Optimum Fly Ash Content for Lower Cost and Sup<rior Durability 

by R. P. Khatri and V. Sirivivatnanon ................................ 205 

Sulfate Resistance ofMortara Containing High-Calcium Fly Ashes and 

Combinations of Highly Reactive Pozzolans and Fly Ash 

by S. G. Shuhiprakasb and M. D. A. Thomas .................... ... .. 221 

Development of a Fly Ash and Epexy Based High-Perf'onnanoe Grout for the 

Repair of Offshore Platfonns 

byT. S. Thandavamoor!hY. A. G. ~bdbava Rao, and A. R. Santbakumar .••. 239 

Fly Ash in Self.COmpoc:ting Concrete 

by R. Khurana and R. Saccone • . .. . . .. ............................. 259 

Resistance of fly Ash and Natural Pozzolans Blended Cement Mortars and 

Concrete to Carbonation, Sulfate Attack and Chloride Ion Penetration by K. K. Sideris and A. E. Savva ........ ................. .. . ........ 27S 

Valorization of Fly Ash from Municipal Solid Waste Incineration Via 

Hydrothennal Treatment 

by A. Guerrero, S. Golli, E. Feminde>, and A. Moclas ...........••... . .. 29S 

Optimizanon ofCLSM Mixture Proportion with Comb1nonon of Clinker Ash and 

Fly Ash 

byTakashi Hongucho, Hodeyuki Okumura, and Noboru Saela ............. 307 

Three New Ash Beneficiation Processes for the 21" Cenrury 

by Bruce W. Ramme, Bryan C. Fisher, and Tarun R. Naik . . .......•• ... .. 325 

Advances in Malaysian Fly Ash Concrete Technology 

by E. U. Kidav, T. P. Soo, Y. Sirivivatnanon, and R. Khatri ........ .. ... .. 343 

Properties of Artificial Pozzolan Blended Cernenu as a Function of Clay 

Precursor Moneraloar and Cement Chemical Parame!en 

by E. Moulin and P. Blanc .. .. . . .. . . . . . . . . . .............. .... ... 361 

Concrtte MixturtS Made: with Tenwy Blended Cernenu Containing Fly Ash and 

Rioe-Husk Ash 

by N. Bhanumathidas and P. Kumar Mehta .................... ... ..... 379 

Time of Setting Influenced by Inclusion of Fly A.1h and Chemical Admi.,tures 

byTarun R. Noik, Sbiw S. Singh, and Bruce W. Rammc ... ..... ..•.. ... . 393 

The Resis1ance of Mortar with Supplementary Ctmcntitious Materials to 

Caustic AnRek 

by H. T. Cao, L Buoe11, R. P. Khatri, andY. Sorivivatnanon . ............. 41 S 

Effects of Co-Combustion of Secondary Fuds on Fly Ash Quality 

by F. J. M. Lamen, J. L J. Yissers, and J. W. ,..., den Berg ••... .......••. 433 

VIII 

SP 199-1 

Leachability of Trace Metal Elements 

from Fly Ashes, and from Concrete 

Incorporating Fly Ashes 

by M. H. Zhang, M. C. Blanchette, and V. M. Malhotra 

Smopsis: .. This pnper presents infonmtion on the ~achability of rrace metal 

elements from a number of Hy ashes from Canadian lllld the U.S. sourees, and from 

the concrete mcorpontlng the Hy ashes. 

Tbeco~tnhODSofaDregulatedelement£Ag, As, 0, Ba,Cd,Cr.Cu. Hg. 

Pb, and Se in the lcachatcs from the nine Hy :uhes testod were wullin the limits o'· 

the Unitod St.otes Enviroruncnt Protr:<:tion Agency and the TransJxmation of 

Dangerous Goods Act Regulaoious of Canada. Tilt k:achong of As, B. Ni, and Se 

from the fly ashes appeared to increase with an iocreRSC in their ooment in dtc 

Ry ll$h; 1to\\1ever, there were some exceptions. Ju genc:rol, lhe concentration of As 

leached from the fly liSbcs derived from the bituminous .ooools was much higher tluw 

that from the li&nite or sul>-bitwninous coals. .I 

.. Regoudle., of the type and pcroc:nt"l:e of the Oy ash used. wfcm of obe 

concrete, and curing coodotioo, none of tbe traee metals on tl.e leachates from obe fly 

ash concrete ~les oxoeedod the regulated concentration bmots by the Uruted 

States Envirom:no:nt Protecuon Agency and the Tnmsponauon of Dangerous 

Goods Act R:fUIIIions of Canada. The «>nc:rete incorporating the Hy aslles is, 

therefore, considered envirownentaDy stable. 

Keywords: concrete; fly ash; leachability; trace metals 

1 
'•' 2 Zhang et al. 

Min-Hong Zhong is Associate Professor at the Department of Civil Engineering, tbe 

National University of Singapore. Prior to joining the university, she walla Research 

Scientist with CANMET, Natural Resources Canada. She is a member of 

ACI Committees 213, Lightweight Aggregate Cooct•ete; 232. Fly Asb ond Nnturol 

Pozzolans in Concrete; and 234, Silica Fume in Concrete. 

Marcia Blond>ette =ages the Tailings and Waste Rock program in CANMET, 

Natural Resources Cauada. She has over 10 yeats experience with envitomnental 

issues facing the mining industry in Canada, through her involvement with the Min~ 

EuvirotUnent Neutral Drainage (~ND) program, and activities within the 

Eoviromnent Laboratory of CANMET. 

ACI Hooorary Member V. Mohan Malhotra i.s Scientist Emeritus. lutenunional 

Centre for Sustainable Development of Cement nod Concrete (ICON), CANMET. 

Ottawa. Canada. He is a t"otmer member of the ACI Board of Ditection and has 

served on numerous ACl cotiUnittees. He is a prolific author, editOJ', ood researcher, 

nod has received lllllllY awards aod honors from ACI and other institutiotL~ 

throughout the world. 

INTRODUCTION 

Portland cemeut conc..Tete is 11nd will remain :;. majo1· construction muteriul 

of choice. Unfortunately, the productkm of port laud cemem. the roost importum 

component of concrete, is very energy intensive. Furthennore. the mauufa~turing of 

portlnud cement is enviroruneut.aUy wtfriendly because fOr each tonne of cen:,ent 

produced, approximately one tonne of co, is released into the attoospbere. Thus, 

replacing port of portland cement by minerlll by-products such os fly ash or ground, 

granulated blast-furoace slag in concrete can coot.l'ibute signiticumly to the reduction 

of col emissions, lllld snvings in energy. 

Tilete is a growing C01)Cel1\ that the ClniSSiOUS O[CQl and Other greeohO\ISe 

gases are affecting adversely tbe global climme. It is. therefore. imperative that 

policits and programs be developed to t·educe the level of CO, emissions. TI1e 

Canadian GOvenlJI)ent has OJJJlOUDCed that Canada, iu accordance with the Kyoto 

Protocol, will reduce CO, emissions to abom 6% below 1990 level by the year 20 l 0. 

By replnci.ng portland cem!nt in concrete with t1y ash. a by-product from th~ bt1nling 

of coal in electric utililies. C02 emissions can be reduced considerably that con h~lp 

to meet the above objective. Typical replacetnent levels of fly ash in portland 

cement concrete are about 20% by mas:; of the total cemenlitiou:. mat~r ul~. With 

inc~asing use of fly ash in concn::te, questions have been raised i.lS to the pCHeutiaJ 

contamination of the surface and ground water by the trace element~ iu fly ush <~S n 

result of the leaching. 

1 

r 

I 

I 

t 

I 

I 

' 

Fly Ash, Silica Fume, and Slag 3 

Tills pElptr presents iufonnation Oil the Jeacbability Of trace eJetnCUIS f i'OJn 

u uumbet' of tly ashes from Canadian aud the U.S. sources, aod fi-om the concrete 

in<:orporuting the fly ushes detcnnined according to the Un.ited States Envi.roJUncnt 

Pt-otection Agency (EPA) re¥ulatorymethod I 31 I -ToxicityCitarocteristic Lcachitll[ 

Procedure (TCLP). The et\'ects of fly ash sout·ce and comeut, wll:m, aud cw·i.ng 

'-'Ondition.s of the coucrett on the leachability of l!'ace ll'letal eletl)(nts were also 

evaluated. 11\is study provides. data that are not available in publislM!d literatt•re. Th~; 

effects or Jeadililg condilious that simulate weuing and d.l'yi.ng aod tbe typc::s of 

leach.am.s ou tl1e Jc::achability of trace metal elements have been discussed elsew hete 

(1,2]. 

LITERATURE REVIEW 

Pt1blished data have shown that the lellchability of trace elemeu1s from a 

tly osh is c.ltpcndeut on the chemical composition of 1be fly ash. n t'uuction of the 

opetatiog couditious of thc.:nnal power plants [3). and lhe exposure cooditioos. 111e 

combu,•aion ttmperotures of the boiler and the operating lemperatures of the 

emission control devices are significant comroU.ing parameters aftfet.iug the 

distribution of the trac.e ek:ments in a coal ash. J.n most cases, tOr ditferem coals 

bu~1tt:d in the same combustion uu.it under similar opel'ating conditions. lhe 

disltibutiou of most eheanicfll species are similar [3]; however, for diffetent conls,. 

bumed undet· tlitft!re.ot combustion conditions, no defm.ite distribution pauen1 of 

u·ace elements c.t~o be detennined. luoomplcte combustion can result in h1gher 

conc~ntl'ation of Leachllble trace eltments in a coal ash; and a coal with a lower heat 

content yields more leachable trace elen::tcuts. probably because of the lower 

combustion tempeJ'.atures in.sitle the fumnce [3). 

De Groot ct al (4) investigated the leaching c~tel'istics of selected trace 

elements such as orseo.ic (As), cadmium (Cd), copper (Cu), antitnouy (Sb), seletliwn 

(Se),molybdenum(Mo), lead (Pb), tungsten (W), vauadium(V),aud zinc (Zo)from 

coa.l fly ashes as a function of tbe acidity of the leacbant • a.ud tlte liquid/solid. '111e 

test consisted ol'three parts: a COhllUU·Ieachi.ug test. a serial batch-leaching test. and 

a test fordeleJ1l\.i.nin.g the maximum Leachability. Fifty tly ashes from a wide variety 

of sources were analysed. and only five fly o.~hes were cested using all the three tests. 

The authors round thol with tespect to leach.in..g. diJ'ferences in elemental 

composition of the fly ashes are far less imponant than the differences in the pH of 

thelenclulnt. The pH level of a Jeachaut is the controlling factor in the leachability 

of trace elements from a tly ash, and at a high pH (> 11) the solubility of u-ace 

elements is limited. All the ashes tested showed common le11ching characteristics 

for severn] groups of elements. The trace elements present in the fonn of species, 

e.g. As, Sb, Se, Mo, W, and V, behove sitnilnrly, and showed a characteristic 

• Leaclulnt is defmed as a solution or liquid used for leaching. 
A 

• 4 Zhang et al . 

mu.imwn leaching at neutral pH. and d<cruse m l<achina rowanls loW<r and higl><r 

pH values. De Groot et •l (4] aiJo foWld that the l<:ogth nf the batcb-leaching t"t 

of24-bourdur.moo is sufficient for 1110$t elements ro rencb equilibrium, and can be 

• sigruficant factor only for a few elements such as arsenic. Sb. ond V nt higbly 

alkaline conditions and lo" liquid/solid for which the reaction kinetics are slow 

The leaching cbaracterisrrcs of • fly !L<bes from the thennal power plane< 

operated by Omario Hydro, TOI'OntO, Canada have been Uocmnented in a review 

repon (5). Fly ashes derived from bitumioou.s conls generally have higher contem 

of tl1e trnce metal elements (As, Se, Cr, V, nnd Ti) tlmn the fly ashes from lignite 

coals. The concentration of trace elements extracted from leacbates· of the fly ashes 

we'7 less tbon 10 times the criteria outlined in Schedule 4 of Ontario Ministry ot 

Envtronment Regulanon 309 (drinking-wa"'r standard). 

The leaching of rrace elen><nu from concrete and mortars incorporating o 

fly ash as panill cement repl..,.mcnt was inv.,hga~ by Vao der Sloo~ de Groo~ 

and Hoede I 6). Ay ashes from con•·ennonal I1ISI&IIaoons and installatioru oper•tina 

with low !\Ox bum<rS were includ<d m the IIUdy, nod cement replacement le•cls in 

ooocrete ranged from 20 ro 40'll>. Both poruand eement and blast-furnace sing 

cements were used in the srudy, and the wattt•tO-Cemcnutious materials ratio (wl<:m) 

or the concrete ranged from 0.50 to 0 64 The lenching of the concrete was 

determined using a modified procedure based oo Dutch standard NEN 73-15. TI1e 

moruu- specimens were crushed m njnw-erusher, nnd separated into three fractions 

(A: 1.5-6 mm, 8:0.5-1.5 mm, and C: <0.5 nun). Th..- samples were then treated 

with demineralized water with different hqutd· to·sohd ratios (500, 100, 20, 4, 1), 

ond the contact times were 0.5, 5, und 50 hours. Afte1· tJ1e treatment. the pH aml the 

concentration of the elements As, Br, Cr, Cu. Gn, Mo, Sb, Sr, w. Zo. Co, Si, Mg, 

Na, K, Cl, F were detennined. The results indicated that the concentrntion of tlltse 

elements in the Jea.:hate from tl1e fly ash concrete was higher ~um tl>at from the 

control ponJand cement concrete. Nc,·ertl\Cless, w&th the exception of Mo, the 

leaching of the above elemenu from the Oy ash concrete was generally witbrn tl>e 

specification of the Building Moterills Decrte of the Netberlonds. This implies that 

replacing pan of pnruand cement by fly ash rs environmentally aooepul>le. 

Hobbctg and Schiess! (7) studied theeftectofthetypeofcementand fly ash, 

wkm. and curing age on the leachlns beha•tour of the monan and couon:te Both 

norml1l pnnland cement and blnst-fumnce sloa cement were used 10 the in\'esUgation. 

Four fly ashes with different heavy metal contenu were Klected for the evaluation 

The Oy asb content was 20% by lnii$S of (Cement + 0.5 Ay Ash), aud the 

W/(C+0.5FA) of the morrars tlln£ed from 0.4 to 0.6, ond the W/(C+0.5FA) of tl>< 

concrete was 0.5. A number of 40 • 40 • 160-tnm prisms and 100-nuu cubes were 

mnde from the mortar oud concrete mixturt:.s, respectively. After Olle day in the 

·Leachate is defmed as a solutjon obtniueU by Jcnch.injJ. 

I 

I 

I 

Fly Ash, Silica Fume, and Slag 5 

moulds. the specimtm "ere cured Ill a ciUlD>ber at 20 'c and 9511> relnti•'C hurniduy 

until theogesof90, ISO, and 360days for leaching t<>ts. Tank-leaching testss111Uiat 

ro that de>cribed in Dutch Standard NEN 1345 with a duratioo of 56 days, and 8 

leacbant renewals we~ perfonnN w1th lbe monnr WKI concrete specimens_ 'The 

results illdrcated a>ar the lcacluog of the metalelemenu (As. Cd, Cr, Cu. Pl>, Nr, and 

Zn) from monars and concrete with and without fly asb was genernlly very low. nnd 

was lnr~e y independent of the tOtol amounr of the fly ash mcorporated. The 

incoaporatiou of the 11y o~h in concrete r!!Ouced the leaching rate in case of most 

U"U~.:eelemen ses ecially zinc. The w/cm had no distinct iotluence on the le-achability 

of the metal clements, nud lonaer curin, led 10 lower leaching rates. 

SCOI'E 

TI>e leachability of traCe eletntl\1$ from K\'ell fly ash .. from the Caoadr:>n 

10un:es and two fly ashes from the U.S sources, and from tbeooncrere incorporating 

the ny ashes is presented. In these DIDC ny ashes. se•·en of them meet the 

requiremenu or ASTh1 Class F fly ash. one of them meers the requiremenu of 

ASThl Oass C fly ash. and the "'mauuna one meets all the reqwrements of AS"N 

Class F ash except for the f=ness The fly ash content w con<reteronged from 10 

10 60'11> by mass of the toto! cemennnou• materills, aod the w/cm of the concrete 

l'llllged from 0.40 to 0. 70 The concrete was cured Wider the following three 

conditions prior ro the leaching t""' (I), l·day molSI cunng ond 27-day air dryiog' 

to simulate the field practice, (2), 7-doy moist curing aod 21 -day air drying to 

simulate the condition most often specified but rarely followed in the fields, oud (3), 

28-c.Lny moist curing tO simulate an ideo I lolx>nuory-curing condition. 

All the fly ash and concrete samples wer·e tesied according to EPA method 

1311-Toxicitycbarnc..,ristic Jeachiuaprocedure ('!'CUP)' , using aO.J N acetic acid 

lenchnnt with a pH of 2.88. · • 

MATERIALS 

tlr Ashes 

Seven fly ashes from locations acroa Canada ..... selected for tbr.s study. 

and they were Point Tupper. Nova Sooua, Llll&ao. Nova Scotia; BeUedune, 1\ew 

Brwuwi<:k; Thunder Boy, Ontario; SWldanee, Alber~>; Forwt>urg, Albena; Genesee, 

'United States Eoviromneotal Protection Agency (1990) "Toxicity characteristic 

leaching procedure, method 1131". In Test Methods for Evoluating Solid Waste, 

BPA SW-846 (Revision 0, November 1990). 
• 

• 

6 Zhang et al. 

Albei'Ul. Two fly ashes from Belews Creek, Georgia ond Con! C=k, North Carolina 

in the United States were also included in the Study. 

·n1e physical properties and chemical composition of major elements, as well 

as the content of trace elements of the fly ashes were detennined, and the resultS are 

summarized in Tables I and 2, respectively. TI>e dat4 on the ttoce elements in coal 

ash, in cement lllld m :10Lls are also in Table 2 for comparison purposes (8,9). 

For the IWIC fly ashes e,·aJuated, seven of them met the requirements of 

ASIM Clnss F ash. and ooe of them ('Thunder Boy asb) met the requirements of 

ASTM Class C ash, However. one fly ash (Genesee) met all except the fmeness 

requirement of AS1M Class F ash, 

ASTM Type I portland cement was used for making concretc.ltS physical properties 

and chemical compositiou are gh•en in Table 3. 

Agrrecate 

The coarse aweaot.e wed ,,,as a crushed granite with 0. muimum nominal size 01 

19 mm, md the fine aggregate was natural sand from the Ottawa region. Both the 

coarse and fine aggregateS were separated iotO different size frnc:tious rut<! 

recombined tO a specified gradation shown in Table 4 The spe<'ific gravities of the 

coarse and fine aggregates were 2.72 and 2.70, respectively; ~ .. com:Sponding 

values for water absorption were 0.5 and 0.8 pe=nt. respectively. 

SuperplasUrlzf::r 

A sulfonated, naphthalene fonnaldehyde-condeusate type superplO.'iticizer 

was used in some of the concrete mixtures. ,le superp1o.s:ticiz.er is a dart: brown 

solution cont4iruog 42 pera:nt solids. 

Air-Entraininr Admirturc 

A mulu-cornpottent synthetic-resin type of oir~entra.ining admixture wos used 

in all the concrete mixturts. 

Fly Ash, Silica Fume, and Slag 7 

CONCRETE MIXTURES 

Mixture Prooortinns 

Twenty concrete m.i.xrures were prepnl'ed,and I 02 x 203-mrocyliuders were 

mode for compressive strength and leaching testS Tho mixture proportions of the 

concrete are &iven in Table 5. A control porllrutd cement concrete with a w/e of 0 S 

was used ll5 the reference. Nine fly ashes were e>•aluated. Tile Lingan fly ><h was 

selected for evnluouna the effects of the pe=mage of fly ash and w/cm on concrete 

leaching because 11 bas the bighcs< As oontent of the wue fly ashes. Tile ny ash 

content ranged from I 0 10 ~bY mass of the tatnl cementitiou.s material The w/em 

ranged from 0.40 to 0.70. Two high-volume fly ash concrete miAtures with a low 

w/cm of 0.32 were aLso in<:luded for evaluation. 

CASTING AND CURING OF CONCRETE SPECIMENS 

The concrete was mixed in a laboratory counter..current mixer for a total of' 

S minutes. 'The proptrtiesoffreshconcrete includmg the slump, air con rent, t10:d unit 

weight were det<mllDed immediately aftts the miAing bad been completed. 

A number of 102 x 203-mm cylinders were cast from each miAture fQr 

determining the compressive strength, and the leochability of metals from concrete. 

The cylinders were cast in two layers and consolidated on a vibnuiog table. 

After casting, n11 the cylinders were left covered with wet burlap in the 

casting room for approximately 24 hours, then demolded lll!d transferred to a moist· 

curing room at 23 :t 2 'C and 100% relative humidity' until required for testing. At 

the time of testing, ll1e couc1'ete cylinders were taken Out or the rooist-curiog room 

either 10 be cured furlller in the laboratory air or tOW: prepared for testing. 

TheoompresSt>esm:ugthoftheooncn:te was detenninedafter7 and 28 days 

of moiSt curing. For vanous leaching tests, tine <hfferent cunng regimes were used 

in this study. Most of the cylinders were cured in a mout·eu.ring room for 7 days 

followed by exposure tO laboratOry air for 21 days before the leaching rests to 

simulate the condition most often specified but rarely followed in tbe field. For 

selected concrete mJxnu·es, additional cylinders were cured in the moist-curing room 

for one day followed by exposure to laboratory air for 27 days to simulate the field 

practice. In the third curing regime. the cylinders were cured in rhe moist-curing 

room for 28 days to s-imulate an idenl laboratoty-curin& condition. 
.. • 

8 Zhang et al . 

PROPERTIES OF FRESH CONCRETE 

The properties of the fresh concrete jocluding the slwnp. unit weight. air 

content, ond 1empernture are summarized iu Table 6. Tile slump of the concrete 

ranged from 65 to 230 rom, and ~1e air content ranged from 4.9 to 6.9%. The unit 

weight of the fresh concrete wns 2350 ± 57 kglm'. and the temperamre of the fresh 

concrete ranged from 19 to 25'C. 

COMPRESSIVE STRENGTH AND DENSITY OF CONCRETE 

11te density and compressive strengtlt of the eoncre1e cylinders at 7 ond 28 

days are given in Table 6. Tlte control portland cement conc..Tete had compressive 

strengths of 29.1 and 34.3 MPa at 7 and 28 days. respectively. The compressive 

strength of the concrete incorporating 30% fly ash but with lbe same w/cm ::tS the 

control coucreteranged from 17.8 to23.0M.Paat 7 days and 24.8 tO 33.9 MPa at 28 

days. 11te 28-day compressive strength of the concrete incol'porating Liugon tly ash 

decreased from35.0 to 15.3 MPa ns the fly ash content increased from 10 to 60%by 

mass of the total cementitious materials.. The density of the concrete dctemtined at 

one day ronged from 2308 to 2444 kglm'. 

LEACHING TESTS 

In gcnernl, a le.aching test involves bringing a waste material in couct!lct with 

a Jeachant to detennioe tbe components that will be dis.~o ved from the waste:. The 

purpose of leaching tests is to either classify n waste for disposal or to detennine tl1e 

leachate quality. 

Leaching tests are divided into two broad categories depending on whether 

the leachant is renewed or not. For extraction testS (batch-leaching tests) tl\e Jc:ac.:ham 

is not renewed; instead a specific amount of waste is brought in contact with a 

specific amount of leachant for a specified time. At the end of the test. the liquid is 

separated from t1te waste and analyzed These tests are short tenu, have good 

reproducibility, are simple to perfoml. and are often used tO simulate the •worst 

case" scenario for leaching of the waste. All regulatory leacbiJlg protocols specify 

extraction testS. 

Dynamic tests are those in which the !enchant is continuously or 

imennittent1y renewed to mainto.in aconstnutdrivi.ng force for lenchiug, c.,g. colulllll· 

leaebing testS. l11e column-leaching test is perfom1ed by packing the material to be 

evaluated in a column. a.od passing a given volwne of leachant through the matetiaJ. 

lltis type of the test provides infonnatiou abotu tbe k.ineticsofwastedissoJution, und 

they are generally coosjdered to be more repre.senuuive of the field conditions. 

~ 

[ 

{ 

I 

1 

Fly Ash, Silica Fume, and Slag 9 

In this study, the leachability of the fly ashes, and concrete incorporatil)g ~~· 

fly nshes was detennlned by the EPA TCLP test (18-hrextraction). The o·e.<ults on 

long·tenn batch-leaching test and co1unm leaching tests have been rep<lrted 

el~wbere [ 1.2). 

Leaching Test for Flv Ashes 

The leachability of the fly ashes was determined according to the EPA (U.S.) 

Testing Metbod 1311-Toxicity Characteristic Leaching Procedw·e (TCLP), that is 

a standal'd regulatory method for classifying materials as hazardous or non· 

hazardous. ll>e matetial to be tested is crushed or grolll)d tO pass ~ugh a 9.5-nun 

sieve. The extraCtion fluid to be used depends on the pH of the material being tested. 

u·the iuitial pH of a 5 gram-sample of the material mixed with 96.5 mL of distilled 

water is greater than 5.0, the wnste is acidilied with 3.5 mL of IN HCI. heated for 

2 minutes, cooled to room temperature, aod then measured agai.u for pH. If the pH 

of the resulting suspeotsion is less than or equal to 5.0, a O.JN sodium acetate buffer 

solution is used. If the pH is greater than 5.0, as in~,. cases of the fly ashes, n O.IN 

acetic acid solution with a pH of 2.88 is added to the solid phase of the waste in a 

liquid-to-solid ratio of 20: I. The tn.ixmre is then agitated for 18 hours and the 

leachate is then filtered, and analyzed for Ag, As, B. Ba, Cd, Co, Cr, Cu, F. Fe, Hg, 

Mn. Ni, Pb, Se, 11, U, V. Zn, and Zr. The TJA IRIS simultaneously inductively 

coupled plasma-oton'ticelnissiou spectrometer (ICP·AES) was used todeterm.iue the 

concentration of B, Fe.Zn, andZr. The VG PlasmaQuad inductively coupled plasnlh 

massspectrOmeter(ICP·MS) was used to detennine ecoocentrat ouof Ag, As, Ba, 

Cd, Co, Cr. Cu, Mn, Ni, Pb, Se, Tl, U. and V. Fluorine was determined by t11e ion· 

selective electrode. Mercury \\1as detennined by the flow-injection cold vapour 

atomic absorption spectrometry. 

Lt aclJipg Test. Cor Contrete lncorporatioc Fly ,\s~es 

··.~ The leachability of the trace elements from the concrete was detenniued 

using the same method as described above. After 28 days of curing, a slice of 

concrete, approxitnmely 9.5-tlltll thick, was cut from the mid-height of a cylinder 

from selected concrete mixtures and cuting regimes. A part of each slice weighing 

approximately 100 grams was cntshed carefully using a hammer so that all particles 

were< 9.5 nun, and the variation in the particJe .. si.ze distribution was not significant. 

The particle- site disuibutiou of the samples can be folll)d in reference [ 1]. 

Each crushed concrete sample was treated with an acetic acid solution of pH 

2.88 at a liquid-to-solid ratio of 20: 1 for n pe1'iod of IS hours. TI1e leachate was 

filtered, and analyzed for pH, As, Cd, Cr, Cu, Pb. Ni, Se, Zu, and Fe. Quantitative 

elemental analy~s of the leachates were performed by ICP· AES for Fe and Zu, and 
• 

• 10 Zhang et al. 

by ICP-MS for A•. 01. Cr, Cu. N1, Pb, nod Se. These elemems were selected by 

comparing the comenland ~"' Jer.chability of the metals from fly ashes ond pol'tland 

cement shown in Tnbles 2 and 7, respectively. 

WATER QUALITY GU!DELL'I/ES 

Uacluna ltsU ~!ermine "'belber lhe WaslO WllJ release OOilromiiJ80U 1010 

an aqueous medJum, and based on lhe dusolvcd ooooeolnltions from lhe oesu, a 

maoerilll can be clwafied as hazardous or ooo-ho::udous Tbe regula10ry leach 

protocol, on which most other tests are based is the Environmental Protecnou 

Agency (EPA) Ex unction Procedure Toxicity'"" (EP Tox) lbat was promulgoted 

inlhe United States in 1980. The criteria for metals ru-e setal 100 times me Naoionnl 

Drinking Water Stoudo1·ds, aod the matel'inls f1'0m which leachrues exceed tht:)C 

criteria are chnracttlized as ho:ardous. Inl990, the U.S EPA replaced the EP Tox 

test with the Toxic Chruactcristic uaching Procedure (TCLP), that incorporates o 

number of procedural and equipment changes but leaves the criterill for the metals 

unchanged. 

In Canoda. lhe provwces bave adopted leac:hate..,xlnlcrioo proc<dures d••• 

""' sunilar 10 those of EP TaL Tbe only maJor difference " in lhe liS! ol 

contaminants in the leachate that vnry from one provux:e to another lbo:;e 

province$ thttt do not have hazardous waste regulations c.an utilize the provisions ut 

lhe Transportation of Dangerous Good• Reaulauons (TDGR). The TDGR 

incorporoted the Leachate Exuoction Procedure CGSB 164-GP-IMP in 1989 in 

which list of COnllllniuruus and munericol crite1·in tu'c identical to thOSQ usc::.J in 

Ontario. 

Wctuue..quality criteria for metals for the ''arious tests discussed is Jive:n in 

TableS. 

RESULTS A11o'O OISCUSSI0:-1 

l&a('habi!ity oC Fly Ashes 

TI1e results of the leachability of the trace elemeocs from the tly ashes are 

slllllllWized iu Tobie 7. The coucenonuion of elements A¥. As, B, Bn, Cd, Cr. Cu, 

Hg, Pb, Se, and Zn in the Jeocbotes from aU the ny ashe• tested were Within the 

limics mentioned above Coocenll'lltions of Ag, B, Ba, 01, Cu, Hg, Pb, and Zn nrc 

at least ao order of magnitude below lhe limiu set out in Table 8 The fly ashes""' 

envU'Oillllentlllly safe wtlh respec110 lhe TCLP reaula:ory test 

' 

I 

Fly Ash, Silica Fume, and Slag 11 

~ o.rscn.ic(A5) content in the leachates from the four fly ashes derived from 

tl1e bttuminous coals (Point Tupper, Lingnn, Belledune, and Belews Creek) ronged 

from 0.85010 1.317 ppm. and this was 111uch hi&her than that of the fly ashes from 

lignite or sub-bituminous coals ( <0.1 ppm). However, even tbe highest ttl'senic 

content in tbe leac:haoe from Belledw1e fly ash wos;ull well below tl>e U.S. EPA and 

Canodian TDGR regulatOry limits. 

Tbe cbrouuwn (Cr) oontenl in lhe leacbates from lhe fly asbes den'·ed from 

lhe birutrunous coals was s 0.070 ppm; this was much lower lbao lbat of the fly 

asbesfrom han ate or sul>-b1tummous oools (0 164. 0.661 ppm). TbeEPA and TDGR 

reaulotory Jurut for lhe Cr IS 5.0 ppm. 

The seleniwn (Se) content of the leachotes from moSt of the tly ashes wn• < 

0.2 ppm except for~,., from the Belews Creek tly "-'h (0.55 ppm). The regulmory 

limit of the selenium specified by EPA of the U.S.A. and d>e province of Ontario, 

Quebec, nod B1•itish Columbia in Canada is 1.0 ppm 

Tbe leachability of As (except lbat from d>e Belews Creek fly asb), B, Nt, 

and Se from lhe tly asbes appeared to ina-use with 111 tDcrease m iu conoeot in lhe 

Oy ashes. wllllelhe leachability of Fe, Ba, 01, Cr, Cu. Pb. andZndid nouppear to 

be related 10 lheor cootr:nl m t11e fly asbes. Fiaure I iiiUSinloes lhe relaaoowps 

between lhe oonctnb'altotu of A$, Cll, Ni, 111d Zn leached from lhe fly asbes ond 

tbeir content in !he fly asbes. ' ' 

Leachabllih• of Mclal Elements' (rom Cgpcrclc 

Tite effects of the fly ash source, fly nsh content. w/cm, aod curing time on 

Lhe c::onc:eutrat:ton of metals As, Cd, Cr, Cu. Fe, Ni, Pb, Se, and Zn in the teachales 

from lhe concrete i• presented in Tables 9 10 12. The' coooeouations of lhe metal 

elemeuu 1n lhe leac:hates were significantly lower thl>.n lhe limiu specified by lhe 

EPA, U.S A, aod lhe TDGR, Canada. 

Tbe neulnlhung pcoential of lhe concrete IS W>Cierhned by lhe general rise in 

lhe pH over lhe 18· hour teSt procedure (final pH rang ina from 5.3 to 6.5) relnttve 

to the pH of tl1e Leacbanl. Measured concentrations of Se were at or below the 

detection limits, and therefore, will not be discuiSed furt11er. For Pb, many of U1e 

vaJues were close to or below detection limi[ again mnking comp3risous difficult A 

summary of t11e observotious of tl1e leaching trends is presented in Table 13. 

EUect of ny ash-In general, all the Oy ash concrete samples showed sinulnr 

or higher mellll values wben compared with lhe conu-ol port1111d cement concrete 

except for Cr. Chrorruum values forlhe fly axbooocrete samples oested were simtlar 

10 or lower than those of lhe OO!lb'OI pcrdand """"'"' oouc~te. 
• 12 Zhang et al . 

Etrrd ofthcsoottc oCOy ash-For fly ash. the parutioningoftrace metals 

be~W«D the spbcri<:8l poruon of the fly ISh (Jlwy stnJCIUI't, relatively immune co 

di<soluuon) and the sutf'oce of the spbere (easily exchangeable or adsorbed 

molecules that""' more prone to diuolutron) will ultuno<ely affect the nature of tbe 

produced leachate (101 A companson of As, Cu. Zn ond Ni leached during tl>e 

TCLP rest versus the traee metal cootent in the moe Oy ashes tested is presemed in 

Fig. 1. 

As shown in Fig. I, the degree ofleachability of As from a fly ash is reflected 

in tlle content of that metal in the fly ash itstlf. The !Uitne is true for the leachability 

of As from the fly ash concrete (Fig. 2). For example, concrete containing Point 

Tupper, Lingon, and Belledune fly ashes (Mix!Un:s Tl, T2, and 17) sltowed the 

highest concentratioo.s of As in !heir lcn<:hJte.l from tlte TCLP test; this is because 

the above fly ashes bad the grenteSt conu:nt of As of 688, 980, and 505 ppm, 

respectively Other metals analyzed dtd n<>t show the same relationship. 

For arseoie. the pctttnla&e leached from the concrete incorporating 60'K. 

Ung111 fly ISh (Mixrure Tl4) of the toul avatlable metalm the mixture have been 

calculated, and summari.zed Ill Table 14. This concrete repre~ntsthe highest anenic 

contenl at -SOmglkg CODCI"t:te, and 11 considered as lhe extreme. 1be total 

oonceotrauon of arsenic leocbed from the concrete was less than 0.5% of the IOta! 

avoilable arsenic from the fly ash in tl>e concrete. 

An assessment of the partitioning of these elements between the g1ass:y and 

surface portions of the fly ashes was oot done in this study. However, in general A~. 

Cd, Pb, mtd Zo have been reported 10 show surfooe enriclunent, while datu for Cr. 

Cu and Ni are reported to be inconclusive [!OJ. 

EUeet of Oy 3.5h content •• Fiaure 3 thows the effect of the percentage of 

Lingan Oy ash _ in concrete on the ooncentrntion.s of As. Cu, Ni, al)d Zn in dM! 

!<110hates from the concrete in the TCLP leachi~Ji te>l. Wbile most of the tD<Uib 

analyzed sucb as As. Cd, Cu, Fe, and Pb in the Jeachates showed increasmg 

leachabihty with an increase in fly osb coment in lhe concrete. Nl showed a sHght 

decre3sing <rend. In fact, most of the Nt wu prohably from the portland cement. 

N'tekd, therefore, sbowed decreasmc trend wtth mcreasmg fly ash content be<:ause 

the c:ement conteo.t in eooc~te with higher fly ash content was lower. No significant 

umd was obser\--ed for Cr with an &Defta!e 111 the fly ash eonteoL Zmc in the 

leachates appct1red to increase sotnewhat with an increase on the fly ash content, and 

the significantly higher value for the concrete witll 10% fly ash (1'10) is prohablydue 

ro e~perimental error. 

Ertet.t of w/gn-Figure 4 shows the effect of the w/cm of coucrere on the 

coneentratioos of As, Cu. Ni, and Zn in the leachates t'I'Om the concrete in tbe TCLP 

leaching test. From the results shown in Table I I nnd Figure 4, it oppe.urs t11at w/cm 

Fly Ash, Silica Fume, and Slag 13 

of concrete did 001 ha'~ any sitcwficmt eflect on the leachability of Cd, Cr. Nt, attd 

Pb. However, as the fly ISh coo tent Ul the concrete with a !ugh wfcm is lower thoo 

that witb a low w/cm, the leachabiluy of Cd md Cr actually increased wttb 

mc:roastng w/cm due to the wcreased porocuy of tho concrete. Coppcs, Fe, aod Zn 

sho""·ed increasing concenttataons with incrt:asmg w/cm even though the fly ash 

content was lower for the concrete with a lujh(r w/cm A.rstnic showed a decreasing 

trend with an increase in tho w/cm. By calculating leached As per kg of the ny ash 

in the concrete, it seems thnt the w/cm did not have significant effect on the Jeuching, 

and the fly ash coment appeared to ben controlling factor on the leaching of As. 

EUect ofcurinc-·As shown io Table 12, the length of tlte moiSt curing does 

not seem co have significant effect on the leaching of the above metal elements. 

CONCLUSIONS 

The coocentratioosofallregulltedelemeotsAg. As. B, Bo. Cd, Cr. Cu. Hg, 

Pb, and Se in the leachates from the nine fly asl>es tested were within the limtu of 

the United States Environment Protecuon Aaency and the Transportauoo of 

Dangerous Goods Act RegulouousofCanada. The concentrations of Ag, B, Ba, Cd, 

Cu. Hg, and Pb were all at least an order of maanitudc below the above limit~ ThC 

leaching of As, B, Ni, and Se from the fly ashes appeared to increase with nu 

increase in their content in the fly ashes: however, there were some exoeptions. In 

general, the concentration of As leached from the lly nshes derived fro10 the 

bituminous coals was much higher tltru\ tllnt from dte lignite or sub-bituminous 

conls. 

Fly Ash Coocate . ' 

Recnrdless of the type and pcrceutage of the fly ash used, wfcm of the 

coocrete, and curing coodition. nooe of the trao:e metals ul the le:>c:bates from the fly 

ash concrete samples e.ceeded the n:gulated concenuauon limits by the Cruted 

StateS Enviromnent Protection -"ency and the Tnnsponauon of Dangerous Goods 

Act n:gulatioos of Canada. The concrete incorporating the Oy ashes is, therefore, 

coosidered Stable. 

In general, all the fly ash concrete Janlples showed similllf or higher values 

of the metals (As, Cd, Cu, Fe, Ni, Pb. Se, Zu) when compared with lhe control 

portland cement concrete excepr for Cr. Chromium value.~ for the fly asb concrete 

samples tested were similar to or lower thon those of the control por~and cement 

concrete. 
• 14 Zhang et al. 

Arsenic showed a «.:l.lrrelntiou between the metal content in fly ash and the 

concentration of tbe metal leached from the fly asb conctere. The total conceotrotiou 

of arsenic leached from the concrete with a w/cm of 0.50 and incorpora.ting 60% 

Ungan fly ash. that contained the greatest concentration of arsenic of the fly ash 

concrete tested, was less than 0.5% of the rotal availoble arsenic fron) the ny ash in 

the concrete. Other metals anaJyzed did not show such a relationshjp. 

Most of the metals analyzed such as As, Cd, Cu, Fe, and Pb in the leachates 

showed increasing leachability with an increase in the tly ashcontentin the concrete. 

Cadmium, Cr, Cu. Fe, and Zn in the leachates showed increased 

concentrations with increasing w/cm even though the fly ash content wns lower for 

concrete with a bigber w/cm. The leaclling of As did not seem to be affected 

significandy by dte wlcm of t11e concrete. 

The length of moisture curing period did not have significant effect on the 

leaching of the trace metals from the fly ash concrete. 

ACKNOWLEDGEMENT 

Tllis project was jointly funded byCANMET, Naturnl ResourcesCuuado ond 

En·\'itonment Canada. Grateful acknowledgement is made to Ray 01evrier nnd 

Annibale Ferro ofMaterinlsTechuology Laboratory nod Ted MacKiruJOU of Mineral 

and Mining Science Laboratory, CANMET for laboratory wotk. 

REFERENCES 

(1] Zhang, M. H., Blnncbette, M., and Mnlhotrn, V. M., •Leachability of Trace 

Metal Elements from Fly Ashes and Concrete Incorporating Fly Ashes," 

CANMEr Report MTL 99-18 (TR), December, 1999, 64 pp. 

(2] Zhang, M.H., Blaachette, M.C .• and Malhotra, V.M., ''LeacbabilityofTrnce 

Metal Elements from Fly Ash Concrete: ResulL< from Colun~l-Leaching and 

Batch·Leacbing Tests", Under publication in the ACI Materiols Joumal. 

[3 J EPRI BA·5 115, Final report· "Chemical Form and Leachability of Inorganic 

Trace Elements in Coal Ash," Prepared by University ofSoutbem California, 

June 1987 

! 

[4) 

[5) 

(6) 

Fly Ash, Silica Fume, and Slag 15 

de Groot, G. J., Wijksrra, J., Hoede, D., and van de Sloot, H. A .• "Leaching 

0\aracterislics of Selected ElementS from Coal Fly Ash as a Function of the 

Acidity of the Contact Solution and Liquid/Solid Ratio, .. Environmemal 

Aspects of Stabilization nod Solidification of Huardous and Radioa<:tive 

Wastes, ASTM STP 1033, P.L.Cotes and T.M.Gilliam. Eds, Amel'ican 

Society for Testing and Materials. Philadelpbia, 1989, pp. 170·183. 

Johnston, H. M. and Eagleson, K. E., "Chem.icaJ Characteristics of Ontario 

Hydro Coal Fly Ash: A Review: Ontario Hydro Research Division. Report 

No. 89·155-K, June 1989,64 pp. 

Van der Sloot, H. A., de Groot, G. J., and Hoede, D., "Classification of 

Pulverized Coal Ash, Part II · Leaching Properties of Concrete wiUl 

Pulverized Coal Fly Asb as Partial Cement Replacemem, "Report ECN-C-93· 

064, Netherlands Energy Resean:h Foundation, P.O. Box!, NL-1755 ZG 

Petten, the Netherlands, November 1993, 73 pp. 

[7) Aohberg, I. And Schiess!, P., •1nnuence of Concrete Technical Parameters 

on the leaching Behaviout of Mortar and Concrete." Waste Materials in 

Coostruction, Published by Elsevier Science B. V. 1997, pp. 253·258. 

[8] Rai, D., "Inorganic and Organic Constiruents in Fossil Fuel Combustion 

Residues, Vol. 1: A Critical Review", EPRI EA-5176, Electric Powe~ 

Research Institute, Palo Alto, Califomin, USA, 1987. 

[9) P011lnod Cement Association Kiln Oust Task Force. ·An Analysis of 

Selected Trace Metals in Cement and Kiln Dust: Portland Cement 

Association, SP 109T, 1992. 

.- J, 

(!OJ Coal Ash Disposal Manual: 'nill-d edition, Cl\hpter 2: Properties of Power 

Plant Ash, EPRI TR-104137, Electric Power Research Institute, Palo Alto, 

California, USA, January 1995. 
"'"" 

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(MiMo,NB) 

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,._ 

-passinc •S!(IIl. 11o 7!.2 ,,. 13.6 "~ 71.6 

-tpoet.fot lUtfaot. Bl.line: .. nAtrs. "·' "·' .,. :mo 3060 1060 ,. , ... ,.,. ·mediaa parbclc: li.u (Om) I• " IH 21J 1,. m 

WMer tl'lq'llirtn:w::nt. ~ 9$.6 ..... .... "·' ,, 93.0 97.1 

Pono\aQic: Aaivily )M)U, .. _,...,. , ... ...I '" 81.7 '" 1$1 .... ·23-lky .... 8b 106.9 ..... 91.0 100 

"·' Solotca ct.cwck ($i0t) .,_,. "'" 52.35 "~ "'" ..... , ... ,.,..._ ou.k(AIPJ) ,.,. IUS "·" 20-&S 21.51 21M 16.61 

FmK ~- {Ft-A) 23.71 "·"' .... ... , .... . . ., ..... Caki1>m ~ick (CIO} .U7 , ... ""' ,.., ..., lUI G.ll 

M.,.__w.Mk ().t,O) IJl 1.04 1.28 I-'S I >I ~~~ 1.14 

Sod10m oxide CN•:OJ ... •n '·"' til '·" 743 ... Pcu:l$i11m (II ide: (K,o} 

·~ 1 .. "" l .n u• 0~ .... EquiYllkfll ..,_li <N•:0+0.6SiKJ0) '" 1.1> , ... .... .... 7,17 110 Ph:llipho!OVS oxide (P,,~} .... OJ< .,. 0.12 .,. OSI . ,.TitanioMio~tek<T~ 0.16 ..., 0 .15 0., o,.ll 1.., 0 .78 

Stdphur v~cucide {SO, 1.60 1.16 OJI .... 0.08 1.79 0.65 

f..(IM.o-;opilio. u. ~ .. ..,, (1.26 = 0.75 ).)4 

~·(C) 2.97 

T:~blc 2 • irace: dement contcnl of the nyashu used 

T,_ ~caMao«(l>'l) eo.- ......... inc:o.l ...... l..illt: ... ..... ~ """"" Altdl:but& ..,......, Bel~ ...... Co.ICrut u~S). Tvppet . .,.0«1< 

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,, ,.. ,,. ... ,. 1<00 3800 290 sao 1700 )0.7,600 

" <10 <10 <10 <10 <10 <10 <10 <10 <10 

\' 160 190 .. 120 S6 " , .. 310 ISO 11·1,130 

I v ,. ,.. " )I )I " " .. " I "" d " d " d d " d d 

z. "0 290 " " " " ,.. 100 " 1"-J..$00 

2< I 'I "' '" 306 ,.. ,,. '" "' m 

...... Coo!Ouk 

Creek 

bicullli- ""*" 

2.28 u. 

, ... , .. 1 

:mo ,.,. 

"·' ... , 

77~ 

.... "·' ... 9 

"" »<> ''" ... " ••• 1.1 15.6 

.. •o .., u ,_, 2.0 

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• 
• 18 Zhang et 

al. 

AST<I"' 

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..,.Will··~ .. .. '111Colic: wtftc,, lhoM. Cln1

Jc ('\I ~QI"'' •rn .. o,~f ~~ IIUIIC\Ibe.t. Ml'~ "" •l•oby ... ·1·1hr ,... 

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Art«Ntat .. r ,-.,., ..-...,,. "' " C!KGW&'! w !»q. '.t 

Sfl"""'6ol..ooe(S!0

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huu-OltiOf(K,,) ,. 6;_~,~;,-.,Utlbh (Na;:O.O~.SI ,O) •• ~,~.-cP~ 02 lliMhlfl'l '";~ lTo01t Sv...,. uionok (:$0,1 " Lou ut1 ij116on " " 

-._Jl!lk!WI ""'!I!"'"'' N199'i!IM fn:aldllmstlicwC,S ,. OlnA.riM'I&"k C,.t .. Tri<a.l(lvmalu.....,c,... • r&Milt..., ...... ,.u.-m~c CAP • 

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"" ~-... ,..,.;,..., J9.0 0 '" ... U1 " ..,, IOU 

9S '10 "' >H "' 100 ... SH .,, ... ... ... ,... ·~·~ 

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Fly -. .... WI 

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rl .._...r<lfl$)tf 30 OS 

11 (;o .. , 

n Sulld~~ 

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to Tllu~8~y 

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~ 

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m Rneslburs 

('A • f;i)(lll¢ IIUI'eJII!C Sl) • •uperplutio:u«,l'lapMWcnc·b:•5«1 

AEA • 11ir<nlr.tinir1a admixture: 

Fly Ash, Silica Fume, and Slag 19 

,,... w ... c~ AyJ~h ''" CA "' 

A.t;A., 

a1Jm0 

160 '" 0 , .. 1129 0 16 

160 ,,. .. ,. 11)')6 0 no I" 226 n "' 110'1 0 1)0 I" "' ., '" 10 .. 0 201 

"' 122 '' ,.. 1061 0 109 

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161 '" " "' 1100 0 " 161 m " "' 1107 0 " ... '" .. "' 1100 0 110 160 "' "' "' 1098 0 111 160 100 100 "' "" 0 '" 160 "' "' "' 1093 0 200 160 , .. 120 101 1053 1.1 IH . 16l 1!9 " 761 IIJ9 0 " ISS "' .. '" 11)6 0 .. 120 166 '" 1l0 1124 1.1 ,.. 121 "' "' '" !Oil S.l 311 
i ~ : : a • 

~ 

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Ek~• 

PoiriiTuppc:r Lin tan St~ntbnce 

"''- Fcrucbvra n .. •aay lid"""~ 

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• 0.2 0.2 lS.J 96 lOA 2J.l ~1 

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"" :1:-I(M 1_076 

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.. 0.021 0.010 0010 0007 0.05. O.OJS <G.OOI 

s. 002A 0.<)16 0.036 0.041 008<0 0.101 0.129 

Tl 0.0213 0.0101 .,.., <() 002 00019 <0.002 

" 0.001 0.001 O.lll 0069 0.0<11 0.031 <0.002 

v 0.113 0.170 O ITt o.m 0.090 O.OSl 0.171 

Zoo <0.1 <0.1 0.3 02 •• 0.2 O.l 

b <0.1 <().I O.'l 0.1 "'·' <0.1 <O.l 

.. 

;l " ~ ~ ~ ;l = 

• f 

~ f f I < f i f i t 5 ! • 

" • i: " ~ " ~ 

~ 

~ ~ 

8 E e ii " i • ~ ~ " l1 ~ g = f 

. ~ ; ; • ~ ~ 

• • ~ ~ 

i w " ~ )1 tl g g t " 

e ~ !: ~ = ~ 

. - ;; 

e ~ • u ~ • ~ 

• -• -

Bdcw~Oed.: Coal Old: 

<0.00< 

U>O "'""' oou .. 1U 

0..243 02*1 

<()001 0-01) 

<0.001 0062 

o.ma ...,.. 

<0.015 ..... <I <I 

<0.2 II 

<0.0002 .0.0002 

<0.01) O.UI 

0.001 0006 

O.S>O O.Oll 

0.002S <0002 

0.003 0.012 

I 2·U 004, 

<0.1 0.2 

<G. I <G. I 

~ ; ff 

f H i 

• • , 

•'j 

e : ~ E! 

~ 

y 

~ ~) 

; e If 

g ¥ {fr 

!: : ·It 

! i (~r 

"-$4 

* ~ 

• I if 

Jl 

2 .. 

~ r h • 

ConeenctMion mtaJMftld m portla11d 

tc.menl leachate 19) 

ppm 

0 00)..0 12 

000$.00$4 

0.49-4_27 

OOOOJ.OOtU 

O.OH..54 

oooot•cmo 

006-0.17 

0002.0.029 

OOOI.o.olS 

0.002.0.021 

• 

N 

= 

N 

-
T:~ble 3: l.,.e3cha~e Quality Cri1.eri2 (eonce:nttadoM in ppm) 

Luehilt~ Extraction Procedure 

f110f1AAic EPA. U.S.A. EPA. U.S.A. Onwio Qoebe< B.C. Tl)(j.R .. Parameter EPTQJC Ta.P l.EI'" SWEP (CGSB 1.£1') 

Sih'¢1'(Ag) 5.0 5.0 . . . . Atstt~ic {As) s.o 5.0 5.0 5.0 5.0 5.0 

8"""' (B) 500 500.0 

:s.rium(B:a) 100 100 100 100.0 

Cadmium (Cd) 1.0 1.0 0.5 o.s o.s 0.5 

Ch.rOG'nlum (Cr) s.o s.o s.o s.o s.o s.o 

c..,.,,<cu) . . . - 100,0 100.0 

Mete'")' (Hi) 0.2 0.2 - 0.1 - 0.1 

M.antanes.e{Mn) . . . . 5.0 

..... (PI>) s.o s.o 5.0 5.0 5.0 s.o Sclernum ($e) 1.0 1.0 1.0 1.0 1.0 

Zinc (Zn) . . 500.0 

Total Met.als - 10 

• Obl:iined by multipl)·•nt the quaJity critena of the. Ontario l.e3d!.ate Exttaetion Procedure (Ol.EP) by 100 10 obc~n the <:onccntmion limit il'l 

the \1,'3$(~ ¢.)(1~1 

11)(jR ~ ir.ltlsportation of Dangerous Goods Regula~ions. The TDGR incorponucd the. Leach3Le Ewa«•On Procedure CGSB J64~P-tr-.iP. 

Table 9 . T'CLP tC!.l results. Effect of the soorte of Oy ash (conereu: w:l~ cured fot 1 days in moi..s.lure COt'lditi-on 3.11d 2 I days inlabonM:ocy air) 

Ry COnOallrllliQon ~od In l~t~ehale, ppm. 

Mb fly,~. .... WI(C.FM "" ... -tt "' A> Ol (• Cv F< ~i "" S< z. 

,.., 0 ., <(1.002 <0.001 0.~2 0014 «1.112 Q.J(Il ~.()01 <0.02'3 0.21 .. TJ Point T IIWt' )0 OS O.<J09 (1.001 0.003 0.03} O.Jl O.lSO 0.002 <0.023 o.« "" T2 lin'UI 0.010 0.002 0 . .,.. 0.000 0.14 O.J43 0.005 <0.02:. ••I 6.0 

T3 Sund..:~ <0.002 <0.001 •. .,. . .,. 0.27 0.141 0.000 <0.0:23 .,. , .. " t-e <6.000 <0.002 0.025 • .,7 o.to 0.011 o.OOl <0.042 0.66 SA 

n F<.ora•bv•r <0.001 """"' .. ,, .. , <0.10 0.145 <Mil <0.016 ... ~· T6 Tt!or«-•Bay <0.001 <.000< . ., """ <0.10 0 1<0 ''''"' <6.ou~ .,. ~· ,., """"'~ o.coa: ....., ... , 0.0)2 <0.10 0.1&2 <.0.001 <O.O·U "" ·~ n Bdr.W$ Crcd; ;..k, -.<.OtJOl """ """ <0.10 0.204 <0.001 <1).042 0.42 5.9 

.,., CoaiCred: • .,1 0.002 -dl.O)l .... , .. , . 0.142 <0.00} <0.007 0-Jl ... T l$:1 Unpo\ ,. . o.:u 0.0}8 ..... MlS 0.106 1.00 0.111 o.rm <0.1101 o.so ,.. 

Tl9 

'""''""' <.0.001 OOOl """ O<J9S 1.4) 0.108 ..,., <0.1101 .... '·' 

t Avcra.ge of lhe results of two analyses 

'• 

• 

N 

N 

N 

w 
T:ble 10 . TCLP 1.«1 rc:~;uh.s. Erfe¢1 of fly Uh OOI\1CBI ~ Wll$ cured fM 1 ~ys in moQtu~ COC'Idrl.loe'l Mid 21 day$ i;n J.lbontol')' air) 

"' Con«uruion ll'le¥Ur~ in tole, pPM M" Ayash. ""· WI(C .. FA) Ni ... -~ .. "' Cd "' c, " "' s. z, 

TOt 0 ., «1.002 <0.001 0.042 0.0)4 <0.0> 0.161 <O.Ckll .:O.Ol~ ... ~ .....,, ~ 0.006 «1.002 0.023 0.017 <0.10 0.116 .....,, <0.042 ... 

~ ~ 0 .010 "'·""" o.o:u Mll <0.10 o.m <0.001 <0.042 ., 

r-1!-- ~ 0 .010 0.002 .... MJO ... 0,14) """ <0.023 ... r-!!!- ~ 0.016 0.002 . .,, .... "" .. , .. .... <0.042 OA$ 

~ ~ 0.014 0.004 <().OJ I 0.110 ., . ., ooos <!J.CtYI OA9 

TJ< .. 0.017 0.006 .... 0.158 ~ o.u~ 0.010 <0.001 OSI 

t Average of lheresulu of two anal)'$~!$ 

T~ l l . TC'I.P test result;, Erfect ot w/c-m (cooertu was coted fot 1 da)'l in moisture condition at1d 21 «b)'$ in laborMOJ)' air) 

Fly Fly Fly ... Owen~rMioa~o31n ~ppm 

"" uh. "'· .. MOM. WI(C+FA) pH 

"' "'"" " ..,..., A> Cd "' (lo .. Ni "' .. z, 

tot 0 0 OS di.Q02 .....,, O.CW2 0.014 «1.01 0.161 <0.001 <O.<IU 0.21 6A 

~ '-' ,. 120 OA 0.0."0 .. ., o.o:n O.(U6 <0.20 0.143 <0.003 dl!YYt 0.20 ••• 

....!:..._ "' o.s 0.010 0.002 """ 0.030 0.14 0.143 0.<105 "'"" 0.41 ' ~ " 0.6 0.007 ...., <O.Oli o.ou OAS O.ll4 0.003 «1.001 0.4~ 5.6 

Tl1 .. 0.) 0.00'> 0.00) <0.0)1 0.061 0.51 0.187 <(1,00] <0.001 s~ 5.9 

~ LilltJill 60 "' 0.5 O.Oil 0.006 .... O.ISS l,l ) O.ll3 0.010 <O.OOl ... .., Tt3t ,,. '" .. , (1.011 0004 oo;s .... .... ().1)7 '·"" <O.OOl 0.50 5.4 

. 

p " : $() . ; )i tt '3 (( $( :;et 

Tnble 12 • TCLP ttsl results, Effca of cunn& 

Fly O>rioo-"'" Conttnll•tion -w i• k~ pprn 

Mi~ Flyt)h, "" WI(CtFA) z. "' "'"" ., _,. .,bail "' Cd 0 c. " Ni Pb " I 17 <(1 ~ <O.«ll O.OlS 0.01 <0.02 ().lSI .. ., .... , 0.2l 

TO 0 "" 1 " «t.OOZ ....0.001 0.041 o .OI "'"' 0.161 MOl <t>.CD3 .,. 

" 0 <0.()01 <0.001 0.045 M l «1.02 l>.t S& 0.002 «.<1,(1!\ ..,. I " 0.013 .. ., 0026 OO> 0.09 OIS5 0.005 <().02] OAA 

Tl ....... ,. OS 1 " M IO 0.002 .... om 0.14 0.143 0.005 <().02] OAJ 

,. 0 MIO "'"' 0.0.2 0.()3 0.10 ., .. <0.001 <().023 0.40 

I :n <0.('" dl.OO< 0.021 O.<J3 <0.10 ~ ... <0.013 4016 0.30 

"' Fotes10.; 30 0, 1 " ""''' «1.004 0.025 o.oo <0.10 0.145 <0.013 401C. 0.41 

28 0 <il.OOI «1.004 0.025 o .. . ..,0.135 <0.013 <.0..016 0.3< 

I , . 0.013 0.009 ().()).4 0.18 .... 0.121 ..... <AWl 0.51 

T" ....... 60 OS , ' .~ . ..... 0.017 0.006 .... 0.16 ),7) (UJ3 0.010 <O.OOJ OSI 

I " Q.Ol4 0.003 <(1.031 0.00 <(),20 0)41 "'·"" <0.001 0 . .&3 

TIS L>''" 30 0.4 1 " """ . ., .. , . .., ....0.20 010 <0.00> <0.001 0.20 

I " 0.010 . .,, <0.031 0.09 0.89 0.12~ <!100> <O.OOl 0.56 

Tl1 Line• "' . , ' " M IO 0.0)3 <0.0}1 0.(16 ., 0.181 <0..<103 4).0)7 .s~ 

The fe.SUtu of tbe.<:oncre.te. Sllmple TO cured !ot 7 days in mo.i$1 room and 21 dll)'$ in l,aboratory air are the average of t'ol'() analysts 

·. 

,.. 

•• 

6.2 

"" "" ,_. 

H 

.., 

,.. 

.5 

... 

... 

6.0 

6.0 

~ 

5.9 

5.9 

5.> 

5.4 

,., 

.., 

.. 

5.1 

5.9 

..., 

< 

> 

.. 

:r 

en 

;::;-

1» 

..., 

c 

3 

~ 

I» 

... = 

~ I» 

"" 

N 

c.n 

• 
~:n s'!" 

~.., 

We) 

0 0 g.€1 

0 " a"'· 0 0 

erg 

0 0 0~ 

'8~ 

0! " c-. " ~8 

=-9 n ~ 

::>E. '<* 

;~ 

"" * <> c Q, 

~·a 8 

e; 

-"' g . ,. 

~ 

!! 

[ 

g 

~ 

<> 

" ., 

g. 

" Q, 

$ 4 .) 

Table I)· Swnmal')' of Leaclting TreOOs: Observed from TClP Tw 

Metal Corn:entn.bons in 

l~.ach3tt from (;OOCre.le increase 

with incl'eaS:ins: 

Content oi Metal In 

fly Ash 

Leach:lbility of fly Alii 

%fly Ash in Conctt"t.e 

WateriBinder Ratio 

yes = tttnd incrcease/decreease 

no = no trend obsct\>ed 

A< Cd 

,.. no 

,... 

,.., .,... no ,... 

• • ean 't interpre1e 4ue to 6etection limits 

Ol>4uv«< T"""' 

c. Cu Ni Pb 

no .. no no 

no no no -

no ,.. no ..,... -yes ,... no no 

Se z, 

- no 

- no 

- -ye~ 

- ,.. 

Table 14: Percet~t$ge ofTo•.al Ars.erUc Leached from theoonettte iocorponting 60'11 l.inpr:~ fly ash {MixtureT14) 

Te~ D~~n~tion M ... or Leach~nt Liqujdf&O]j Avail3ble (At) in Total As ~ Atsenic 

Melhod of test Concrete Vol~.me dtiitiO Anenie Le&chant leO<hod Leocl>ed 

(g) (L) {mg) (Wo>) (mg) 

TCLP 18"" 100 2 20:1 8 0.011 0.034 0.41 

• ln this: test. no ana1yses "''ere pecformed at lbe eM of the fitst five weeks. 'l"hc only aMt)'$C$ ""'ere perfotmed ~the end of the &ixth 

weel:;. Jt \\':l'l assumed thM fltlhe crwl: of e&eh ~k lhe metaJ content kaclled wu the same. as: thatlt3Chcd in ~J~-ctk silt, 

" . ' l . t))l(-• $pQ it r -• we a L 4 z 

N 

en 

N 

:::r 

"' ... "' 

-

"' 

"' ,.. 

- sar s a , .. _, _ au lil 

Metal leached from concrete (ppm) g~ 

g.· Metal leached from fly ash (ppm) 0 0 0 0 0 ...... ...... ...... ...... <> -

~ i-v ~ Q, , 0 N 0> ():) 0 0> a·g 0 9 0 9 9 _. _. ~ 0- i3 9 0 "" ~ O'l co 0 tv 0 o• .... • ~'g oo • • • a§ 0 . 0 f •• • • . . If = • ~ • • I :s: * 0 .. <> ::· - • 

~~ .. :s: 

r " ~ 0 • o& E. 

Ol i.li () 01 ..., 0 0 0 < ~ 0 (1) 0 

c. .. ~ ::l ,.. ~ 

::p " 8 (1) 

!'! "' ~ ::l 

0 ~ 0 ?" 

8 s· en " 0:'"r1 : \. 0 ::::!> c;· -< ~c.~ ..., '< "' 0 g. _. ...... 0 ~ ..., )> <> 0 0 c "' 0 ;:, :::r 0 3 ;:r o .... "< "" 0 ~ 

•l~f ~ S" :g ••• "0 .... 0 ! - ,. 1f 8 Hn 8 * • ! } "' 8 "' ._, ~ ~ cr.. I! j '---- 0 Q, en 

;;; c:. ... " _. ...... ~ 01 ... ·-- ··------- 0 N Ol ~ 0 ...... * 
tB Zhang et al. 

,-. 

E 

Q, 0.20 

5 

., • 

<i 0.15 ... 

0 

c: 

0 

0 • 

E 

~ 0.10 

"0 

., 

..c 

0 

«< 

~ 

0.05 0 

Oj • - 0.00 ., 

~ 

0 

• 

• 

0 0 

• • • • ... 

·'."' 

20 

0 

• 

40 

0 

• 

• 

o Arsenic x 10 

• Copper 

• Zinc/10 

·Nickel 

60 80 

Lingan Fly Ash in Concrete, % 

Fig. 3. Effect of the fly ash content in concrete incorporating Lingan fly ash on the . 

concentrations of As, Cu, Ni, and Zn in the leachates from concrete Ill the TCLP 

leaching test. 

co 

-

e 

0 

c: 

0 

0 

,-. 

co 

o; 

..c 

0 

«< 

~ 

c: 

E 

Q, 

Q, .._, 

0.25 

0.20 o Arsenic x 10 

0.15 

• Copper 

• Zinc /10 

• Nickel 

0.10 

0.05 

0.00 

0 0.2 

0 

• • 

0 

• 

0 0 

I 

• • • • 

0.4 0.6 0.8 

W/CM 

Fig. 4 • Effect of the w/cm of concrete on the concentrations of As, Cu, Ni, and Zu 

in the leacbates from concrete in TCLP leachin2 test. 

SP 199-2 

Classification of Fly Ash According to 

Japan Industrial Standard, 

JIS A 6201-1999 

by S. Nagataki, F. Tomosawa, T. Kanazu, 

and T. Yamamoto 

The Japan Industrial Standard (JlS) of"Fiy Asb for Use in Concrete, JJS A 

620 I, " was revised in 1999 in order to widen the utilizable amount of fly ash as 

a mineral admixture. The featured points in this revision were that; (I) fly ash 

with high loss on ignition (LOl) ranging from 5.0% to 8.0% is specified as 

Class-Ill, [2] fly ash with low Blaine fineness ranging from 1500cm2

/g to 

2500cm2

/g is specified as Class-IV, [3] high quality fly ash with LOI less than 

3.0% and Blame fineness more than 5000cnl/g was specified as Class-!. Most of 

the fly ash qualified inns A 6201-1996 would be specified as Class-11. Class·lll 

and Class-IV fly ash wouldn't meet the requirement of JIS A 6201 -1996. Tltis 

paper describes the background and the contentS oftl1e revision of ns A 6201. 

K!l~words : fly ash; Japan industrial standard; mineral admixture; 

utilization 
• 

• 

' 

v 

,_ 

Seventh CANMET/ACI 

International Conference on Fly 

Ash, Silica .. Fume, Slag, and 

Natural Pozzolans in Concrete 

Volume I 

Editor 

V. M. Malhotra 

e 

international 

SP-199 

•