Conservation and Recovery Act (RCRA) of1976 have focused attention on coal fly ash and its subsequent disposalproblems. The prevalent method of fly ash disposal is by sluicing the ashslurries from the power plants into some type of natural or man-made basinwhere the ash settles. The resulting supernatant may contain potentiallytoxic trace constituents, leached from the fly ash, which could poseproblems to the aquatic ecosystems into which they eventually flow.Several studies assessing the environmental impact of coal fly ash havedealt largely with fly ashes generated from coals from the Appalachianregion (Chu et al., 1978; Furr et al., 1977; Klein et al., 1975; Plank etal., 1975) and from western bituminous, subbituminous, and lignite coals(Elseewi et al., 1980; Mann et al., 1978; Ondov et al., 1979; Swanson etal., 1976).Fly ashes produced by the combustion of coals from the Illinois coal basinhave also been studied (Cox et al., 1978; Davison et a1 ., 1974; Griffin etal., 1980; Linton et al., 1976; Natusch et ale, 1977; Theis and Mirth,1977). However, as indicated in literature reviews by Adriano et al. (1980),Page et al. (1979), and Roy et al. (1981), the physicochemical propertiesof fly ash may vary from plant to plant and even from different boilerswithin a particular plant. Moreover, 1 aboratory leaching and disposal pondstudies of the aqueous chemical interactions with fly ashes generated fromIllinois Basin coals have also produced varying results. Additional workwith Illinois fly ashes is needed in order to assess the possibleenvironmental impacts of coal fly ash disposal.Elevated pH levels of fly ash leachates have been shown to be toxic toaquatic organisms (Cairns et a1 ., 1972; Wasserman et a1 ., 1974). Otherstudies (Birge, 1978; Thompson, 1963) have examined the role of traceelements in the aquatic toxicology of leachates from coal and fly ash.Trace elements leached from fly ash can accumulate in the ti,ssues of fishand fish forage (Cherry et al., 1976; Ryther et al., 1979). Contaminatedfish from cooling lakes or other aquatic ecosystems exposed to fly asheffluent may pose potential health hazards to fishermen.

The overall purpose of this investigation was to provide information thatmay be of assistance in predicting the environmental impacts of coal flyash disposal. Data resulting from this investigation should be useful toutilities, consultants, and state, local, and federal agencies concernedwith 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 andaqueous solubility of fly ashes derived from Illinois Basin coals,and compare these fly ashes to those generated from western U.S.coal s.Determine if the extracts generated from fly ash were acutelytoxic to fishes.- Determine if the soluble trace metals in the fly ashextracts were accumul ated by fishes under 1 aboratoryconditions.Nine fly ash samples generated from Illinois Basin coals--predominantly silts (USDA classification)--varied in color from verydark grayish brown (10YR Munsell soil colors) to gray (2.5Y - 5Y). Theaverage specific gravity of the nine samples was about 2.4. Two flyashes generated by the combustion of western U.S. lignite coals werelighter in color (light gray) and had greater specific gravities (about3.05), whereas a western subbituminous coal fly ash had a darker gray(10YR) color and a specific gravity of 2.2.The general mineralogical composition of the Illinois Basin fly asheswas comparable to that of fly ashes generated from eastern 1J.S.bituminous coals, as reported elsewhere. They were essentiallyspherical particles composed of an amorphous alumino-silicate glass,quartz, mu1 1 i te (A16Si 2013), and iron oxides. The subbi tuminouswestern ash was similar in mineralogical composition to the Illinoissamples, except for the presence of calcite in the western ash. The twowestern lignite samples had higher concentrations of some alkalinemetals and matrix sulfur, primarily in the form of anhydrite (CaS04)and pericl ase ( MgD) .Most of the matrix sulfur in all 12 samples existed as sulfatecompounds. The average ratio of sulfate S to sulfide S in the Illinoissamples was about 5:l.The trace constituent concentrations in the samples were highlyvariable, but the Illinois fly ash samples generally had greaterconcentrat ions of (in decreasing order of concentrat ion) Zn , N i , Rb,Cs, Cr, Co, U, Ge, Mo, V, Li, Cd, TI, Sm, Pb, Be, Eu, Tb, Ga, Ce, As,

Cu, Lu, and Sc than did the three western fly ashes. Similar trendsfor certain transitional metals have been reported elsewhere for ashesfrom eastern and western coals.5. IJnder 1 aboratory conditions, the seven gray samples produced a1 kal ineextracts, whereas the two reddish fly ashes generated acidic extracts.Color may be useful in predicting the initial pH of a fly ash slurry orleachate in the field-6. The ratio of matrix CaO to SO3 may influence the pH of extractsduring the initial stages. Short-term acidic extracts were associatedwith samples having a CaO/S03 ratio of less than 2; alkalinesolutions were produced from samples having matrix CaO/S03 ratiosexceeding 2.7. The general trend of EP solubility for the Illinois Basin fly ashes wasfound to be S04-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 thesubbituminous fly ash was S04-S > B > As > Ca > Se > Mg, Zn > Mn > Na> K, Ba, and for the two lignite fly ashes, S04-S > 6 > K, Mo >> Se,Na > Ca > Zn, Mg > Be, Cr > Mn, Si, Ba.8. Although all fly ashes are currently exempt from the list of hazardouswastes under RCRA, EP data indicated that one of the 12 samples wouldbe classified as a hazardous waste by present criteria. One acidic flyash contained enough soluble Cd to classify it as a hazardous waste ifthe 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, theconcentrations of several potential pollutants began to decrease almostimmediately after the first day of extraction, and this decreasecontinued for 60 to 120 days until steady state conditions developed.The pH of the acidic extracts became neutral after about 3 to 5 weeksand consequently several potential pollutants were less soluble in theresulting nonacidic solution. In all five long-term equilibrations,several constituents reached a metastable equilibrium, persisting atinvariant concentrations for the latter part of the extractioninterval .10. The specific concentrations of some of the inorganic constituents inthe solutions (prior to equilibration and after steady state conditionsdeveloped) exceeded the EPA interim primary or secondary drinking waterstandards and irrigation water cri teri a.11. Organic compounds identified in the fly ashes were only slightlysoluble in the aqueous extracts. Although some of the organics presentin the samples are on the priority pollutant list, they are present insuch low concentrations that it is doubtful that they would pose anysignificant environmental problems during landfilling operations orpond i n g .12. Fly ashes--particularly acidic types--are probably most toxic toaquatic ecosystems when initially slurried to disposal ponds; theirtoxicity may decrease with time. If the potential contaminants achieve

steady state conditions in the disposal pond, they may have longresidence times in the ash effluent, thus increasing the probability ofbioaccumulation by aquatic organisms.13. Of the 12 fly ash samples evaluated, five were selected for toxicitytesting 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 toxicityof the fly ash extracts to fish were pH, Al, ionic strength, and Zn.Because of the complex composition of some extracts and the unknownsynergistic and antagonistic effects of the chemical constituents ofthe extracts, it was not possible from these experiments to determinewhich chemical constituents specifically were responsible for theobserved mortality.15. The fly ash extracts were diluted to levels presumed subacutely toxicfor use in bioaccu~nul at ion experiments. The growth of fathead minnowsand green sunfish exposed to these diluted fly ash extracts was notsignificantly different from that of control test organisms exposed tofiltered tap water under similar conditions.16. The fathead minnows and green sunfish accumulated similar elements fromthe fly ash extracts; the six chemical constituents most commonlyaccumulated from fly ash extracts were Al, B, Cd, Mn, Mo, and Ni. Ofthese six chemical constituents, Cd appeared to be of greatestimportance because of its highly toxic nature.1. An apparent relationship was observed between the initial pHcharacter of a fly ash leachate and its color and the matrixCaO/S03 ratio in the solid waste. Further study of the less commonlyproduced acidic high-iron fly ashes should be done.2. The long-term equilibration (LTE) extraction procedure was designed tosimulate equilibrated ash ponds. Although obtaining representative pondsamples is difficult, such field work should be done to assess theaccuracy of the LTE procedure.3. Fly ash laboratory extracts often undergo complex changes in chemistrywith time and should be studied to determine which mineral phasescontrol the aqueous solubility of the components. The chemistry ofslurry water and disposal ponds should also be studied and modeled todetermine whether the same types of changes that occur in laboratoryextracts occur in the field,4. Grab samples were collected from only nine power plants, seven of whichwere in Illinois. To provide a more complete picture of fly ashcomposition and variability, samples from other Illinois power plantsand from other states should be studied.5. The scope of the ecological analyses of fly ash in this study consistedof acute static bioassays using fathead minnow fry and bioaccumulation

experiments using fathead minnows and green sunfish. It is appropriateto expand the scope of ecological analysis to a multi-tier approach(Brown and Suloway, 1982; Lee et al., 1979) including bioaccumulation,bioconcentration, and biomagnification experiments. Several species oftest organisms representing different trophic levels should be used inchronic or subchronic bioassays.6. A battery of health effects tests should be conducted to evaluate eachfly ash and its extracts. The U.S. EPA has recommended (for a level 1assessment) that solid wastes be tested for the presence of microbialmutagenicity, rodent acute toxicity, and cytotoxicity. The specifictests include the Ames Test, the Rabbit A1 veol ar Macrophage (RAM)assay, the Human Lung Fibroblast (MI-38) Assays, and acute toxicitybioassays 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.A summary of the origin and general characteristics of grab samples of 12fly ashes collected for this study is given in Table 1. All of the sampleswere collected from the hoppers below the electrostatic precipitators atnine individual power plants. Two samples, each derived from differentboilers, were collected at each of three of the facilities.Nine of the fly ash samples, identified as I1 through 19, were generated bythe combustion of Illinois Basin coals (predominantly the Herrin No. 6 coalseam) in Illinois and Indiana. One fly ash (Wl) was produced by a powerplant in Illinois using a low-sulfur subbituminous coal from Colorado(Fishcreek Seam), and the remaining two fly ashes (W2 and W3) were fromplants outside Illinois using lignite from western North Dakota. Figure 1shows the areal extent of the Illinois Basin and the approximate locationof the parent coals of fly ashes I1 through I9 (coals from two mines wereused to generate fly ash 15). All chemical and solubility studies weredone with the bulk samples as taken from precipitator hoppers. The bulksamples were riffled to insure that representative samples were used foreach experiment.s for inorganic, mineralogical, anThe 12 solid wastes were analyzed both chemically and mineralogically.Chemical analyses of the samples for Si, Al, Mg, Ca, K, Fe, Ti, and P wereperformed 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 activationanalysis. Mercury determinations were carried out by neutron activationwith radiochernical separation. Boron, Cu, Ge, Li , Mo, Pb, Sn, and Vconcentrations were measured by optical emission spectrochemicalprocedures. A detailed discussion of sample preparation, detection limits,and procedures for these techniques can be found in Gluskoter et a1.(1977). The sulfur determinations were done by ASTM method 0-2492, and

total carbon determinations were carri'ed out by IS0 method 609-1975E.mineralogy of the samples was determined by x-ray diffraction with aPhil ips Norelco x-ray diffractometer using CuKa radiation (Russel 1 andRimmer, 1979).TheNost of the chemical analyses of the supernatant solutions were determinedby inductively coupled argon plasma spectrometry (ICAP) with a Jarrell -AshTable '1. Summary of the origin and general characteristics of the 12 fly ash samples.Color of Location of Location ofFly ash samplea coal source power plant Boiler typegrayish brown2.5Y 6/2very darkgrayish brown10YR 31'2IllinoisIllinoisIndianaIllinoisccyclonepulverizedpul ver i zedIndianaI1 1 i noi scpulveri zedgrayish brown2.5Y 5.512IllinoisI1 linoispulverizedIllinoisIllinoispu1 veri zedvery darkgrayish brownlOYR 312IllinoisIllinoiscycloneI1 linois11 1 inoisdpul ver i zedI1 1 inois~llinoisdpul veri zedgraylOYR 611light gray2.511 712Co 1 or adoN. DakotaIllinoisMi nnesotapul veri zedpulverizedgray - lightgray2.5Y 6.512M. DakotaN. DakotacycloneaDry Munsell soi 1 colorsbc,d~amples indicated were taken from same individual power plant but werederived from different boilers.

Figure 1. Areal extent of Pennsylvanian strata in which coal resources of the l llinois Basin are found and the approximatelocation of the parent coals of fly ashes I1 through 19.Model 975 Plasma AtornComp. The constituents determined by ICAP were A1 ,As, €3, 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 instrumentare discussed in a Fisher Scientific Company publication by the Jarrell-AshDivision (1978). Sulfate content was measured turbidi~netrical ly (StandardMethods, 1975). Alkalinity was determined by titrations with dilutesulfuric acid, and oxidation-reduction potential (Eh), pH, and electricalconductance were measured by electrodes (1J.S. EPA, 1974).Most of the samples were characterized in terms of particle sizedistribution by pipet and wet sieving methods (Soi 1 Conservation Service,1972). Specific gravity determinations were made by ASTM method C128.Analytical methods for organic matter characterizationSolvent extraction. The organic material in the solid fly ash samples wasextracted with benzene, using a large (70inm x 300mm body) Soxhletapparatus. 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

y passing the extract through a column of activated copper according to amethod described by Blumer (1957). After removal of the sulfur, the finaltraces of solvent were removed with gentle heat (50°C) under a stream ofdry nitrogen. The benzene-extractable material s, determinedgravimetrically, were denoted as "total extractable organics."The extracts were separated into seven fractions according to the U.S. EPALevel 1 (Revised) Procedure for Organic Analysis (U.S. €PA, 1978). Thisseparation was done by liquid chromatography (LC) on a silica gel coluinnusing a gradual gradient of solvents from nonpolar to polar. An infraredspectrum was run on each extract and on each LC fraction. Gaschromatography (GC) , high pressure 1 i quid chromatography (YPLC) , and gaschromatography-mass spectroscopy (GC-MS) were used to further characterizethe organic fractions.PyroZysis study. A 5- to 10-gram sample of fly ash was placed in thebottom of a 300-mm x 13-mm-ID Pyrex tube, and a wad of organic-free quartzwool was positioned just above the fly ash to act as a retainer. Thediameter of the tube was then constricted by heating with an oxygen-naturalgas torch just above the quartz wool retainer. The top of the tube wasthen sealed with a skirted-septum stopper and the tube was evacuated forseveral minutes, using a vacuum pump linked to the tube via a hypodermicneedle through the septum.Following the evacuation, the sample end of the tube was heated in ahorizontal position at 450°C in a tube furnace while the upper end of thetube was cooled with powdered dry ice. After a 5minute heating period thetube was immediately sealed and separated at the point of the constrictionby melting the glass with an oxygen-natural gas torch. Thus, the volatileorganics were condensed and trapped in the upper, cooled portion of thetube.The headspace gas (noncondensable at room temperature) was analyzed by GC,and the components were identified by comparison of retention times withknown standards. The condensable portion was taken up in isooctane andanalyzed by GC; one sample (derived from fly ash W1) was also analyzed byGC-MS. The major components in the samples were deterained by comparisonwith the GC-MS analysis and with the retention times of referencestandards.The infrared spectra were obtained with a Perkin-Elmer Model 283B InfraredSpectrophotometer. The samples were mounted as neat smears or thin filmsbetween sodium chloride prisms. Normally the spectra were obtained byusing a 12-minute scan time with response setting 1 and slit program 6.Interpretation of the spectra was made with the help of the followingreferences: Barnes et ale (l944), Be1 lamy (l958), Nakanishi (l962),Si lverstein and Bassler (l963), and Szymanski (1967).A rough indication of the absorption intensities in the IR spectra obtainedfrom the fly ash samples is reported in the Results Section; the absorptionintensities are given as "strong," "medi um," and "weak". "Strong" isdefined as the strongest absorption in a given spectrum. "Medium" and"weak" designations relative to the strongest absorption within the samespectrum are then determined.

A Perkin-Elmer Sigma 1 gas chromatographic system with a flame ionizationdetector was used for GC analysis. A 2-rn x 3mm stainless steel columnpacked with Chrornosorb 102 was used for the noncondensable gas analyses.The carrier gas (helium) flow rate was 30 mLfmin, the injection porttemperature was 125"C, and the detector temperature was 200°C- The columnoven temperature was programmed for an initial hold of 50°C for 1 minute, atemperature rise to 170°C at 10°/min, and a final hold at 170°C for 5minutes.A 1.25-m X 3-mm stainless steel column packed with 3% SP-2100 on 100/120mesh Supelcoport (Supelco Inc., Bellefonte, PA) was used for the analysisof the condensables from the pyrolysis study and for the extracts andsubfractions of the extracts. The carrier gas (helium) flow rate was 35mL/min, injection port temperature was 250°C, and the detector (FID)temperature was 315°C. The column oven temperature was programaed for aninitial hold at 100°C for 2 minutes, a temperature rise rate of 4"fmin to260°C, with a final hold of 10minutes. The latter colu,nn and conditionswere also used for the Level 1 LC fractions.A Perkin-Elmer Series 3 Liquid Chromatograph with UV detection was used forHPLC determinations. An A1 tex Ultrasphere@ ODs, 5-pm sphere size, 4.6 x250-mm (Beckman Instruments, Inc., Berkeley, CA) HPLC column was used. A5-cm guard column with LC-18 pel 1 icular packing (Supelco, Inc., Bellefonte,PA) was placed between the sampling valve and the top of the analyticalcolumn. The elution solvent was methanokwater (80:209 v:v) with a1 -mL/min flow rate under isocratic conditions. The order of elution underthese parameters was shown to be phenols followed by toluene and thenaromatic and polyaromatic hydrocarbons (PAHs) with ascending molecularweights (Fig. 2). Toluene was used as an internal reference standard.Figure 2. HPLC of a known mixture of phenols and polyaromatic hydrocarbons referenced to toluene. Peakidentification: 1. phenol; 2. p-cresol; 3. 2,3-dimethylphenol;4. 2,4,5-trimethyphenol; 5. toluene;6. phenanthrene;7. pyrene; 8. chrysene; 9. benzo (a) pyrene.

The GC-MS analyses were performed by t e Institute for EnvironmentalStudies at the University of Illinois, Urbana, using a Hewlett-Packard 5985AGC/MS/data system equipped with a capi 11 ary col umn coated with SP-2100.The proposed U.S. EPA Extraction Procedure (EP) (U.S. EPA, 1980) was usedto study the solubility of the 12 fly ashes. The EP was intended to serveas a quick test for identifying wastes capable of posing potentialpollution hazards when improperly disposed. The EP method calls for mixing200 g of a solid waste with 3200 mL of deionized water and agitating themixture by a shaking motion for 24 hours. During the 24-hoursolubilization 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 aqueousp5ase 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, thesolid and liquid phases were separated by filtration, and the filtrate wasdiluted to 4,000 mL with deionized water. In this study, the mixtures werefiltered through a 0.45-pm-pore-size Millipore@ filter membrane, and thefiltrates (extracts) were acidified to a pH

The acute bioassays were conducted at a constant temperature (21' 2 1°C)and photoperiod (16L-8D) in an environmental chamber. Test organi sms werenot fed, and the solutions were not aerated during the bioassay. Duringa1 1 bioassays, pH, dissolved oxygen, and temperature were moni tored.Mortal ity data were collected at 24, 48, 72, and 96 hours after thebioassays had begun. Diluted and undiluted extracts were sampled at theconclusion of the bioassays for chemical analyses.The acute toxicity of the five undiluted LTE extracts was determined withthe screening procedure. The LC-50 determinations demonstrated therelative acute toxicities of the solutions and were used to identify the -nost toxic extracts, to estiinate the dilution necessary to eliminatemortality during a 96-hour static bioassay, and to establish extractconcentrations for use in the bioaccumulation experiments. LC-50 valueswere calculated using graphic methods (Litchf ield and W i lcoxon, 1949).In the bioaccumulation experiments for each fly ash extract, five adultfathead minnows were put into each of two 60-liter aquaria containing 40liters of diluted extract. Control tanks contained aerated, filtered tapwater. The five fish from each aquarium jointly constituted a singlereplicate for tissue analysis. This procedure was repeated using juvenilegreen sunf i sh (~e~ornis cyaneZ2us). Rioaccumul at ion experiments wereconducted at a constant temperature (23" - + 3°C) and photoperiod (16L-8D) ina large environmental chamber.To insure the size similarity of test organisms used in eachbioaccumulation experiment, each fish was weighed and measured before thetest. At the conclusion of the experiment or at death if prematuremortal i ty occurred, the fish were ~ eghed i and measured agai n, frozen, andstored for chemical analysis. Water samples were analyzed weekly tomonitor fluctuations in the chemical composition of the diluted leachates.Temperature was inoni twed dai ly and dissolved oxygen and pH were rnoni toredtwice per week. The fish were fed frozen brine shrimp daily and excessfood was removed each day. Tests were conducted for 30 days. One-wayanalysis of variance (ANOVA) was used to determine if test organisms usedin each replicate were significantly different in size. ANOVA was alsoused to compare final lengths and deights of fish with initial values todetermine if the test organisas exposed to the extracts grew at differentrates than those of the controls.The two replicate frozen green sunfish and fathead minnow groups for eachfly ash extract and control were freeze-dried whole, using a Virtis Unitrap10-100 Freeze Dryer with a Welch Duo-Seal Model 1402 Vacuum Pump, placedinto polystyrene bottles with several glass beads, and homogenized using aSpex 5000-11 "lxer Mill. Polyethylene bottles were used to store thehomogenized samples.Total digestion was required to analyze the fish samples for chemicalconstituents. A 5:l mixture of HNO3 and redistilled perchloric (HC104)acid was added to 1-g subsamples of fish in 150-mL round bottom distillationflasks. Flasks were heated on a Kontes Rotary Kjeldahl DistillationApparatus until HClO4 fumes began to form. After cooling, the digestedsamples were transferred to 50-mL volumetric flasks and diluted to volume

with ultrapure water. The final HClO4 concentration (5%) was within therange compatible with ICAP techniques. Diluted solutions were stored in60-mL polyethylene bottles and refrigerated unt i 1 analysi s.Results for the particle size determinations are presented in Table 2.Most of the samples fell within the silt category (USDA soilclassification), predominantly in the 8- to 31-micron range. The siltsizedcomponent of the ashes (less than 62-micron- to 2-micron-diameterparticles) ranged from 53 to about 90 percent (Table 2). The particle sizedistribution of three of the fly ashes is shown in Figure 3; these sampleswere selected for the illustration as best demonstrating the variabilityand range of the textural distributions of the samples. Fly ash I 2 was asilt loam; I6 and I7 were both loams. The specific gravity of the flyashes (Table 2) ranged from 2.2 to 3.1 c~/crn3; the Illinois Basin samplesaveraged about 2.4. Comparable measurements have been reported elsewhere(EPKI, 1979).Chetnical and mineralogical analyses of the fly ash sasples indicated thatthe ashes generated from I1 1 inoi s Basin coals (samples I 1 -19) consistedDiameter (pm) ISGS 1981Figure 3. The particle size distribution in fly ashes 12, 16, and 17.

essentially of Si, Al, and Fe as amorphous alumino-silicate glass, quartz(Si02), mullite (A16Si2013), and various iron oxide species such asmagnetite (Fe304) and hematite (Fe203) (Table 3). Comparable resultswere reported by Natusch et al. (1977) and Griffin et al. (1980) for otherI1 linois Basin fly ashes. A small amount of lime (Ca0) was also detectedby x-ray diffractometry in four of the Illinois Basin samples. Silicon,reported as percent silica (Si02), ranged frorn about 43 to 52% (Table 4).A1 urninum and Fe, reported in their oxide forms, represented approximately20% of the material. The reddish-brown colors (IOYR, dry Munsell soilcolors) associated with I2 and I7 were probably due to the Fe levels, about2 to 3% greater than the average levels of the seven other Illinois Basinfly ashes lacking the reddish-brown hues and having 2.5Y-5Y colors. TheCa, Mg, Na, Ti, K, and S together (as oxides) constituted about 10% of thesamples. Other minor constituents (less than 0.01%) were Ba, Sr, P, andMn. The total S content of the Illinois Basin samples ranged frorn 0.32 to1.06% (Table 5). Most of the total S (62 - 92%) was present as sulfatecompounds. The remaining S (8 - 38%) was in sulfide forms. The averageratio of sulfate4 to sulfide-S in the Illinois Basin samples was about5:1.In contrast to the Illinois Basin fly ashes, the two lignite-base samples(W2 and W3) consisted of about 30% Si02, 25% CaO, and 8% MgO. Themineralogical composition of these samples was predominantly periclase(MgO) , quartz ( SiOz), and anhydri te (CaSO4). The 1 ignite-base flyTable 2. Particle size data for the 12 fly ashes by pipet analysis (percent weight) and specific gravity.Particle size (p)SpecificFly ash >62 31 -62 16-31 8-16 4-8 2-4 1-2 0.5-1

Be 3. Wlir~eraiogical composi'tion of the I2 fly ash samples.MineralQuartz (SiO2) X X X X ~ X X X X X XMu1 1 i t e (A1 6Si 2013) x x x x x x x x"Magnet i t e -mag hemieesuite" (Fe304-Fe203)Hematite (Fe203) ~ ~ x x x x ~Lime (CaO) x x x x xCalcite (CaC03)xPericl ase (MgO) x xAnhydri te (CaS04) x xUnidentified x xChemical composition of the 11 2 fly ashes: major and minor constituents (percent weight).ChemicalFly ashconstituent I1 P 2 I3 I4 15 I6 I7 I8 I9 Ld 1 W2 W 3Si 02Ti 02203Fe203CaOMg 0Mn 0Na20K20p2059'3Total CHz0 -

Table 6. Sulfur species in the 12 fly ashes (percent weight).Fly ash Sulfate S Sulfide S Total Sashes were also characterized by greater amounts of Na, Ba, and Sr, whileA1 and Fe were lower as compared with the amounts in the Illinois Basinsamples. These findings are similar to those reported in the coal and flyash literature, in which higher levels of Ba, Ca, Mg, Na, and Sr have beengeneral ly associated with western l ignite coal s ( Abernathy, 1969; Furr etal., 1977; Gluskoter et al., 1977; and Natusch et al., 1977).The specific gravities reported in Table 2 for the Illinois Basin fly ashesare close to the specific gravity of pure quartz (GO2), 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 thedominant mineral s--periclase (MgO), with a density of 3.58 and anhydri te(C~SO~), at about 2.92.The trace constituent concentrations in the fly ashes (Table 6) wereextremely variable. Arsenic in the I1 linoi s Basin samples (11-19) rangedfrom 21 to 360 mg/kg; Co varied from 38 to 88 mg/kg. Zinc was the mostvariable, ranging from 90 to 2,100 mg/kg. In spite of the variable natureof fly ash, the Illinois Basin samples can be broadly characterized ashaving greater trace constituent concentrations than the three westernsamples have. These trace constituents are (in order of decreasing averageconcentrations in the solid) Zn, Ni, Rb, Cs, Cr, Co, U, Ge, Mo, V, Li, Cd,TI, Sm, Pb, Be, Eu, Tb, Ga, Ce, As, Cu, Lu, and Sc. Manyof theseelementshave been cited in the literature as generally occurring in greaterconcentrations in eastern Paleozoic coals and their ashes than in westerncoals of Mesozoic and Terti ary-age (Abernathy, 1969; Gl uskoter et a1 . ,1977; Natusch et al., 1977; and Page et al., 1979). The averageconcentrations of Hf, Sb, Se, Ta, Th, W, and Yb in the fly ashes were notfound to correlate with coal type in this study.

Table 6. Trace constituent concentrations (rnglkg) in the 12 fly ashes.Fly ashConstituent I1 I2 I3 I4 I5 I6 I7 I8 19 W 1 N2 W3ly ash classif icatisnsThe 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 chemicalcomposition of the solid waste and the pH of an askdistilled water mixture(I:) Seven of the nine Illinois Basin fly ashes were alkaline Modicsilts (Fig. 4). Fly ashes fitting into the Modic field have a sialiccornponent (% weight of Si02 + A1 203 + TiOz), which indicates that theseelements consist of a combination of from >48% to 88% of the total mass.The ferric cornponent (% weight of Fez03 + S03) is from 0 to 23%, and theCalcic component (CaO + MgO + Na?O + K20) is from 0 to 29%. These seven

% Calcic Group -Figure 4. The 12 fly ashes plotted on the Sialic-Ferric-Calcic diagram for classification.ISGS la3fly ashes produced alkaline leachates with pH values greater than 9.0 andhad silt textures. The other two Illinois Basin samples differed inchemical composition: I2 was an acid C-Modic silt loam, and I7 was an acidC,Zn-Fersic silt. These two fly ashes produced acidic extracts. Both flyashes had total C levels exceeding 5% and I2 was characterized by a highferric component (Fig. 4) and Zn content (>0.2%). The two ligni te-basefly ashes (W2 and W3) plotted more toward the Calcic end member than didthe 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 flyash (W1) was an alkaline Ba-Modic silt. A summation of the classificationsof all 12 fly ashes is given in Table 7.Figure 5 shows the positions of the fly ashes in this study and 27 otherfly ashes on the sialic-ferric-calcic compositional field diagram.Twenty-one of the samples were fly ashes generated from eastern U.S.

Table 7. Fly ash sample classifications.SampleTypealkaline Modic siltacid C-Modic silt loamalkaline Modic siltalkaline Modic siltalkaline Modic siltalkaline Modic siltacid C, Zn-Fersic siltalkaline Modic siltalkaline Modic silta1 kal ine Ba-Modic si 1 talkaline B, Ba, Sr-Calsialicaalkaline 8, Ba, Sr-Calcica--aTexture was not determinedbituminous coals, one from a German bituminous coal and the other 17, samples were derived from subbituminous and lignite coals from the westernUS., India, and Australia.Fly ashes from eastern U.S. bituminous coals tended to fall on the leftside of the diagram in the Modic and Fersic fields (Fig. 5): this patternis reasonable, because the eastern U.S. coals generally have higherconcentrations of Fe than do western coals (Gluskoter et al., 1977). Flyashes from western U.S. lignite and subbituminous coals tended to plot onthe 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- odic boundary are three f 1 yashes generated from lignite coals in India. Indian lignite coal ischaracteristically low in Ca (Chopra et al., 1979); therefore, these flyashes did not fit the general pattern fordhe U.S. ashes. Additional workwith high-iron fly ashes is needed to provide a clearer indication of thedistribution of Ferrics and Fercalcics; few such fly ashes are completelycharacterized in the literature. However, the magnetic fractions of someFersics and Modics can be classified as Ferrics, as shown in Figure 5.Solvent extractionFive fly ashes were extracted with benzene. An amount of elemental sulfurequivalent to about 10% of the total extractable material in each ash wasco-extracted with the organic matter and interfered with the quantification

of the total extractable organics. The elemental sulfur was removed bypassing the extract through activated copper powder following the firstconcentration step. The amount of the benzene-extractable organic matterin each fly ash sample is reported as mg/kg of fly ash and as a percentweight of the organic C contained in the sample (Table 8). The C and Svalues for each fly ash sample are also reported in Table 8. In twowestern fly ashes (W1 and W2), less than 1% of the total organic C wasbenzene-extractable; in two other fly ashes (I6 and I8), less than 0.1% ofthe C was extracted into benzene. The unburned and partly burned coalparticles in the fly ashes are presumed to be the source of most of theorganic C. These coal particles would be only slightly soluble inbenzene.1. Bobrowski and Pistilli ( 1979)@ fly ashes from bituminous coals 2. Chou et al. (1976)3. Chopra et at. (1979)fly ashes from subbituminous4. Cooper (unpub. data)and lignite coals5. Foster (unpub. data)magnetic fractions of bituminous6. Griffin et al. (1980) 7. Harvey (unpub. data).fly ashes 8. Hood (1976)9. Hurst and Sty ron ( 1979)10. Murtha and Burnet (1979)1 1. Rose et al. ( 1979)12. Ryan et al. (1 976)13. Santhanam and Ulrich (1979)14. This investigation. Thornton et al. (1976). van der Sloot and Nieuwendijk(1981)17. Wochok et al. (1 976)13FerricCalcicm9\/ / / \12 29 52% Calcic Group(rare or not known to exist)Figure 5. The 12 fly ash samples and 27 other fly ash samples from the literature plotted on the Sialic-Ferric-Calcicdiagram for classification.ISGS 1983

Table 8. Carbon, sulfur, and benzene-extractable organic matter of selected fly ashes.Total Inorganic Organic Total Benzene ExtractableFl Y C C C S Organic CAsh (%I (%) (%) (%I (mg/kd (%IThe infrared spectrum (Fig. 6, for example) of the benzene extracts wasused for comparison with the infrared spectra of the corresponding LCfractions of the extracts. Absorption peaks due to aliphatic and aromaticstructures and from hydroxyl, carbonyl, ether, and nitrogen containinggroups were evident in all the extracts.The benzene extracts of four of the fly ashes were separated into seven LCfractions according to the Level 1 procedure. Only 11 mg of extract wasobtained from fly ash 16; because the LC separation could not be done withthis small amount of extract, the analysis of this sample was discontinued.The results from LC fractionation are expressed gravimetrically asmilligrams of solvent-free LC fraction per kilogram of fly ash (Table 9).Except for the extract from W1, the major portions of the organics in theextracts were found in fractions LC-1 and LC-6. The LC fractions of the W1extract were more evenly distributed on a weight percent basis than werethose of the other fly ashes. The IR spectrum indicated that the W1extract had a somewhat different distribution of compounds (Fig. 7) thandid the other fly ashes examined.aoQo 2000 lajb0 1000 sdoWave number (cm-' 1Figure 6. Infrared spectrum of the benzene-extractable organic material in fly ash 18.

. Liquid chromatographic fractionation of the benzene extracts of four fly ashes.Fly AshThe infrared spectra of the LC-1 fractions of all the fly ash samples werevery similar and were typical of aliphatic hydrocarbons showing strong -CH3and -CH2 stretching absorptions, medi um -CHz-C(CH3) 2, and symmetrical-C-CH3 deformation absorptions (Fig. 8). Gas chromatograms of thesefractions contained peaks for all n-paraffins from C1approximately C36, and numerous peaks due to much smaconcentrations of branched-chain aliphatics.The infrared spectra of the LC-2 fractions showed that the fractions werehighly al iphatic, with very weak aromatic absorptions, indicating a1 kylsubstitutedand/or fused-ring aromatics. The gas chromatograms of thesefractions indicated that the major constituents were n-paraffins. The HPLCchromatogram of the LC-2 fraction of fly ash W1 (Fig. 9) had nine majorpeaks including phenanthrene, pyrene, and chrysene. Phenanthrene andpyrene 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 srnal lerquantities of polynuclear aromatic hydrocarbons other than chrysene (oflower molecul ar weight - than chrysene and phenol s) were possibly present inthe fly ash.Wave number (cm-' 1Figure 7. Infrared spectrum of the benzene-extractable organic material in fly ash W1.

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 aliphaticabsorption peaks and weak aromatic peaks except for the W1 LC-3 fraction(Fig. lo), which appeared to have more aromatic compounds than theremaining three LC-3 fractions. There were also strong absorptions in thecarbonyl (1750-1 700 cm-1) regions of the W1 LC-3 spectrum. Becausethese appeared in fraction LC-3, they were likely due to long-chainaliphatic esters or aryl esters. The aryl esters were first thought to becontaminants of plasticizers introduced during sample handling. Plasticbags were used as storage containers prior to organic analysis (both ethyland diethyl phthalate were identified by GC-YS in the 450°C pyrolysate offly ash Wl). However, aryl esters have been recently indicated in a charFigure 9. HPLC chromatogram of the LC-2 fraction from the benzene extract of fly ash W1. See Figure 2for identification of the numbered peaks.

Wave number (cm-' ) ISGS 1983Figure 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 froma power plant (F. Harrison, Lawrence Li vermore National Laboratory,personal communication, 1982). The gas chromatograms of the LC-3samples showed the presence of eight to ten dominant components, whichare as yet unidentified (Fig. 11).The PAHs (phenanthrene, pyrene, and chrysene) were identified in the LC-3samples using HPLC. Numerous other smaller peaks due to aromatics havingmolecular weights higher than chrysene were also detected. The HPLCchromatogram of W1 LC-3 is shown in Figure 12.Figure 11. Gas chromatogram of the LC-3 fraction from the benzene-extractable organic matter in fly ash W1.

Figure 12. HPLC chromatogram of the LC-3 fraction from the benzene extract of fly ash W1. See Figure 2for identification of the numbered peaks.The infrared spectra of the LC-4 fractions showed the beginning of majordifferences in the compositions of the organics derived from the variousfly ashes. The LC-4 fraction of W1 (like the LC-3 fraction) contained morearomatic compounds and was more complex in composition than were theorganics in the other fly ashes. The peaks due to carbonyl absorption wereresolved into at least two distinct peaks (Fig. 13), indicating thepresence of both aliphatic and aryl esters or long-chain aldehydes andketones. Phenanthrene and pyrene were again identified by HPLC (Fig. 14).Other smaller peaks eluted earlier than pyrene; this was interpreted toindicate that polar compounds were beginning to be eluted. There were nomajor peaks later than that of pyrene.Wave number (cm-I ) lSGS 1983Figure 13. Infrared spectrum of the LC-4 fraction from the benzene extract of fly ash W1.

ISGS 1983Figure 14. HPLC chromatogram of the LC-4 fraction from the benzene extract of fly ash W1. See Figure 2for identification of the numbered peaks.The infrared spectra of the LC-5 fractions were similar to the spectra ofthe LC-4 samples, except that the LC-5 fraction from I8 had anomalous andunassigned peaks at 2340 and 1690 cm-1 (Fig. 15). The W1 sample hadmore carbonyl peaks than the other fly ash samples (such as the peak at1630 cm-1) indicating the possible presence of additional a1 dehydes andketones. The 1675 cm-1 peak may be due to hydroxyl overtones.The HPLC chromatogram of the LC-5 fraction from the W1 fly ash extract(Fig. 16) showed numerous peaks with retention times in the same range asthose of PAHs. According to the Level 1 scheme, this fraction containsaromatics with pol ar functional groups.The infrared spectra of the LC-6 fractions for 15, 18, and W2 were quitesimilar, with strong hydroxyl, carboxyl, and carbonyl absorptions. Theinfrared spectrum of the LC-6 fraction from W1 (Fig. 17) had we1 1-resolvedWave number (cm-' ISGS 1983Figure 15. Infrared spectrum of the LC-5 fraction from the benzene extract of fly ash 18.

Figure 16. HPLC chromatogram of the LC-5 fraction from the benzene extract of fly ash W1. Peak 5 istoluene, the internal standard.absorptions at 3190 and 3355 cm-1, overriding a broad hydroxyl peak andthe peaks indicating aromatic character. These latter peaks were probablyamino-nitrogen peaks. HPLC analysis showed that the sample probablycontained a-large number of phenolic compounds as we1 1 as other polararomatics (Fig. 18).Wave number (ern-' ISGS 1983Figure 17. Infrared spectrum of the LC-6 fraction from the benzene extract of fly ash W1.

Figure 18. HPLC chromatogram of the LC-6 fraction from the benzene extract of fly ash W1. Peak 5 istoluene, the internal standard.The LC-7 fractions were quite small and appeared to be contaminated withsilica gel from the column. Infrared intensities were weak, but theabsorptions were essentially comparable to the absorptions in therespective LC-6 fractions. The HPLC results showed only one major peak,which eluted earlier than toluene and was assumed to be a strongly polarcompound.Some of the organics identified with these fly ashes are on the prioritypollutant list; however, they are present in very small quantities (ppblevels at most), which are comparable to results reported elsewhere (EPRI,1979). However, the organics associated with these fly ash samples do notappear to be present in concentrations that would pose any significantenvironmental hazard during landfilling operations or to the aquaticenvironment during ponding.The noncondensable gas in the headspace was analyzed by gas chromatography.The results of these analyses are given in Table 10. Thedetection of a particular component is indicated by an "x" in theappropriate column. Because the headspace was still at a reduced pressureat the time of analysis, no attempt was made to quantify the amount of anyof the individual components. Only saturated and unsaturated hydrocarbonsof low molecular weight--typically found in the pyrolysates of higherhydrocarbons--were etecled. In the W1 pyro te, carbon dioxideaccounted for more han 50% of the total ~hr0 ographabl e gases.

Table 11. Organic components in the condensable pyrolysates of the fly ashes: (x) detected; (xx) detected in largerquantity; (t) trace; (7) retention time does not match.OrganicFly AshComponent I2 I3 I4 I5 I6 I7 I8 I9 W1 W2 W3to1 ueneethylphthal aten-C14n-C15n-C16i-C17n-C17i'C18n-Cl8n-C19diethylphthalaten-C2 0i-C21n-C2 1i-C22n-C22n-C2 3n-C24n-C2 5n-C2 6n-C2 7c28 ?c28?The "GC-fingerprints" of the noncondensable gas produced from the 11, 12,13, 14, and I7 samples were similar in the kind and quantity of any givencomponent (Figs. 19, 20; Table 11). The 15, W1, W2, and 3 condensateswere also similar to each other (Figs. 21, 22); however, the two groupswere quite dissimilar in that the non-condensables from the latter fourashes contained major components that were present in much lower quantitiesor did not appear in the former group.

. Gas chromatogram of the noncondensable hydrocarbons produced by pyrolysis at 45Q°C of flyash 12. Peak identification: 1. methane; 2. ethylene; 3. ethane; 4. Cjls; 5. C4's; 6. C5's.Figure 20. Gas chromatogram of the noncondensable hydrocarbons produced by pyrolysis at 450'6 of flyash 13. See Figure 19 for identification of the numbered peaks.The condensable fraction from the yrolysis of the W1 sampleby GC-MS. The major components detected were the n-paraffins with 13 to 28carbon atoms per molecule. The compounds present in the largest quantitieswere n-Clj, n-Cl8. n-C2 and n-Cz8 (Fig. 23). In a studydiscussed in EPRI (1-C2z9 and n-C27-31 were thedominant hydrocarbons iin the 575 to 816 ug/kgconcentration range. This ra e is consistentanalysis reported here*The results from this study areis pyrolyzed under similar condiconclusion that a probable source oparticles present in the ash. Howediethyl phthalate were deteceared to be thees used in thiscondensates may have been the plast

Figure 21. Gas chromatogram of the noncondensable hydrocarbons produced by pyrolysis at 45O0C of flyash W2. See Figure 19 for identification of the numbered peaks.Figure 22. Gas chromatogram of the noncondensable hydrocarbons produced by pyrolysis at 450°C of flyash 15. See Figure 19 for identification of the numbered peaks.similar result was observed from benzene extracts of these ashes. However,others (Fuller et ale, 1personal communication, 1982) havereported aryl esters inin a manner that would precludearyl ester contamination ly ash wash water.

Figure 23. Gas chromatogram of the condensable organics produced by pyrolysis at 30$~ af fly ash W1. Peak identification1. n-tridecane; 2. n-tetradecane; 3. 11-pentadecane; 4. ethyl pkthalate; 5. n-hexacieeane; 6. n-heptadecane; 7. n-octadecane;8. n-nondecane; 9. diethyl phthalate; 98. n-eicosane; 19, n-heneicosane; 12. n-docosaner 93. n-tetracosane; 14. n-octtpcOsen@.a1 uminosi 1 icate glass

4.Jrcrm c o mQU"* 'tn U.a-U U O NrOK53I *I%b*c,*wa+ a X cnca CVmc-6.) 07 C a r Ls- K 3 c awtc-Uz3ZBf.r- Lv-0 >arc)mU~~ O C Wrd%waam+ m L6= ? Xa EU aa-L E L 7aega + O-.:ymm?&JqjmW % E E fSi=-Lb4f-6 OWa , ~ > b t m aL-Cr6'4- 0M S v-CCD -0 -6-, 0.1-'P -cna,au-ab] U > cawrdOP 3 L W P06aua,m31E 0 Y,-1- U?a0 a, L-h=* w ~n x a,9s-MYU O C ,uam WgJW L OauPLc, h4-J EDa-,XP 'riaxQUCUmmW $4CWa, a 0 ascZ:c E-f- L-%,*'f=-.8-)Cdu x%-m m-"a, c 0 0u, 3.- E ma,+-'rbUCu s-79WEm-+-'?-3ma,5-a,V)BP_g61L 0as0.I----&'UWL-6-,Xa,th]0.r-aa,2sf--03wIlr0UsQJQ)Ba,2.Wca-,0C2E

Table 12. Chemical constituent concentrations obtained by the proposed U.S. EPA Extraction Procedure (EP)performed on the 12 fly ashes (concentrations in mg/L).pHTotal al kal in ityaphenolphthalein al kaaE.C.in mmnhos/cm~h in m~bA1AsI3BaBeCaCdCrCuFeKk4Fl y ashI1 12 I3 14 I5 I6 I7 18 19 W 1 W2 W3a ~ mg/L s CaC03b~el at i ve to a norm lhydrogen el ectrode

constituents. The amount of soluble Mn averaged 12.88 - + 6.29% in theIllinois Basin samples.The general trend of EP s lubility for t e Illinois Basin fly ashes was:S04-S > Ca, B > Cd > Sb, n, Mg > Zn, Na Mo > K, Ni, Cr, Cu > Be, Ba,Si , Al , and Fe. The gene a1 pattern of EP solu i 1 i ty for the suI3b-i -iNninousfly ash W1 was: S04-S > , As > Ca > Se > Mg, n > Mn > Na > KB and Ba;S04-S > B > K > Mo >> Se, Na > Ca > Zn, Mg > Be Cr > Mn, 5, and Ba wasthe order for the lignite fly ashes 2 and W3. However, these solubi 1 itytrends apply only to EP extracts; in dissimilar leaching environments,different extractability trends may be observed. In solubility or leachingexperiments in which extraction takes place in alkaline conditions (astypical with many fly ash leachates), different solubility regimes in theresulting alkaline solutions may take place, since the pH of the extract isoften the dominant factor controlling the solubility of many inorganicconstituents.The Cd level in the EP extract from I7 exceeded the recommended leveloutlined by the proposed 1J.S. EPA Resource Conservation and Recovery Act(RCRA) (Table 13). The concentrations listed are 100 times the EPA'sNational Interim Primary Drinking Water Standards (U.S. EPA, 1976).If the EP extract contains any constituent exceeding the maximum allowablelevel for that given contaminant in an EP aqueous extract, the parent wastemay be classified as a hazardous waste. The classification of a waste aspotentially hazardous may also be based on criteria other than the EP data(U.S. EPA, 1980). Fly ash was recently removed from the 1 ist of Subtitle Cin Section 3001 of RCRA. Therefore, all fly ashes are classified asTable 13. Contaminant concentrations (mg/L) in EP extracts qualifying for hazardous waste classification (U.S. EPA,1980).ConstituentArsenicBar i umCadmi umChromiumLe adivlercurySeleniumSi 1 verEndrinLi ndaneMethoxychlorToxaphene2,4-D2,4,5-TP Si lvexConcentration(mg/L)

nonhazardous wastes under present criteri ever, these gui deli nes arestill in a period of revision, and the status of fly ash as a nonhazardouswaste may be modified.If the status of power plant by-products were to be revised, one fly ash(17) would fall into the hazardous aste classif ication. There73.9% soluble Cd in this sample, releasing 1.38 mg Cd/L in solution; themaximum allowable extract level for Cd is 1.00 mg/L. On the basis of thesedata, the parent ashes of the other 11 EP extracts ould not be classifiedas hazardous wastes under the present criteria.Most aqueous systems of fly ash do not reach equilibrium in mostshort-term (24-hour) extraction tests (Elsee80) . Short -termextraction procedures w i l l leach out the morts, but otherelements such as Sb, As, Ba, and Se (James et al., 1977); and Ca, Cu, Fe,and Zn (Natusch et al., 1977) may be continuously leache into solution forperiods longer than 24 hours* Therefore, as a first apppredicting the water quality of ponded fly ash leachate, a long-termequilibration extraction procedure was designed to produce a solutionpotentially equilibrated with the solid waste. Fly ash ponds may reachmetastable equilibrium conditions if the rates of the chemical reactionscontrolling the solubility of the particular mineral phases involved areslow 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 thislong-term equi 1 i bration (LTE) procedure to suggest the general chemicalcharacter of disposal ponds that may develop after these ashes have beenslurried. In the LTE procedure (in contrast to the EP method), the pH ofthe solutions was not adjusted, and a greater solid-to-1 iquid ratio (a 20%slurry wt/vol ) was used. These solutions were periodical ly sampled duringthe extraction period. Results for the two acidic fly ashes (12, I7), twoalkaline samples (13, I%), and one of the western samples (W2) arepresented in Tables 14, 15, 16, 17, and 18.It is difficult to make direct comparisons between the LTE data and thosefrom the EP because of the different pHs of the extractants, the length ofthe solubilization period, the method of agitation, and the ratios of solidto liquid used in each procedure. After 24 hours (the duration of the EPmethod), the two LTE solutions generated from the Illinois Basin fly ashes(I2 and 17) were acidic (pH 4.1), while the other two (I3 and 18) werealkaline (about pH 11). The western fly ash extract, 2, was highlyalkaline (pH 12.4).As suggested by the data in Tables 14-18, the solutions were probably notin chemical equilibrium with the solid phase after the first 24 hours ofsolubilization, because the concentrations of many aqueous speciescontinued to change for several weeks. Figures 24, 25. nd 26 graphicallydemonstrate the changes in concentrations of selected constituents forthree of the samples.

Table 14. Change in chemical composition as a function of time of fly ash I2 extract generated by long-term (142days) equilibration procedure (concentrations in mg/L).1 hour 24 hours 48 hours 7 days 21 days 36 days 65 days 95 days 108 days 124 days 142 dayspHTotal alkal inityaEOC. in mmhos/cmEh in mvbA lAsBBaBsCaCdCPCuFeKMgMnMoNaN iPbSbseS iSnVZn504a ~ mg/L s CaC03b~el at i ve to a norma l hydrogen el ectrode.

Table 15. Change in chemical composition as a function of time of fly ash I3 extract generated by long-term (141days) equilibration procedure (concentrations in mg/L).1 hour 24 hours 48 hours 7 days 21 days 36 days 64 days 94 days 107 days 123 days 141 daysPH 11.7 11.6 1 1,5 12.3 12.8 12.1 11.5 11.2 11.4 11.4 1 1 ,ITotal alkal initya 406 457 457 1530 1043 526 283 256 238 232 23 1phenol phthal ein al kma 350 398 398 1403 950 497 213 213 187 183 183EmC. in mmhos/crn 2,38 2.17 2.07 4.96 4,17 2.29 1.43 1e15 1.11 0.91 0, 89~h in mvb +43 5 +430 +422 +38 5 +303 +339 +320 +408 +336 +354 +38 1aAs mg/L CaC03%el a t i ve to a normal hydrogen el ectrode.

Table 16. Change in chemical composition as a function of time of fly ash I7 extract generated by long-term (106days) equilibration procedure (concentrations in rng/L).pHTotal al kal in ityaE.CO in mmhos/cmEh in mvbAlAsBBaBeCaCdCrCuFeKMgMnMoNaN iPbSbSeS iSnvZnso4a ~ mg/L s CaC03b~el at i ve to a norm l hydrogen el ectrode.1 hour 24 hours 48 hours 7 days 21 days 36 days 76 days 95 days 106 days

Table 17. Change in chemical composition as a function of time of fly ash I8 extract generated by long-term (140days) equilibration procedure (concentrations in mg/L).- -1 hour 24 hour 48 hour 7 days 21 days 37 days 63 days 93 days 106 days 122 days 140 daysmgdL CaCO3%el at ive to a norm l hydrogen el eetrode.

Change in chemical composition as a function of time of fly ash W2 extract generated b.y iong-term (140days) equilibration procedure (concentrations in mg/L). .pH 32.4Total al kal in itya 2194phenolphthalein alkea 2022EeCe in rnmhos/crn8e82~h ~n m~b ~349Ai1 e38ASOe05B 120Ba0,lOB@

Time (days) ISGS 1981Figure 24. Changes in the concentrations of selected aqueous constituents in the LTE extract of fly ash I3 with time.02 7 2 1 3 6 76 95 106Time (days) ISGS 1981Figure 25. Changes in the concentrations of selected aqueous constituents in the LTE extract of fly ash I7 with time.

Figure 26. Changes in the concentrations of selected aqueous constituents in the LTE extract of fly ash W2 with time.In each solution, most of the constituents were in greater concentrationsduring the first week of extraction than they were later. Beginning almostirrmediately after the first day, these same constituents decreased inconcentration, and this trend prevailed for about 60 to 120 days. Afterthat interval, the concentrations of these constituents no longer changedsignificantly, having reached relatively steady state conditions.In both the initially acidic solutions (I2 and 17) the concentrations of B,Ba, Ca, Cd, Mg, Mn, Na, Ni, Si, S04, and Zn as well as pH becameconstant in 3 to 5 weeks (Tables 14, 16). The dominant factor controllingthe solubility of inany metals is pH. Both acidic extracts became neutralin pH and, as a consequence, several constituents were less soluble in theresulting nonacidic solution. Therefore, Al, Be, Cd, Cr, Cu, Fe, and Niwere in greater concentrations during the early phase of the extractions.Molybdenum steadily increased during the entire extraction interval of theacidic fly ashes and had not reached a steady state when the LTEs wereterminated.These changes in solubility over time make generalized solubility trendsdifficult to predict with certainty. For example, the ranking of theamount in solution versus the total amount in the solid for fly ash I2after 24 hours of extraction was Cd, Zn > S04-S > B > Ca, Mg > Cu > Na,Be, Ni, K > Mn > Cr > A1 > Ba, Si, Mo, Pb, and Fe. After 142 days, therelative solubilities were: S04-S > B > Mg > Mo, Ca > Cd > Na > Se > Mn> Zn > Sb, K > Ni > Ba > Cu, Cr, Pb, and Si. The change in solubility

trends is a reflection of the shifts in equilibria controlling thesolubility of the constituents during the extraction interval.In contrast, the pH of the two alkaline solutions (I3 and 18) remainedabove pH 10 during the entire extraction interval (140 days), and slowlydecreased thereafter. In both the acidic and alkaline solutions, A1 wasmore soluble during the ea ly phases of the procedure but significantlydecreased i n concentrat ion with time. In contrast to the two alkalinesolutions produced by the llinois Basin fly ashes, the pH of the solutiongenerated by the lignite f y ash (W2) was essentially invariant for theentire solubilization-equi ibration interval (140 days). Moreover, thesolubility of A1 from the ignite sarople steadily increased with time.Other studies dealing with fly ash extracts have also noted analogouschanges in concentrations with time. Talbot et al. (1978) equilibrated awestern U.S. fly ash for 6 months in an open system. The pH of thealkaline extract decreased from 11 to 8.8 after 1 month, having reached asteady state.Townsend and Hodgson (1973) equilibrated an alkaline fly ash generated fromBri tish coals in a closed system. They observed that the pH and the OH andCa concentrations increased initially, and then became invariant, whereasthe B and SO concentrations decreased during the extraction interval.Helm et al. 41976) also noted that concentrations of SO4 and B decreasedwith time in solutions generated from shake tests with an alkaline fly ashproduced from eastern bituminous coals. Page et al. (1979) equilibrated a1:l fly ash-water mixture for 30 days. In the resulting alkaline solution,Ca and OH concentrations steadily decreased, whereas the pH remainedconstant.The present study may have several implications concerning the waterquality of ash disposal ponds in a chronological framework. The two flyashes that formed acidic extracts initially contained potentially toxictrace metals, such as Cd, dith time, these acidic solutions becameneutral, and several such trace constituents were no longer soluble,although other potential pollutants persisted in solution for longerperiods. The fly ashes that produced alkaline extracts generated solutionsthat reqained alkaline, and similarly, several potential pollutants alsopersisted in solution.These results indicate that fly ash, particularly acidic samples, are most .toxic to aquatic ecosystems when initially slurried to disposal ponds andthat their toxicity may decrease with time. However, if potentialpollutants are in metastable equilibrium in the pond, they may have longresidence times in the ash effluent, increasing the probability ofbioaccumulation by aquatic organisms. Excessive levels of Se have beendetected in various species of fish inhabiting a cooling lake associatedwith a coal-fired power plant in Illinois (Larimore and Tranquilli, 1979).Intermittent overflow of a nearby ash pond into the cooling lake may havebeen the source af the Se.The specific concentrations of the constituents exceeding EPM interimprimary or secondary drinking water standards or irrigation water criteriaare listed in Table 19. Depending on the solid waste, As, Cd, Cr, and Se

Table 19. Corytituents in the long-term equilibrations exceeding EPA interim primary or secondary drinking waterstandards or irrigation water criteria as a function of time (concentrations in mg/L).Constituent121 hour 142 days13I hour141 daysFly ash -I7I hour 106 days18I hour140daysW2I hour140 daysPrimary drinking waterAr sen i c 0,05Cadm i urn 0.010.44Chromi um 0.051 mooSel en i urn 0.01Secondary drinking waterCopper 1 .O2.1 3l ron 0.3018.6Manganese 0,052.65Su l fate 2 502972Zinc 5.014.0pH (units) 5,5 - 9.54.1Irrigation waterAluminum 20,O1 96Boron 2.065.2Moi ybdenum 0.05Ni ckel 2.0

were in concentrations exceeding the primary standards after 1 hour in theLTE solutions. After 106 to 140 days of extraction, the concentrations ofthese constituents changed, but the levels of some of the potentialpollutants still remained above recommended levels. In each solution,other constituents exceeded the secondary standards and the recommendedlevels for irrigation water (U.S. EPA, 1976). As ith the primarystandards, certain potential pollutants remained in solution in excessivelevels. Boron, Mo, and SO4 were constituents common to all five extractsthat remained above recommended levels during the entire extract ioninterval .All five undiluted fly ash LTE extracts were acutely toxic to fatheadminnows, causing total mortality (Table 20). Three of the extracts (13, and 18) were very alkaline (pH >10.0), and mortality due to ionic shockwas expected. In a previous study (Suloway, et al., lWl), test solutionsin which the pH was greater than 9.2 were acutely toxic to fathead minnowfry. However, two of the samples in the present study (I2 and 17) wererelatively 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 wasmore than 60% of saturation. The pHs of the extracts remained relativelystable during the bioassays with the exception of 18, in which the pHdecreased almost an entire pH unit. There was a 5% mortality in thecontrols.LC-50 determinations (Table 21) were made to measure the relativetoxicities of the extracts and to determine the dilutions necessary toensure survival during a %-hour bioassay of the toxic extracts. Aninverse relationship existed between toxicity and the LC-50 value for anextract. The LC-50 values for W2 and I3 were 2.8 and 63.0 (Table 21),respectively. Sixty-three mL of 13, diluted with 37.0 mL of dilutionwater, was just as toxic as only 2.8 mL of W2 diluted with 97.2 1nL ofdilution water. Therefore, with an increase in toxicity, there was adecrease in the LC-50 value.TABLE 20. The percentage of mortality of 9-to-6 day-old fathead minnow fry (Pimephales promelas) resulting from96-hour exposures to full-strength extracts generated from five fly ashes. Initial and final pHs and concentrations ofdissolved oxygen (mg/L) are listed.Samp 1 e PH i pHf 0.O.i D-0.f Mortality (%)

Table 21. The LC-50 values, amount of dilution necessary to eliminate mortality, and the initial pH values for extractsgenerated from five fly ashes.Fly ash LC-50 Confidence intervalsa Di lution for zerosample PH i mL/100mL mL/ 1 O0mL percent mortal i tyaThere is a 95 percent probability that the LC-50 falls within the confidenceinterval listed.The results of the LC-50 determinations indicate that W2 was the fly ashextract most toxic to young fathead minnows; it required as much as a1:1000 dilution to eliminate mortality. The I3 ash produced the secondmost toxic extract; the remaining three extracts had similar LC-50 values.The acute toxicity of a leachate should be partly a function of itschemical composition. Simple linear and multiple regression analyses wereused to determine, for each extract, the relationship between the mortalitydata and the chemical data collected during the LC-50 determinations(Tables 22-25) The I8 test solutions were not chemically analyzed. Therange of concentrations for each chemical constituent, the recommendedwater quality level for each chemical constituent, the change in r2 forthe multiple regression, and the r value for the simple linear regressionare listed in each table. In statistical analysis, the values for r andr2 w i l l vary from 0.70). When the results of these statisticalanalyses are considered with the levels of various chemical constituentspresent in the test solutions, the importance of various chemicalconstituents with respect to acute toxicity of a particular fly ash extractcan be assessed.A strong relationship existed between the acute toxicity of the W2 leachateand its pH. Alkaline (pH > 9.2) solutions have been shown to be acutelytoxic 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 andsuggested that the principal lethal agent was the high pH level. Wassermanet al. (1974) reported that runoff from alkaline ash ponds was lethal tocatfish because the increased pH caused the precipitation of ferrichydroxide, which might have clogged the gi l apparatus, causing asphyxiation.

Table 22. The range of concentrations and recommended water quality levels for chemical constituents measured intest solutions of W2.Range ofRecommended waterChemical concentrations quality levels r2constituent (mg/L)a (m!mb Changec r CaAl 1 values in mg/L except pH.b~alues are MATES cited from Cleland and Kin'gsbury (1977) unless anothersource is indicated.CValues of r2 and r represent the results from mul tiple and simple l inearregression analyses of the relationship between mortal ity observed in the testsolutions of the extract and the concentrations of each chemical constituentmeasured in those test solutions.d~rom Quality Criteria for Water 1976 (U.S. EPA, 1976).The extract of 13, like that generated from W2, was very alkaline andrelatively toxic. The regression analyses indicated strong relationshipsbetween the final and initial pH and fish mortality (Table 23). Althoughthe range of values for the final pH regression was rather narrow, therewere 16 data points between the minimum and mximum pH values. The initialpli values were also elevated enough to cause mortality. Aluminum, As, andCa were present in concentrations that exceeded recommended values;however, probably only A1 was present at sufficient levels to be acutelytoxic.The extract generated From I7 was slightly acidic (pH < 6.7) when the LC-50determinations were calculated (Table 24). The extract was much less toxicthan those of W2 and 13; therefore, test solutions used to determine theLC-50 value did not require large dilutions. The high percentage ofextract in the test solutions (75 to 100%) and the lower pH resulted in

Table 23. The range of concentrations and recommended water quality levels for chemical constituents measuredin test solutions of 13.Range ofRecommended waterChemical concentrations qua1 i ty 1 eve1 s r2 (d)constituent (mg/L) a ( m w Change' rcaAl 1 values in mg/L except pH.balues are MATES cited from Cleland and Kingsbury (1977) unless another source isindicated.CValues of r2 and r represent the results from multiple and simple linearregression analyses of the relationship between mortality observed in the testsolutions of the extract and the concentrations of each chemical constituentmeasured in those test solutions.d~rom Quality Criteria for Water 1976 (U.S. EPA, 1976).higher concentrations of various chemical constituents in the testsolutions of I7 than were found for I3 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 insufficient concentrations by thelnselves to cause mortality according totoxicity data available in the 1 iterature (Cardwell, 1976; Cleland andKingsbury, 1977; Pickering and Gast, 1972; Pickering, 1974; Pickering andHenderson, 1966).Zinc concentrations ranged from 0.21 mg/L to 0.63 mg/L in the I7 testsolutions (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 bioassaysincluded mortal ity at concentrations as low as 0.294 mg/L of Zn (Benoit andHolcombe, 1978). However, 8-week-old fathead minnows and soft water (46mg/L as CaC03) were used in their experiments. Chapman (1978) reported that

Table 24. The range of concentrations and recommended water quality levels for chemical constituents measuredin test solutions of 17.Range ofRecommended waterChemical concentrations qua1 i ty levels r2constituent (mdL) a (md~) ChangeC YCaAl 1 values in mg/L except pH.b~alues are MATES cited from Cl eland and Kingsbury (1977) unless another source isindicated.CValues o f r2 and r represent the results from mu1 tiple and simple 1 inearregression analyses of the relationship between mortality observed in the testsolutions of the extract and the concentrations of each chemical constituent measuredin those test solutions.d~rorn Quality Criteria for Water 1976 (U.S. EPA, 1976).96-hour LC-50s for Zn for steelhead trout varied, depending on whichlife stage was exposed. Mount (1966) found an inverse relationship betweenZn toxicity and water hardness for fathead minnows. Mount tested the acutetoxicity of Zn under various pH and hardness conditions, making directcorrelations of Zn and toxicity difficult. Using hard (200 mg/L asCaC03) and alkaline (nominal pH = 8.0) dilution water, the LC-50 wasapproximately 8.2 mg/L of Zn. These data suggest that Zn might be partlyresponsible for the mortality caused by I7 test solutions.Sulfate and other ions were present in relatively high concentrations,contributing to the electrical conductivity (EC) , whic varied between 4.1and 5.29 mmhos/crn (Table 16) in the undiluted extract of 17. Significantmortality of fathead minnow fry has been observed in reconstituted water in

Table 25. The range of concentrations and recommended water quality levels for chemical constituents measuredin test solutions of 12.Range ofRecommended waterChemical concentrations qua1 i ty 1 eve1 s r2constituent (mdL) a (m3/Ub Ch angec rcaAl 1 values in mg/L except pH.b~alues are MATES cited from Cleland and Kingsbury (1977) unless another source isindicated.cValues of r2 and r represent the results from multiple and simple 1 inearregression analyses of the relationship between mortality observed in the testsolutions of the extract and the concentrations of each chemical constituent measuredin those test solutions.d~rom Quality Criteria for Water 1976 (U.S. EPA, 1976).which the EC exceeded 4.0 mmhos/cm (Suloway et al., 1981). Thus, the totalionic strength of the test solutions of I7 also probably contributed to theacute toxicity of this fly ash extract.The extract generated from I2 was nearly neutral in pH when the LC-50determinations were made (Table 24). This extract was much less toxic thanwere the W2 and I3 extracts (Table 21); therefore, test solutions used todetermine the LC-50 value were comprised of 50 to 100% extract. Because ofthe high percentage of extract used in the test solutions, concentrationsof various chemical constituents were higher in the test solutions of I2than in I3 and W2. The concentrations of B, Mn, Mo, Ni, SO4, and Zn intest solutions of I2 exceeded recommended water quality levels andcorrelated well with mortality data based on the simple linear regressions.

Boron concentrations were high, but extremely high concentrations of B arerequired to produce toxic effects in aquatic life (Becker and Thatcher,1973). For example, the minimum lethal dose for minnows exposed to boricacid at 20' C for 6 hours was reported to be 18,000 to 19,000 mg/L indistilled water and 19,000 to 19,500 mg/L in hard water (Le Clerc andDevlaminck, 1955; Le Clerc, 1960).According to toxicity data available inthe 1 iterature (Cardwell, 1976; Cleland and Kingsbury, 1977; Mount, 1966;Pickering, 1974; Pickering and Gast, 1972; Pickering and Henderson, 1966).The individual concentrations of Mn, 0, Ni, SO4, and Zn were probablynot. high enough to cause the mortality observed in the test solutions of 12.The total ionic strength of the I2 extract as measured by EC was less thanthat of the I7 extract (Tables 14 and 16). The EC of the undiluted I2extract ranged from 2.74 to 3.80. Insignificant mortality was observed inreconstituted water in which the EC was less than 3.0 (Suloway et al.,1981). Because of the complex chemical composition of the I2 fly ashextract and the unknown synergistic and antagonistic effects of thechemical constituents composing the extract, it is not possible from theseexperiments to determine specifically which chemical constituents weredirectly responsible for the observed mortality.Analyses of variance of fish lengths and weights (Tables 26 and 27)showed that only the fathead minnows were different in weight for sample13, and so all duplicates were combined for each organism for each sample.The mean initial length and weight of fathead minnows used in thebioaccumulation experiments were approximately 50 mm and 1 g, respectively(Table 28). The mean initial length and weight of the green sunfish usedTable 26. The mean initial lengths and weights of adult fathead minnows used in the bioaccumulation experiments.Mean lengthMean weightSample N (md F valued (9) F valuedaResults of the analysis of variance indicate that if F(1,8)than 3.46, the replicates are significantly different.-- -- -- -- - -is greater

Table 27. The mean initial lengths and weights of juvenile green sunfish used in the bioaccumulation experiments.Mean lengthMean weightSamp 1 e r\l (mm) F valuea (9) F valuedControl -A 5 47.8 1.356Control-B 5 48.6 0.133 1.326 0.01 3aResults of the analysis of variance indicate that if F(1,8)than 3.46, replicates are significantly different.is greaterwere 50 mm and 1.3 g, respectively (Table 29). Fathead minnows and greensunfish in the control solutions were essentially the same size as thoseexposed to the fly ash extracts (Table 30).At the conclusion of the experiments, all the duplicates that could beanalyzed proved to be homogeneous (Tables 31 and 32). The mean finallengths and weights of the fathead minnows and green sunfish betweenreplicates were not significantly different from each other (Tables 33 and34). Although the concentrations of the extracts to which the organismswere exposed should not have caused mortality, it was hypothesized that thetoxic components may have been of sufficient concentration to causesublethal, physiological perturbations resulting in decreased growth. Theresults of the ANOVA demonstrated that at the termination of thebioaccumulation experiments the green sunfish and fathead minnows in theTable 28. Initial mean total lengths and weights of adult fathead minnows exposed to extracts from five fly ashesand a control.Me an St andard Mean StandardSamp 1 e N length (mm) devi ation weight (g) deviationControl 10 47.9 3.33 0.998 0.230W2 10 49.8 4.09 1.135 0-300I3 10 52.0 3.66 1 .I60 0.252I8 10 49.3 4.76 1.110 0.389I7 10 49.4 4.34 1 .I34 0.334I2 10 47.8 4.81 1.132 0.432

Table 29, Initial mean total lengths and weights of juvenile green sunfish exposed to extracts from five fly ashesand a control.Me an Standard Me an St andardSample N length (mm) deviation weight (g) deviationControl 10 48.2 3.1 1.341 0.379W2 10 48.1 5.1 1.194 0.433I3 10 48.9 3.0 1.324 0.328I8 10 48.8 4.0 1.240 0.374I7 10 51 -1 4.0 1.491 0.431I2 10 50.9 3.9 1.573 0.366Table 30. Comparison of the mean initial lengths and weights between the control test organisms and the organismsexposed to fly ash extracts.Green sunf i shaFathead mi nno,wa1 ength weight 1 ength weightControl vs ~ 2 b 0.002 0.585 1.167 1.178Control vs I3 0.229 0.010 2.618 0.748Control vs I8 0.1 24 0.322 0.242 0.551Control vs I7 0.613 2.883 0.677 1.001Control vs I2 2.61 9 1.738 0.003 0.673aThe values listed are F 1,18) values generated by one-wayanalysis of variance. f f the F value is greater than 3.01, the meansare significantly different.b~ = 10 for each test and control group.Table 31. The mean final lengths and weights of juvenile green sunfish used in the bioaccumulation experiments.Mean lengthMean weightSamp 1 e N (mm) F valued (9) F valueaaResults of the analysis of variance indicate that if F(1,8)than 3.46, the replicates are significantly different.is greater54

Table 32. The mean final lengths and weights of adult fathead minnows used in the bioaccumulation experiments.Mean lengthMean weightSample (mm) F valuea (9) F valuedControl -AControl-BaResults of the analysis of variance indicate that if F(1,8)than 3.46, the replicates are significantly different.b~nsufficient data for statistical analysis.is greaterTable 33. Final mean total lengths and weights of adult fathead minnows exposed to extracts from five fly ashes anda control.Me an St andard Me an St andardSample N length (mm) deviation weight (g) deviationControl 10 49.9 4.0 1.305 0.373W2 10 52.1 3.6 1.515 0- 456I3 7 51 -4 3.5 1.433 0.123IS 10 51 -2 5.0 1.398 0.51 0I7 6 51.7 8. 2 1.522 0.563I2 10 47.9 4.6 1.135 0.453Table 34. Final mean total lengths and weights of juvenile green sunfish exposed to extracts from five fly ashes anda control.Me anSt andardSamp 1 e .N length (mm) deviationControl 10 56.0 6.6W2 10 54.3 6-3I3 10 54.4 4.4I8 10 55.1 6.1I7 10 59.9 7.1I2 10 58.5 6.3Me anweight (g)2.9972.6372.5892.6613.6963.380Standarddeviation

controls were essentially the same length and weight as those exposed tothe extracts (Table 35). Furthermore, when the differences between i niti a1and final mean lengths and weights for fathead minnows (Table 36) and greensunfish (Table 37) were compared, the growth of the control andexperimental animals was approximately the same. Only the fathead minnowsexposed to I3 and I2 extracts grew appreciably less than the controls, butthe differences were not significant.Table 35. Comparison of the mean final lengths and weights between the control test organisms and the organismsexposed to fly ash extracts.Green sunfishaFathead minnowa1 ength weight length weightControl vs ~ 2 b 0.31 3 0.457 1.503 1 .I41Control vs I3 0.368 0.773 0.585 0.446Control vs I8 0.091 0. 508 0.369 0.195Control vs 17 1.467 1.447 0.291 0-516Control vs I2 2.676 0.470 0.968 0.753aThe values listed are F(1 18) values generated by one-way analysisof variance. If the F value is greater then 3.01, the means aresignificantly different.b~ = 10 for each test and control group, except for I3 fathead minnows,N = 7, and for I7 fathead minnows, N = 6.Table 36. Differences between initial and final mean lengths and weights of adult fathead minnows exposed to extractsfrom five fly ashes and a control.Control +2.0W2 +2.3I3 +0.6I8 +1.9I7 4-2.3I2 4-0. 1Di fference i nDifference inmean length Percent increase mean weight Percent increase(mm) in mean length (9) in mean weightTable 37. Differences between initial and final mean lengths and weights of juvenile green sunfish exposed to extractsfrom five fly ashes and a control.Di fferences inDi ff erences i nmean length Percent increase mean weight Percent increase(mm) in mean length (9) in mean weightControl +7.8 16.2W2 +6.2 12.9I3 +5.5 11.2I8 +6.3 12.9I7 +8.8 17.2I2 +7.6 14.9

Several of the extrbivalves ( ~ arena ~ aDepending on the orIn, Cl, and Ca were concconstituent most concentExcessive levels of Se(Larimore and Tranqui 11crayfish accumulatehe Similar accumulationsof Al, As, and Ni intimes, respectively,Concentrat ion factor i s78) as the ratioorganism (or a particularthat substance in thele, an organismpg Cu/L hasentration factorby green sunfish were both greater than 15.Both green sunfisminnows concentrated Mo from I3 extract.The concentration t in the I3 extract did not exceed primary orsecondary drinkin ards (Table 1 eed the levelable 23). Yet the greenre Mo than did the controlen the levels ofto the control soThe concentrationows accumu 1 ate extract The concentrat ion; the level of A1 present

Table 38. The mean concentrations of various chemical constituents measured in adult fathead minnows exposed toextracts from five fly ashes and a control.Fly ashControl kJ2 I3 I8 I7 I2% Extract 0.0in the fathead minnows exposed to the I3 extract was four times greaterthan the level measured in the control fish (Table 38). Green sunfish didnot accumulate A1 frorn 13, but they did accumulate Pb. The concentrationof Pb in the tissues of green sunfish exposed to the I3 extract was twicethat present in the controls. The concentration factor for Pb was greaterthan 25. Neither the concentration of A1 nor of Pb exceeded primary orsecondary drinking water standards in the I3 extract (Table 19). Theresults of the LC-50 determinations gave some indications of a problem withA1 in the I3 extract, because the level of A1 exceeded the recommendedlevel for the protection of aquatic life (Table 23).As occurred with the extract frorn 13, Mo was accumulated frorn the I8extract by both the fathead minnows and the green sunfish. Molybdenuinlevels in the green sunfish tissue exposed to the I8 extract were almost 40times greater than those in the control fish. The level of Mo accumulatedin fathead minnows exposed to I8 extract was more than 20 times that found

The mean concentrations of various chemical constituents measured in juvenile green sunfish exposed toextracts from five fly ashes and a control.Fly ashControl W2 I3 I8 I7 I2% Extract 0-0in the controls- The concentration factors of o for green sunfish andfathead minnows exposed to I8 extract were 1.1 nd 0.50, respectively.These relatively low concentration factors indicate that there were higho in the I8 extract and that the level of o in the fish tissuemight increase further with longer exposure.Fathead minnow osed to extract generated from I7 accumulated Al, B, Cd,in the I7 ext act exceeded the primarythe level of n exceeded the secondaryj The bioconcentration factors of Al, B,nows exposed to the I7 extract were >162,.8, respectively, The levels of these elementsin the fathead minnows exposed to the I7 extract were at least twice thosefound in the control fathead minnows. In fact, the levels of five of thesesix elements (all but Al) were 5 times tin the controls.

The green sunfish exposed to t t accumulated e same elementsas the fathead minnows althoug ese constitue accumulated to alesser degree.resent in the green sunfishexposed to thecontrols. Theexposed to the IFinally, the composition of the extracts generated from samples I7 and I2were similar. The accumulation of elements Prom the I2 extract by the testorganisms also was similar to that observe in test organisms exposed to17. The chemical constituents accumul ated to the reatest degree by thefathead minnows were B, Cd, Mn, NO, and 8). The concentrationfactors for 5, Cd, Mn, Ma, and Ni in fat posed to the 12extract were 0.3, >Q.3, 81.8, L2, and >22.1, respectively.The green sunfish exposed to the I2 extract accumulated the same chemicalcsnsti tuents awere accumul atsunf i sh expose7.0 times, respectively,those measuredors for B and Mo ingreen sunfishThe six most frequently accumulated chemical constituents from the fly ashextracts were Al, B, C , Mn, MO, and i, Other chemical constituents wereaccumulated, but these elements were accumulated to the greatest extent.In most situations, the results of the chemical analyses of the extractsand the LC-50 determinations did not indicate which chemical constituentswould be accumulated. The United States Food and Drug Admini tration (FDA)currently lists Hg, Pb, Cd, As, Se, and Zn at the top of the riority listin its program concerning toxic elements in food (Jelinek and Cornel i ussen,77). Of these, only Hg has an FDB-specified regulatory limit for fishd shellfish (Anonymous, 1974); FDA guidelines for other metals in foodshave no% been establishe (Phi l l ips and Russo, 1978).Aluminum is an elementand it rarely prAluminum has a ronsumption ofthe low toxicity of A1is relatively inert on biological processes,raeder and Darndency in fresBoron is used in a process for bleaching ulverized wood by the pulp andpaper industry (Thompson et al., l976), a(Phi 11 ips and Russo, l978), and as a neutroinstallations (National Academy of Science,fly ash from fossil fuels. Boron generallytendency in freshwater fish and a low toxicity to aquatic organisms and tohurnans (Phi 11 ips and Russo, 1978).Cadmium is rare in nature, but is highly toxic (National Academy ofScience, 1973). Inhalation or ingestion of Cd produces both acute andchronic health effects. Cadmium poisonings in urnans resulting from oralconsumption or inhalation are well documented ( assett, 1975; Flick et al.,1971; Voors and Shuman, 1977; American ConIndustrial Hygientists, 1974; Stokinger, 1

1972). Cadmium is a dangerous cumulative poison. A concentration factorof up to 1,000 has been reported (National Academy of Science, 1973).Several authors have measured Cd uptake by freshwater organisms. Theaccumulation of Cd by freshwater fish has been studied in white catfish,IctaZurms catus (Rowe and Massaro, 1974) ; goldfish, Camssius aumtus(Marafante, 1976); bluegill, Lepomis macrochirus (Mount and Stephan, 1967;Eaton, 1974) ; zebra fish, Brachydanio rerio (Rehwolt and Karimi an-Teherani ,76) ; stickleback, Gasterosteus aeuZeatus (Pascoe and Mattey, 1977) ;guppy, Poecilia reticulata (Ki nkade and Erdman, 1975) ; brook trout,SaZueZinu fontirrzlis (Benoi t et a1 . , 1976) ; rainbow trout, SaZm gairdneri(Kumada et a1 . , 1973) ; and 1 argemouth bass, Micropterus salmaides (Cearleyand Coleman, 1974). Very little Cd is accumulated in the edible portionsof fishes; it is usually concentrated in the gills, liver, and kidneys.Cadmium in fishes, therefore, does not appear to represent a hazard tohuman consumers. However, oysters, abalone, and mussels are capable ofaccumulating extremely high levels of Cd in edible portions (Phillips andRusso, 1978).Manganese has a relatively low tendency for bioaccumulation in freshwateranganese has a low toxicity to humans, but poisonings haveoccurred from excessive exposures to Mn in plants (Berry et a1 . , 1974).ronic poisoning may result from the inhalation of Mn compounds (Sullivan,69). Manganese has been detected in marine and freshwater fishes and haseen shown to be accumulated via the food chain in marine and freshwaterinvertebrates. However, Mn appears to be a relatively nonhazardous elementin most waters due to the low toxicity of Mn to humans and aquatic life(Phi 11 ips and Russo, 1978).Molybdenum has a low bioaccumulative tendency in fish. Bioaccumulation ofMo by lake trout, SaZveZims nzmycush, 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 andhas a relatively low toxicity to humans (Phillips and Russo, 1978).A1 though Ni is present in considerable amounts in plant and animal tissues,dietary intake of Ni is not harmful to humans. Workers exposed to Ni maydevelop a sensitivity to it and even dermatitis. Because of Nik low toxicityto humans, almost no information is available on the accumulation of Ni byaquatic organisms (Phillips and Russo, 1978).In industrial situations Ni dust has been shown to cause lung and nasal cancersin exposed workers (Do11,1958), and Ni metal can cause eczema i ti sensitizedworkers (Browning, 1969). Nickel carbonyl, an intermediate in the nickelrefining process (also found in cigarette smoke and a possible product of theincomplete combustion of coal), can cause cancer in rats and humans andrepresents the primary nickel related hazard to human health (Sunderman andDonnelly, 1965; Schroeder, 1970). The low toxicity of nickel when orallyingested has been demonstrated for several animals (Underwood, 1971). Nickelconstantly occurs in food, many waters, and all forms of life, both marine andterrestrial (Bowen, 1966).The results of this study demonstrated that fly ash extracts were acutely toxicto fathead minnows and that various trace elements are accumlated in both

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