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RODOrt/ArtiOl B Titl O Aquati cToxicolog yo f Trac e Element s o f Coa l an d Fl y

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97 7 AQUATI C TOXICOLOG YO F TRAC E ELEMENT S O F COA L AN D FL YAS H

WESJ_Ey. T SI RGK T

. H

. Morga nSchoo l o f Biologica l Sciences , Universit y o f Kentucky , Lexington , Kentuck y

ABSTRAC T Aquati c bioassay s wer e performe do n2 2 coa l elements , wit hdevelopmenta l an d juvenil e stage s o f

fis han damphibian s use da s tes t organisms

. Fo r

mor e sensitiv e tes t species , LC 5 0 value s o f 0. 1 pp mo r

les s wer e observe dfo r

1 5 trac e elements , an dLC ] value s range ddow nt o 0. 1 t o 0. 2 pp b fo r mercur y an dsilver

. Studie s als o wer e performe do nth e aqueou s leachin g characteristic s an dtoxicologica l propertie s o f

coal-produce dfl y ash

. A 52-k g sampl e o f precipitator-collecte dfl y as hwa s subjecte dt o continuou s flow-throug hwashin g fo r 200 0 consecutiv e hour s i nabench-scal e ash-settlin g pond

. Chemica l characteristic s o f th e simulate deffluen t

compare dclosel y wit hthos e recorde dfo r actua l ash-settlin g ponds

. Durin g th e firs t 50 0 h r

o f operation , conductivit y average d69 0 iUmhos/cm , an damea no f 0.5 6 g/lite r

wa s observe dfo r

tota l dissolve dsolids

. Gradua l decrease s wer e observe dthereafter

. Effluen t p H average d4. 3 durin g th e firs t 50 0 h r bu t approache dth e leve l o f influen t wate r (7. 1 t o 7.9 ) b y 200 0 hr

. Maximu meffluen t

concentration s detecte dfo r seve nselecte dmetal s wer e 12 6 pp mAl , 76 6 pp b Zn , 51 8 pp b Cu , 50 0 pp b Cd , 37 0 pp b Ni , 8 7 pp b Hg , an d8 pp b Ag

. Mea nconcentration s fo r th e firs t 50 0 h r o f elutio nwer e 32. 6 pp mAl , 35 0 pp b Zn , 15 6 pp b Cd , 1 5 5 pp b Ni , 1 1 0 pp b Cu

. '2. 1 pp b Ag , an d1. 8 pp b Hg

. Al l metal s excep t

mercur y reache dmaximu mlevel s withi n50 0 hr , an d concentration s decline dthereafter

. Mea nmercur y level s increase dt o 2 7 an d1 5 pp b fo r th e secon dan dthir d500-h r elutio ninterval s Afte r 52 2 an d103 3 h r

o f elutio ntime , continuous-flo w treatmen t wit hundilute das heffluen t produce d 100 % mortalit y o f

fro g an d.sunt'is heggs . A0. 1 dilutio na t 103 3 h r resulte di n 42' " hatehabiiit y o f

sunfis heggs . Afte r

177 5 h r

o f continuou s leaching , undilute das heffluen t

an d0. 1 an d0.0 1 dilution s gav e surviva l frequencie s o f 57 , 76 , an d(S89 f

fo r goldfis heggs , compare dwit h92 ~ fo r controls

. Metal s analyze d fo r undilute deffluen t

administere dt o goldfis hwer e wel l belo w LC j determina

tions , excep t

aluminum , whic hwa s presen t a t th e LC ; ; , level

.22 0 BIRG E 

### Withth e increasin g dependenc e o n coal a s anationa l energ y source , ther e i s aseriou s nee dt o investigate furthe r th e effect s o f

coal productio n an dus e o n environmenta l health

. Numerou s recen t studie s emphasiz e th e exten t t o whic hcoa l utilizatio n ha s grow n beyon dou r

abilit y t o identif

y full y th e hazardou s trac e element s i n coal , quantif

y thei r releas e rate s int o th e environment , an ddefin e thei r biological an dhealth-relate deffect s (Ayer , 1974 ; Yavorsk y an d Akhtar , 1974 ; Babu , 1975 ; Vaugha ne t al. , 1975)

. Approximatel y two-thikd s o f

th e ove r

6 0 element s tha t

occu r i n coal hav e bee n detecte da s environmental pollutant s (Vitez , 1976)

. Althoug htoxico

logical dat aar e largel y incomplete , mos t o f th e element s foun di n coal an dothe r

fossi l fuel s ar e know n t o hav e at leas t som e toxi c effect s o nanima l specie s (Nationa l Academ y o f Sciences—Nationa l Academ y o f

Engineering , Committee , 1973 ; Smith , Ferguson , an d Carlson , 1975 ; Vitez , 1976)

. Th e annua l combustio n o f 60 0 millio n ton s o f

coal constitute s th e majo r

sourc e o f

environmenta l contaminatio n withcoal trac e element s (Abe l an dRancitelli , 1975 ; Bolto n e t al. , 1975 ; Sheibley , 1975)

. Th e mai n source s o f wate r pollutio n ar e powe r

plants , whic h dispos e o f

more tha n 5 0 millio n tons/year o f botto mas han d precipitate dfl y as h(Rubi nan dMcMichael , 1974 ; Chu , Nicholas , an d Ruane , 1975)

. Larg e quantitie s o f wate r ar e use di nsluicin g as h residue s t o settlin g ponds , an dpon deffluent s contai n toxi c metal s tha t affec t th e qualit y o f

receivin g water s (Theis , 1975 ; Hildebrand , Cushman , an dCarter , 1976)

. Fo r eac h1000-M

Wcapacity , sluicing

wate r requirement s fo r

Tennesse e Valle y Authorit y (TVA ) powe r Station s averag e 11. 5 millio n gal/da y o r 4. 2 billio n gal/yea r

(Environ

menta l Protectio n Agency , 1974 ; Chu , Nicholas , an dRuane , 1975)

. Curren t projection s indicat e tha t th e rat e o f

coal combustio n wil l 1 

### doubl e b y th e mi d1980 s (Vaugha n e t al. , 1975)

. Therefore , abetter ; understandin g o f

th e aquati c toxicolog y o f coal-derive dcontami

- \ nant s i s essentia l i f

w e ar e t o maximiz e coal us e an dals o institut e Jsafeguard s necessary t o maintai n reasonabl e an dprope r environ

- : menta l health

. * I nthi s study , aquati c bioassay s were performe dt o establis ha comparativ e toxicologica l rankin g fo r 2 2 coa l elements , identif y thos e whic hma y b e particularl y hazardou s t o aquati c ecosystems , an dprovid e quantitativ e dat afo r us e i nfurthe r

evaluation s o f environmenta l standard s an dpollution-abatemen t technology

. I n addition , abench-scal e settlin g pon dwa s develope dt o simulat e fly-as heffluent s an dt o investigat e th e aqueou s leachin g o f toxi c elements

. Continuou s flo w embryo—larva l bioassay s wer e use dfo r i n sit u monitorin g o f

as heffluent s t o provid e direc t toxicologica l evaluation s o ncomple x suite s o f trac e cloments

.AQUATI C TOXICOLOG YO F TRAC E ELEMENT S 22 1 MATERIAL S AN D METHOD S Aquati c Bioassay s Semistati c embryo—larva l bioassay s wer e performe do n th e goldfis h(Carassius auratus), th e rainbo w trou t (Salmo gairdneri), an d th e narrow-mouthe dtoa d(Gastrophryne carolinensis) wit hrapid

scan procedure s previousl y describe d(Birg e an dJust , 1975)

. Egg s were expose dt o coal element s fro mfertilizatio n throug h4 day s posthatching , givin g treatmen t period s o f

7 day s fo r

toad s an d goldfis han d2 8 day s fo r trout
. Tes t

wate r an dtoxican t

wer e renewe da t

regular 12-h r intervals

. Mea n wate r hardness , wit h standar derror , wa s 19 5 ± 5. 4 pp mCaCO 3 fo r goldfis han dtoa d stage s an d10 4 ± 2. 0 fo r trout
. Tes t

wate r p H average d7. 4 ± 0.1

. Dissolve doxyge n wa s maintaine dnea r saturatio n b y continuous , moderat e aeration

. Othe r chemica l an dphysica l characteristic s o f th e reconstitute dtes t

wate r wer e describe db y Birg e an dBlac k (1977)

. Wate r temperatur e wa s 13. 0 ± 0.5° C fo r trou t egg s an d22. 0 ± 1.0° C fo r othe r species

. Tes t organism s wer e examine ddail y t o tabulat e frequencie s o f mortalit y an dteratogenesis

. Contro l adjuste dLC 1 an dLC S O value s wer e calculate dfo r

combine dtes t

response s b y lo g probi t analysi s (Daum , 1969)

. Anomalou s survivor s wer e counte da s lethals

. Contro l egg s wer e culture dsimultaneousl y withexperimental s an dunde r identica l conditions , excep t fo r omissio n o f

toxi c coal elements

. Minimu msampl e siz e wa s se t at 15 0 egg s pe r

culture

. Th e 2 2 coal element s an dtes t compound s selecte dfo r bioassay analysi s ar e give n i n Tabl e 1

. Dependin g o n th e degre e o f anticipate d toxicity , exposur e concentration s wer e initiate dat 1 0 t o 10 0 pp m an dcontinue da t

two

- t o tenfol ddilution s unti l surviva l o f experimenta l animal s equale do r approache dthat

observe dfo r controls

. Eac hcoa l elemen t wa s administere dat

1 0 t o 1 4 exposur e levels

. Elementa l concentration s o f tes t wate r wer e monitore db y atomi c absorptio n spectrophotornetr y wit hamode l 50 3 Perkin

— Elme r uni t equippe dwit ha n HGA-210 0 graphit e furnac e an da mercur y analyze r

(Perkin—Elme r

Corp. , 1973)

. Aqueou s Leachin g o fFl yAs h A bench-scal e Plexigla s settlin g pon dwa s designe dt o investigat e th e aqueou s leachin g characteristic s o f precipitator-collecte dfl y as h obtaine dfro maloca l 1000-M Wcoal-fire dpowe r plant

. A 52-k g sampl e o f

dr y as hwa s deposite di na n88.2-lite r settlin g chamber

. A Gilso nMinipul s I I peristalti c pum p (Gilso nMedica l Electronics , Inc. ) provide dacnnuni'ou ^ flo w o f wate r o\v r th e as hbee 1 a t

arat e o f

122 2 BIRG E TABL E1 

### COA LTRAC EELEMENT S SELECTE D FO RBI O ASSA Y EVALUATION S Trac e elemen t Aluminu m Antimon y Arseni c Cadmiu m Cobal t Chromiu m Coppe r Germaniu m Lanthanu m Lea d Manganes e Mercur y Molybdenu m Nicke l Silve r Seleniu m Strontiu m Thalliu m Ti n Tungste n Vanadiu m Zin c Bioassa y tes t compoun d A1C1 3 SbCl 3 NaAsO 2 CdCl 2 Co(NCM 2 Cr0 3 CuSC- 4 Ge0 2 LaCl 3 PbCl 2 MnCl 2 HgCl 2 Na 2 MoO 4 NiCl 2 AgN0 3 Na 2 SeO 4 SrCl 2 T1C1 3 SnCl 2 Na 2 WO 4 V 2 0 5 ZnCl 2 Concentration *

i n coal , pp m 10,440—12,90 0 0.50—1.2 6 4.45-14.0 2 0.47—2.5 2 2.90—9.5 7 13.75—18.0 0 8.30-15.1 6 1.00—6.5 9 3.80—10.0 0 4.90—34.7 8 33.80-49.4 0 0.12—0.2 0 5.00-7.5 4 16.00—21.0 7 0.03-0.1 2 2.08-2.2 0 10.00—23.0 0 0.29—2.0 0 0.03-4.7 9 0.10—3.0 0 28.50-32.7 1 46—27 2 *Th e majorit y o f

value s ar e fro mRuch , Gluskoter , an dShim p (1974) , Fulkerso n e t al

. (1975) , an dCarte r

(1975 ) an drepresen t

mean s fo r multipl e coa l sample s take nlargel y fro mwester n •Kentuck y an dsouther n Illinois

. Lowe r mean s fo r Ag , Tl , Sn , an dWar e fro mLloy d(1976) , an dth e uppe r mea n fo r

A g i s fro mVaugha ne t al

. (1975)

. 

### liter/hr , givin g adetentio ntim e o f 4 2 hr

. Wate r

wa s discharge dfro m th e settlin g chambe r

int o a noverflow-equippe deffluen t reservoir

. Th e ash-to-wate r

rati o an dth e detentio ntim e wer e calculate dt o approac hcondition s observe dfo r aloca l ash-settlin g pon d(Freema n an dBirge , 1978)

. Also , th e detentio n tim e wa s i n goo dagreemen t wit htime s reporte dfo r

anumbe r

o f TV A as hpond s (Chu , Ruane , an dSteiner , 1976)

. Influen t an deffluen t

wate r sample s wer e take n a t 1

- t o 2-da y interval s fo r 200 0 h r

o f continuou s operatio nt o observ e change s i nwater-qualit y parameters
. Determination s wer e mad e o npH , conductivity , alkalinity , an dtota l dissolve dsolids , an dAQUATI C TOXICOLOG YO F TRAC E ELEMENT S 22 3 

### analyse s were performe dfo r seve n selecte dmetal s (Ag , Al , Cd , Cu , Hg , Ni , an dZn)

. Alkalinit y an dtota l dissolve dsolid s wer e deter

mine daccordin g t o standar dmethod s (America n Publi c Health Association , 1975) , an dmetal s were analyze db y atomi c absorptio n spectrophotometry

. Fl y as hdisplaye dgoo dsettlin g characteristics , an deffluen t

wate r wa s essentiall y fre e o f

as hparticipates

. Th e fly-as h be dcompacte dsufficientl y t o imped e interstitial percolation , limit

in g wate r movemen t

primaril y t o surfac e flow

. Throug hth e firs t 77 0 h r o f operation , influen t

wate r wa s distille dan ddeionize dan dha da conductivit

y les s tha n 0.2 5 jumhos/c man dap H o f 6.8

. Tota

l dissolve dsolid s an dtrac e metal s were no t detectable

. Durin g th e remainde r o f th e leachin g period , th e settlin g chambe r wa s supplie d wit hcarbon-filtere dta

p water , whic hha dap H o f 7. 1 t o 7.9 , conductivit y o f

14 1 t o 25 2 jumhos/cm , alkalinit y o f 5 4 t o 7 0 pp m CaCO 3 

### , an dtota l dissolve dsolid s o f 0.1 9 t o 0.2 4 g/liter

. Wate r temperature s range dfro m24. 4 t o 26.0°C

. BioassayMonitorin g o fFly-As h Effluen t 

### Continuous-flo w bioassay s wer e performe do n th e simulate das h effluen t t o evaluate toxicological propertie s o f th e aqueou s leachates

. Egg s o f th e goldfis h(Carassius auratus), redea r sunfis h(Lepomis microlophus), leopar dfro g (Rana pipiens), an dFowler' s toa d(Bufo fowleri) wer e use da s tes t organisms

. Full-strengt heffluen t an dseria l dilution s thereo f

wer e perfuse dcontinuousl y throug h300-m l eg g chamber s at

flo w rate s o f

20 0 t o 30 0 ml/hr

. Effluen t dilution s o f 0.1 , 0.01 , 0.001 , an d0.000 1 wer e achieve dwit haproportiona l dilute r (Freema n an dBirge , 1978)

. Exposur e wa s maintaine dfro m fertilizatio n throug hhatching , an dresult s wer e expresse da s percen t surviva l (hatchability)

. Hatchin g time s average d1. 5 day s fo r Fowler' s toad , 2. 5 day s fo r

th e leopar dfrog , an d3 day s fo r sunfis han d goldfish

. Minimu msampl e siz e wa s se t a t 10 0 eggs . Contro l eg g chamber s receive dth e sam e influen t wate r a s tha t supplie dt o th e simulate dash-settlin g pond

. Bioassay s wer e initiate dafte r 522 , 1033 , an d177 5 h r

o f continuou s aqueou s leachin g o f th e origina l 52-k g fly-as hsample

. RESULT S Embryo-Larva l Bioassay s 

### Fis han damphibia n egg s wer e expose dt o eac ho f 2 2 select e coal element s (Tabl e 1 ) fro mfertilizatio nthroug h4 day s po s hatching , givin g treatmen t period s o f

2 8 day s fo r

trou t an d7 da \ fo r th e narrow-mouthe dtoa dan dgoldfish

. Probit-derive dLC ? 0 

### an .22 4 BIRG E 

### LCj value s expresse di n part s per millio nan dpart s per

billion , respectively , ar e summarize di nTabl e 2

. I norde r o f decreasin g toxicity , o n th e basi s o f

LC S O 

### determinations , th e 1 2 element s mos t letha l t o trou t

wer e Hg , Ag , La , Ge , Ni , Cu , Cd , V , Tl , Pb , Cr , an dSr

. Th e LC S O 

### value s wer e 0.005 , 0.01 , an d0.0 2 fo r Hg , Ag , an dLa , respectively ; 0.0 5 fo r

G e an dNi ; 0.0 9 fo r

Cu ; 0.1 3 fo r

Cd ; an d0.1 6 t o 0.2 0 fo r

V , Tl , Pb , Cr , an dSr

. Th e calculate dLC , ' s fo r th e more toxi c element s wer e 0. 2 fo r H g an dAg , 0. 4 fo r

Ge , 0. 6 fo r

Ni , 0. 8 fo r La , 1. 8 fo r

Cu , 2. 5 fo r

Pb , an d6. 0 t o 6. 1 fo r S r an dC d 

### (Tabl e 2)

. Th e goldfis hwa s th e leas t sensitiv e o f

th e thre e tes t

species

. Th e 1 2 element s mos t

toxi c to goldfis hegg s were Ag , Hg , Al , Cd , As , Cr , Co , Pb , Ni , Sn , Zn , an dV

. Th e LC 5 0 

### value s wer e 0.03 , 0.12 , 0.15 , 0.17 , 0.49 , 0.66 , 0.81 , an d1.66 fo r th e firs t eight , respectively ; 2.1 4 fo r N i an dSn ; 2.5 4 fo r

Zn ; an d4.6 0 fo r

V

. Th e LC j value s obtaine d fo r thes e metal s range dfro ma s lo w a s 0. 4 an d0. 6 pp b fo r A l an dA g t o 40 0 pp b fo r

Zn

. Certai ncoa

l element s (e.g. , A g an dHg ) were mor e toxi c t o fis hembryos ; other s (e.g. , Al , Cd , Ge , an dPb ) exhibite dconsiderabl e toxicity t o posthatche djuveniles

. I nbioassay s withth e narrow-mouthe dtoad , th e 1 2 mos t letha l element s were Hg , Ag , Zn , Cr , Pb , Cd , Cu , As , Ge , Co , Ni , an dAl

. Th e LC 5 0 

### value s wer e 0.001 , 0.01 , 0.01 , an d0.0 3 pp mfo r th e firs t fou r elements , respectively ; 0.0 4 pp mfo r Pb , Cd , Cu , an dAs ; an d 0.0 5 pp mfo r

Ge , Co , Ni , an dAl

. Th e calculate dLC j ' s range d onl y fro m0. 1 an d0. 6 pp b fo r H g an dA g t o 1. 6 an d3. 2 pp b fo r C d an dPb

. 

### Th e LC S 

### o value s were average dfo r al l anima l specie s (Tabl e 3 ) t o provid e asimplifie dtoxicological inde x fo r th e 2 2 elements

. Thi s mea ntoxicit y inde x provide daconvenien t ranking , consistin g o f thre e genera

l toxicity groups . Grou p 1 include dte n highl y toxi c element s withmea nLC 5 0 

### value s belo w 1 ppm ; grou p 2 include d nin e element s withLC 5 0 

### value s o f 1 t o 5 ppm ; an dgrou p 3 include d thre e element s wit ha n LC 5 0 

### rang e o f 2 0 t o 4 7 ppm . Th e selecte dcoa l element s wer e als o ranke daccordin g t o amos t sensitiv e specie s inde x (Tabl e 3 ) base do nmedia nletha l concentra

tion s determine dfo r

th e anima l specie s exhibitin g highes t sensitivit y t o eac ho f

th e 2 2 elements

. Th e LC 5 0 

### value s range dfro m0.00 1 pp m H g t o 2.9 0 pp mW

. Element s wit happroximatel y th e sam e LC 5 0 

### concentratio n were furthe r differentiate do n th e basi s o f LC i values

. Aqueou s Leachin g o fFl yAs h 

### A52-k g sampl e o f

precipitator-collecte dfl y as hwa s subjecte dt o continuou s washin g fo r 200 0 h r

a t aflo w rat e o f

1 liter'hr

.AQUATI C TOXICOLOG YO F TRAC E ELEMENT S
TABL E 2 

### COAL-ELEMEN T LC , ANDLC 5 0 

### VALUE S WIT H 95 % CONFIDENC ELIMIT S Elemen t an d anima l specie s Aluminu m Trou t Goldfis h Toa d Antimon y Trou t Goldfis h Toa d Arseni c Trou t Goldfis h Toa d Cadmiu m Trou t Goldfis h Toa d Chromiu m Trou t Goldfis h Toa d Cobal t Trou t Goldfis h Toa d Coppe r Trou t Goldfis h Toa d Germaniu m Trou t Goldfis h Toa d Lanthanu m Trou t Goldfis h Toa d Lea d Trou t Goldfis h Toa d Manganes e Trou t Goldfis h I'oa d . _Confidenc e limi t
_ c pp m
0.5 6 0.1 5 0.0 5 0.5 8 11. 3 0.3 0 0.5 4 0.4 9 0.0 4 0.1 3 0.1 7 0.0 4 0.1 8 0.6 6 0.0 3 0.4 7 0.8 1 0.0 5 0.0 9 5.2 0 0.0 4 0.0 5 5.6 0 0.0 5 0.0 2 60. 4 0.2 9 0.1 8 1.6 6 0.0- 1 2.9 1 *v2 2 I-1 2 Lowe r

0.4 0 0.0 2 0.0 4 0.3 4 3.9 9 0.1 8 0.4 2 0.3 9 0.0 2 0.1 0 0.1 3 0.0 3 0.0 7 0.4 0 0.0 3 0.3 8 0.2 7 0.0 2 0.0 5 4.1 3 0.0 3 0.0 3 1.7 6 0.0 3 0.0 1 30. 3 0.1 9 0.1 0 0.8 5 0.0 2 1.N 5 2.3 9 0 ,- 1 \ Uppe r

0.7 0 0.8 2 0.0 8 0.9 2 55. 0 0.5 1 0.6 7 0.6 1 0.0 7 0.1 8 0.2 1 0.0 5 0.3 1 1.1 0 0.0 4 0.5 8 2.2 7 0.0 8 0.1 5 6.4 1 0.0 5 0.0 7 7.8 4 0.0 8 0.0- 1 10 5 0.4 3 0.3 2 3.0 5 0.0 7 1.3 7 2-1. 6 2 ! D pp b

25 6 0. 4 2. 3 28. 6 11 1 3. 8 39. 7 15. 5 1. 6 6. 1 15. 0 1. 6 19. 1 8. 1 1. 0 34. 2 6. 8 0. 9 1. 8 29 9 1. 0 0. 4 14 3 1. 2 0. 8 198 7 7. 5 2. 5 14. 6 3. 2 3h b 2 1

. :> '} 0 Confidenc e limi t -\

- Lowe r
52. 7 0. 0 0. 7 4. 6 0. 1 0. 7 15. 5 7. 5 0. 2 1. 8 4. 4 0. 9 0. 4 1. 5 0. 6 13. 8 0. 0 0. 3 1. 0 10 1 0. 3 0. 1 2. 7 0 1 0. 0 13 6 2. 3 U. 2 1. 4 0. 1 6 6 2 0 1

: ' ~ Uppe r
37 1 5. 6 4. 8 72. 2 66 3 10. 7 71. 6 26. 6 4. 4 12. 9 19. 2 2. 5 56. 5 22. 1 1. 5 60. 8 42. 6 2. 0 4. 5 57 1 1. 3 0 56 7 3 > 2 7 650 3 16. 2 8. ! 53. 1 9. 1 80 0 I h 2 9 X22 6 BIRG E TABL E2 (Continued ) Elemen t an d anima l specie s Mercur y Trou t Goldfis h Toa d Molybdenu m Trou t Goldfis h Toa d Nicke l Trou t Goldfis h Toa d Seleniu m Trou t Goldfis h Toad Silve r Trou t Goldfis h Toa d Strontiu m Trou t Goldfis h Toa d Thalliu m Trou t Goldfis h Toa d Ti n Trou t Goldfis h Toa d Tungste n Trou t Goldfis h Toa d Vanadiu m Trou t Goldfis h Toa d Zin c Trou t Goldfis h Toa d j

_ , Confidenc e limi t

pp m
0.00 5 0.1 2 0.00 1 0.7 3 60. 0 0.9 6 0.0 5 2.1 4 0.0 5 4.1 8 8.7 8 0.0 9 0.0 1 0.0 3 0.0 1 0.2 0 8.5 8 0.1 6 0.1 7 7.0 0 0.1 1 0.4 0 2.1 4 0.0 9 15.6 1 12 0 2.9 0 0.1 6 4.6 0 0.2 5 1.0 6 2.5 4 0,0 1 Lowe r

0.00 4 0.1 0 0.00 1 0.3 0 7.9 4 0.5 8 0.0 4 1.1 9 0.0 3 2.8 2 7.2 3 0.0 8 0.0 1 0.0 2 0.0 1 0.1 0 2.1 1 0.1 2 0.0 9 1.9 4 0.0 9 0.2 3 0.3 6 0.0 8 6.7 1 92. 3 2.4 4 0.0 7 0.5 1 0.1 3 0.7 5 1.5 9 0.0 1 Uppe r

0.00 5 0.1 4 0.00 2 1.4 0 92. 2 1.6 0 0.0 6 3.6 3 0.0 9 5.8 2 10. 6 0.1 5 0.0 2 0.0 3 0.0 3 0.3 8 21. 2 0.2 1 0.3 0 9.9 6 0.1 4 0.6 7 3.4 5 0.1 3 31.9 8 15 6 3.5 0 0.3 0 9.1 0 0.4 4 1.3 9 4.1 8 0.0 4 LC, ,

pp b
0. 2 14. 3 0. 1 22. 3 39. 3 3. 1 0. 6 55. 8 0. 4 79. 5 50 6 5. 0 0. 2 0. 6 0. 6 6. 0 45. 3 2. 4 8. 4 52. 5 2. 4 15. 5 68. 8 1. 7 82 8 34 5 10. 7 6. 9 55. 2 7. 4 20. 0 40 0 0. 6 Confidenc e limi t Lowe r
0. 1 8. 2 0. 0 1. 2 0. 9 0. 6 0. 2 7. 9 0. 0 17. 5 26 7 0. 7 0. 1 0. 4 0. 0 0. 3 0. 0 1. 0 0. 7 1. 1 1. 1 2. 1 0. 0 0. 3 14. 2 4. 7 4. 5 0. 3 0. 0 0. 6 5. 7 26. 5 0. 0 Uppe r

0. 3 21. 2 0. 3 83. 4 26 1 9. 5 1. 2 160 1. 5 20 2 80 5 7. 3 0. 4 0. 9 2. 0 19. 9 39 6 4. 6 24. 8 26 6 4. 5 42. 5 39 0 4. 5 281 0 213 9 21. 2 22. 8 11 6 23. 0 33. 2 50 0 2. 2AQUATI C TOXICOLOG YO F TRAC E ELEMENT S 22 7 TABL E 3 COMPARATIV E TOXICIT Y O F COA L ELEMENT S T O FIS H AN D AMPHIBIA N EMBRYO-LARVA L STAGE S Mea n toxieit y index * Mos tsensitive specie s index Element Toxicit y grou p 1 Silve r Mercur y Cadmiu m Aluminu m Cobal t Arseni c Chromiu m Lea d Nicke l Tin Toxicit y grou p 2 Zin c Vanadiu m Coppe r Germaniu m Thalliu m Strontiu m Antimon y Manganes e Seleniu m Toxicit y grou p 3 Lanthanu m Molybdenu m Tungste n LCso ,

pp mElement
0.0 2 0.0 4 0.1 1 0.2 5 0.2 9 0.3 6 0.4 5 0.6 2 0.7 5 0.8 8 1.2 0 1.6 7 1.7 8 1.9 0 2.4 3 2.9 8 4.0 7 4.1 8 4.3 5 20.2 5 20.5 6 47.1 7 Mercur y Silver Zin c Lanthanu m Chromiu m Copper Cadmiu m Arseni c Lea d Nicke l Cobalt Germaniu m Aluminu m Ti n Seleniu m Thalliu m Strontiu m Vanadiu m Antimon y Molybdenu m Manganes e Tungste n Specie s

Toa d Trou t Toa d Trou t Toa d Toad Toa d Toa d Toa d Trou t Toa d Toa d Toa d Toa d Toa d Toa d Toa d Trou t Toa d Trou t Toa d Toa d LCso ,

pp m 0.00 1 0.0 1 0.0 1 0.0 2 0.0 3 0.0 4 0.0 4 0.0 4 0.0 4 0.0 5 0.0 5 0.0 5 0.0 5 0.0 9 0.0 9 0.1 1 0.1 6 0.1 6 0.3 0 0.7 3 1.42 2.9 0 LC, ,

pp b 0. 1 0. 2 0. 6 0. 8 1. 0 1. 0 1. 6 1. 6 3. 2 0. 6 0. 9 1. 2 2. 3 1. 7 5. 0 2. 4 2. 4 6. 9 3. 8 22. 3 3. 0 10. 7

*LC 5 o value s a t4 day s posthatchin g average d fo rthre e species , narrow-mouthe d toad , goldfish , an d rainbo w trout .
Detentio n tim e wa s 4 2 hr , an dwater-qualit y parameter s wer e plotte d an daverage dfo r

eac ho f

fou r 500-hr elutio n intervals

. Tota l dissolve dsolids , conductivity , an dp H showe dmarke ddecrease s durin g th e firs t

10 0 h r o f elutio n tim e {Fig

. 1)

. Tota l dissolve d solid s decrease dfro m2. 2 g/lite r a t 1 8 h r t o 0. 5 g/lite r

a t 9 4 hr , averagin g 0.5 6 g/lite r

fo r th e firs t

50 0 hr

. Conductivit y (jUmhos ) decrease dfro m240 0 a t 2 0 h r t o 90 0 a t

9 4 h r an dcontinue dt o dro p slowl y t o 20 0 a t

50 0 hr

. Th e sharpes t

declin e wa s observe dfo r pH , whic hdecrease dfro m7. 7 a t 1 h r t o abou t 4. 0 a t 1 8 hr , averagin g 4. 322 8 BIRG E
8. 0

,p H A , Tota l dissolve d solid s
• , Conductivit y

10 0 20 0 30 0

FL YAS H LEACHIN G TIME , h r 40 0 50 0 0. 0
Fig . 1 Change s i n fly-as h effluen twit h leachin g time . fo r th e firs t

elutio n interval

. A s see n i n Fig

. 1 , change s i n thes e effluen t parameter s wer e mos t

pronounce ddurin g th e initia l 4 day s o f ash-leachin g time , presumabl y correlatin g wit hth e perio ddurin g whic hleachabl e component s wer e mos t rapidl y remove dfro mth e fl y ash

. Mean , value s fo r

th e firs t 50 0 h r ar e give n i n Table 4

. Midwa y i n th e secon delutio n interval , a t 77 0 hr , th e influen t
• sourc e wa s change dt o carbon-filtere dtap water
. Thi s actio n wa s take n t o determin e whethe r influen t wate r o f highe r p H an dgreate r bufferin g capacit y woul dalte r th e leachin g process . Initially , conductivit y an dtota l dissolve dsolid s o f th e effluen t

ros e propor tionatel y wit hincrease s observe dfo r th e ne w influen t

water , bu t value s fo r

thes e parameter s decline dsteadil y ove r th e thir dan d fourt helutio n intervals , closel y approachin g thos e obtaine dfo r influen t wate r b y 200 0 h r

(se e Material s an dMethod s section)

. Afte r th e chang e t o influen t

ta p water , effluen t

p H fo r th e secon delutio n interva l increase dsteadil y fro m4. 5 t o 7.1

. A gradua l increas e continue dthereafter , and , durin g th e las t tw o elutio n intervals , p H range s o f 7. 1 t o 7. 9 an d7. 0 t o 7. 7 wer e recorde dfo r influen t an d effluen t water , respectively

. Althoug htota l alkalinit y wa s no t determine ddurin g th e firs t 100 0 hr , range s fo r

th e thir dan dfourt h elutio ninterval s wer e 3 2 t o 5 5 an d4 6 t o 6 2 pp mCaCO 3 , compare d wit h5 4 t o 6 9 pp mfo r influen t ta p water
. Afte r

200 0 h r

o f continuou s washin g o f th e origina l fly-as hsample , influen t an dAQUATI C TOXICOLOG YO F TRAC E ELEMENT S 22 9 

### TABL E4 CHARACTERISTIC S O FSIMULATE D ASH-PON D EFFLUEN T

Characteristi c Simulate deffluent * TV A range * Total dissolve dsolids , g/lite r p H Conductivity , /jmhos/c m Alkalinity , $ mg/lite r

CaCO 3 Ag , Mg/lite r Al , mg/lite r Cd , Mg/lite r Cu , Mg/lite r Hg , Mg/lite r Ni , Mg/lite r Zn , Mg/lite r Input , ml/h r Output , ml/h r % evaporatio n 0.5 6 ±0.1 7 4. 3 ±0. 1 69 0 + 8 0 4 3 + 3 2. 1 ± 0. 9 32. 6 + 6. 1 15 6 + 3 5 11 0 + 2 6 1. 8 + 0. 5 15 5 ±1 6 35 0 ± 3 3 96 9 + 1 0 89 7 + 1 8 8 + 2 0.14—0.5 2

4.4—11. 3 242—85 5 40—15 4 1.4-7. 2 1-3 7 10—31 0 0.2-3 8 31—110 0 30—151 0

*Mea n±standar derro r

fo r initia l 50 0 h r

o f continuou s operation

. tRang e o f

mea nvalue s fo r

1 4 TV A as hpond s (Chu , Ruane , an dSteiner , 1976)

. I Alkalinit y determine dfo r th e thir d500-h r

elutio ninterval

. 

### effluen t wate r di dno t diffe r substantiall y i npH , alkalinity , conduc

tivity , o r tota l dissolve dsolids

. Effluen t concentration s fo r

th e seve nselecte dmetal s monitore d throug h150 0 h r

ar e summarize di n Tabl e 5

. Maximu mconcentra

tions , whic hi n mos t

instance s wer e observe ddurin g th e firs t 10 0 hr o f elutio ntime , wer e 12 6 pp mAl , 76 6 pp b Zn , 51 8 pp b Cu , 50 0 pp b Cd , 37 0 pp b Ni , 8 7 pp b Hg , an d8 pp b Ag

. Mea nconcentration s fo r th e firs t 50 0 hour s wer e 32. 6 pp mAl , 35 0 pp b Zn , 15 6 pp b Cd , 15 5 pp b Ni , 11 0 pp b Cu , 2. 1 pp b Ag , an d1. 8 pp b Hg

. Th e 500-h r elutio r pattern s fo r

Al , Cu , Ni , an dZ nar e illustrate di nFig

. 2

. Eleva f concentration s observe da t abou t 30 0 h r correlate dwit hmechani c disturbance s tha t

temporaril y facilitate dwate r filtratio nthroug hth e fly-as hbed

. Concentration s fo r al l metal s excep t

mercur y continue d t o declin e progressivel y wit hfurthe r leachin g time , resultin g i nmea n value s fo r

th e thir delutio n interva l o f 54 0 pp b Al , 61. 4 pp b Zn , 33. 6 pp b Ni , 25. 7 pp b Cd , 4. 1 pp b Cu , an d0. 2 pp b A g (Tabl e 5)

. Mercun

. fluctuate dfro m0. 3 t o 7. 4 pp b durin g th e firs t 50 0 h r bu t increase i substantiall y thereafter , wit hmea nvalue s o f 27. 4 an d14. 9 pp b fo < th e secon dan dthir delutio nintervals

. However , th e mercur y leve i droppe dmarkedl y towar dth e en do f th e thir delutio nperiod , averagin g 2. 6 + 0. 7 pp b afte r 136 0 hr

. Metal s wer e no t detecte di r23d BIRG E
TABL E 5 META LCONCENTRATION S FO RFLY-AS H EFFLUEN T

Elemen t A g A l C d C u H g N i Z n Maximu m tration , pp b 8 126,00 0 50 0 51 8 8 7 37 0 76 6 Meanconcentratio n fo r thre e elutio n intervals , ppb * 0—50 0 h r 2. 1 ±0. 9 32,60 0 + 6,10 0 15 6 ± 3 5 110 + 2 6 1. 8 ±0. 5 15 5 + 1 6 35 0 + 3 3 500—1000 hr

0. 2 + 0. 2 1,57 0 ±26 0 93. 8 + 24. 8 1 4 + 1. 8 27. 4 + 11. 7 5 8 + 1 0 10 6 ±2 0 1000

—150 0 h r 0. 2 + 0. 2 54 0 + 8 0 25. 7 ±11. 3 4. 1 ±0. 8 14. 9 + 5. 3 33. 6 + 2. 3 61. 4 +4. 1 Influen t

concen tration , pp b 0. 0 23 0 ± 2 9 1. 7 + 0. 8 3. 5 ±0. 9 0. 0 3. 3 + 1. 4 4. 9 + 3. 1 *Mea n value s wit h standar d error s were base d o n analyse s take n a t1 - t o 3-da y intervals .

10 0 20 0 30 0

FL YAS H LEACHIN G TIME , h r 40 0 50 0 Fig . 2 Leachin g pattern s fo rfly-as h metals . th e distilled—deionize dinfluen t wate r use dfo r th e firs t 77 0 hr , an d backgroun dvalue s fo r

th e carbon-filtere dtap wate r ar e give ni n Tabl e 5

. Bioassa yAnalysi s o fFly-As h Effluen t Fou r set s o f embryo—larva l bioassay s wer e performe do nfly-as h effluen t b y us e o f

acontinuous-flo w system
. Test s wer e initiate dAQUATI C TOXICOLOG YO F TRAC E ELEMENT S 23 1 

### afte r 522 , 1033 , an d177 5 hr o f continuou s aqueou s leachin g o f th e origina l 52-k g sampl e o f precipitator-collecte dfl y ash

. A t 52 2 h r test s wer e conducte do n egg s o f th e leopar dfro g an dFowler' s toa d withundilute das heffluent

. Pro g egg s suffere drapi dan dcomplet e mortality , an dahatchin g frequenc y o f 46 % wa s observe dfo r Fowler' s toad

. Surviva l wa s 9 7 t o 99 % fo r contro l population s treate dwithth e same influen t water sourc e use dt o suppl y th e fly

as hleachin g chambe r

(Tabl e 6)

. Bioassay s were initiate dat 103 3 hr o n egg s o f

th e redear

sunfish

. Undilute deffluen t produce dcomplete mortality , an d0. 1 an d0.0 1 dilution s gav e survival frequencie s o f 4 2 an d90% , whic hclosel y approache dcontro l survival

. I n test s with goldfis hegg s conducte dat 177 5 hr , surviva l average d57 , 76 , an d 88 % fo r undilute deffluen t

an d0. 1 an d0.0 1 dilutions , respectively

. Contro l survival wa s 92%

. Effluen t meta l concentration s observe dfo r th e amphibia n bioassay s approximate dmea n value s give n fo r th e secon delutio n interva l (Tabl e 5)

. Althoug has htoxicant s produce danear-LC 5 0 

### respons e fo r

toa deggs , th e exposur e perio dwa s limite dt o onl y 1. 5 days

. I n addition , developmenta l stage s o f Fowler' s toa dar e highl y resistan t t o trac e metals , compare dwit hothe r amphibia n an dpiscin e specie s (Birge , 1976)

. Anima l specie s use dfo r th e initia l toxicologica l

TABL E6 EMBRYO-LARVA LBIOASSAY S O N FLY-AS H EFFLUEN T
Specie s Leopar dfro g (Rana pipiens) Fowler' s toa d (Bufo fowleri) Redea r sunfis h (Lepomix microlophux)

Goldfis h (Carasxius aura tun) Elutio n

interval , h r 522-58 2 522-55 8 1033—110 5

1775-184 7 Exposur e

time , day s 2. 5 1. 5 3. 0

3. 0 Bioassa

y solutio n As heffluen t Contro l As heffluen t Contro l As heffluen t Dilute deffluen t 0. 1 0.0 1 0.00 1 0.000 1 Contro l As heffluen t Dilute deffluen t 0. 1 0.0 1 Contro l Percen t

surviva l a t hatchin g 0 9 7 4 6 9 9 0 4 2 9 0 9 3 9 5 8 9 5 7 7 6 8 8 9 223 2 BIRG E 

### characterizatio n o f

coal element s wer e no t availabl e fo r

th e firs t tw o set s o f effluen t bioassays

. Sunfis heggs , however , hav e th e same hatchin g tim e (exposur e period ) a s goldfis han dgenerall y exhibi t simila r sensitivit

y whe n use di n aquati c bioassay s (Birge , Black , an dWesterman , 1978)

. Durin g th e exposur e perio dfo r sunfis heggs , mean effluen t

meta l concentrations , wit hstandar derrors , wer e 

### 0. 4 ±0. 2 pp b Ag , 

### 107 0 

### ± 23 0 pp b Al , 

### 72. 0 

### ±

43. 0 pp b Cd , 5. 5 ±1. 8 pp b Cu , 

### 20. 6 ±4. 8 pp b Hg , 

### 31. 5 ±1. 4 pp b Ni , an d

### 70. 0 ±6. 7 pp b Zn

. A t th e 0. 1 dilution , whic hgav e 42 % surviva l fo r sunfis hegg s (Tabl e 6) , al l analyze dmetal s excep t aluminu mwer e wel l belo w goldfis hLC ! values

. Aluminu mwa s presen t a t approximatel y two-third s o f

th e LC S O 

### value

. Althoug hth e effluen t wa s no t analyze dfo r

al l possibl e toxicants , thi s correlatio n tend s t o suppor t applicatio n o f

th e toxicologica l inde x give n fo r coal element s (Table s 2 an d3)

. Befor e th e goldfis hbioassay s wer e initiated , effluen t meta l concentration s ha ddroppe dt o 0 pp b Ag , 16 0 ± 1 0 

### pp b Al , 1. 5 

### ±1. 5 pp b Cd , 4. 5 ±1. 8 pp b Cu , 3. 8 ±0. 7 pp b Hg , 23. 0 ±3. 0 pp b Ni , an d44. 5 ±8. 0 pp b Zn

. Thes e value s wer e al l belo w LC i ' s calculate dfo r goldfish , excep t

aluminum , whic hwa s presen t a t abou t th e LC 5 0 

### leve l (Table 2)

. Th e undilute deffluen t gav e 57 % survival

. DISCUSSIO N Th e embryo—larva l bioassay s reporte di n Tabl e 2 demonstrat e 'th e hig htoxicit y o f

numerou s inorgani c coa l element s t o aquati c biota

. Dependin g o n th e anima l species , LC 5 0 

### value s o f 0. 1 pp mo r les s wer e observe dfo r 1 5 coal elements , an dcalculate dLC ] ' s range ddown , t o 0. 1 t o 0. 2 pp b fo r mercur y an dsilver

. Tungste n wa s th e leas t toxi c elemen t

i nal l cases , wit hLC 5 0 

### value s rangin g fro m 2.9 0 pp mfo r

th e toa dt o 12 0 pp mfo r th e goldfish

. Whe nth e tes t 1 

### dat awer e averaged , th e increasin g orde r o f sensitivit y o f

anima l specie s wa s goldfish , trout , an dtoad

. Th e orde r

o f toxicit y o f

th e 2 2 elements , a s determine db y LC 5 0 

### values , varie dsomewha t fo r embryo—larva l stage s o f th e thre e species

. Onl y Ag , Cd , Cr , Hg , Ni , an dP b occurre damon g th e 1 2 mos t toxi c element s fo r

al l three , bu t

Al , As , Co , Cu , Ge , V , an dZ nwer e include di nthi s grou p fo r tw o specie s (Tabl e 2)

. O f particula r interes t wer e th e consisten t

extrem e toxicit y o f

mercur y an dsilve r

t o developmenta l stage s o f al l specie s an dcertai n selectiv e responses , suc ha s th e hig hrelativ e toxicit y o f aluminu mt o goldfish , germa niu man dlanthanu mt o trout , an dseleniu man dzin c t o th e toad

.AQUATI C TOXICOLOG YO F TRAC E ELEMENT S 23 3
100 H £

0 - 0.000 1 0.00 1 0.0 1 0. 1 SILVE R CONCENTRATION , pp m Fig . 3 Effect s o f

silve ro n embryo—larva l stages . 1. 0

Severa l pattern s o f

respons e wer e discernibl e concernin g th e differentia l sensitivity o f th e thre e tes t

organisms

. Highes t

uniformit y wa s obtaine dfo r

silver , whic hgav e a n exceptionall y narro w rang e o f LC 5 0 value s (0.0 1 t o 0.0 3 ppm)

. A s see n i n Fig

. 3 , thi s relationshi p hel dfo r th e ful l rang e o f

exposur e concentrations

. Germaniu m produce dsimilar

effect s o n th e tw o mos t sensitiv e tes t

animals , trou t an dtoads , bu t

wa s substantiall y les s toxi c t o th e goldfis h(Fig

. 4)

. Thi s sam e patter n wa s give n b y Cu , Mo , Ni , Sb , Sr , Tl , an dV

. A stil l mor e heterogeneou s respons e occurre dfo r P b (Fig

. 5) , Hg , an d certai n othe r

element s (e.g. , La , Sn , an dW)

. Considerin g th e respons e pattern s summarize di n Figs

. 3 t o 5 , i t i s probabl e tha t

th e diversit y o f aquati c specie s affecte db y pollutio n woul dincreas e i nth e orde r o f Pb , Ge , an dAg

. Althoug helement s suc ha s P b an dG e likel y woul daffec t

fewe r species , thes e toxicant s probabl y woul dcon tribut e t o a n ecologica l imbalanc e o f aquati c biota

. A s noted , Se , Zn , an dcertai n othe r

element s (e.g. , A s an dCo ) wer e mor e selectiv e fo r th e toad , and , o n th e basi s o f LC 5 0 values , th e toa dwa s th e mos t sensitiv e specie s fo r

1 7 o f th e 2 2 elements

. Thi s suggest s tha t amphibian s ma y constitut e particularl y sensitiv e targe t site s fo r cor d contaminants

. Fo r

example , goldfis hLC S ( ldetermination s fo r seleniu man dzin c exceede dthos e fo r th e toa dabou t

10 0 an d25 0 times , respectively

.23 4 BIRG E

0 - 0.00 1 0.0 1 0. 1 1 GERMANIU M CONCENTRATION , pp m Fig . 4 Effect s of

germanium o n embryo—larval stages . 10 0

100

0 - I 0.00 1 0.0 1 0. 1 1 LEA D CONCENTRATION , pp m 10 0 Fig . 5 Effect s o f

lea d o n embryo—larva l stages .AQUATI C TOXICOLOG YO F TRAC E ELEMENT S 23 5 

### Th e heterogeneit y o f

respons e observe dfo r

th e thre e anima l specie s somewha t

complicate s applicatio n o f th e bioassa

y dat ao n coal element s t o impac t assessment

an dpollution-abatemen t tech

nology

. Therefore , th e mean LC S 0 

### an dsensitiv e specie s indexe s (Tabl e 3 ) were develope dt o provid e asimplifie ddat abas e fo r energ y an denvironmental engineers

. Th e sensitive-specie s rankin g fo r coal element s wa s use dt o delineate uppe r limit s o f toxicit y observe dfo r th e 6 6 independen t

bioassays , an dth e mean inde x summarize d averag e tes t

responses . Despit

e some notabl e exception s (e.g. , A l an d La) , th e toxicological order s give n i n th e tw o indexe s were generall y similar

. Principal difference s i n relativ e orde r were attribute dt o element s exhibitin g disproportionat e selectiv e toxicit y fo r aparticu

lar anima l species

. Th e onl y extrem e disparit y involve dlanthanum , fo r whic hmea n an dsensitiv e specie s LC 5 0 

### value s differe db y thre e order s o f magnitude

. W e shoul dnot e tha t severa l recen t

publication s revie w additiona l bioassay dat afo r som e o f th e trac e metal s foun di n coal (Nationa l Academ y o f Sciences—Nationa l Academ y o f Engineer

ing , Committee , 1973 ; Vaugha n e t al. , 1975 ; Environmenta l Protec

tio n Agency , 1976)

. I nth e fly-as hleachin g study , characteristic s o f th e simulate d effluen t wer e compare dwit hthos e recorde dfo r 1 4 TV A as hponds

. A s see n i n Tabl e 4 , goo dagreemen t wa s obtaine dfo r

al l tes t parameter s excep t

aluminu man dcadmium , bu t concentration s fo r thes e metal s were withi n TV A range s earl y i n th e thir delutio n interval

. Th e hig hinitia l value s fo r aluminu man dcadmiu mma y hav e resulte dfro mus e o f

distille dinfluen t

water , whic hcontribute dt o lo w p H i n th e simulate das hpond

. Thes e an dothe r result s indicat e tha t th e qualit y o f

effluen t wate r ma y b e improve dsomewha t b y regulatin g certai n parameter s (e.g. , p H an dalkalinity ) o f influen t wate r use dfo r as hsluicing

. Appreciabl e meta l leachin g continued , however , eve n afte r 77 0 hr , whe n th e chang e wa s mad e i n influen t wate r (Tabl e 5)

. Th e resultin g suit e o f

toxi c metal s produce dlethalit y o f tes t organism s throug h177 5 t o 1847 h r o f continuou s elutio n tim e (Tabl e 6)

. Effluen t meta l concentration s (Tabl e 5 ) wer e compare dt o fresh

wate r guideline s (Nationa l Academ y o f Sciences—Nationa l Academ y o f Engineering , Committee , 1973 ; Environmenta l Protectio n Agency , 1976 ) t o furthe r

evaluat e potentia l effect s o f fly-as hleachin g o n aquati c biota

. Throug h177 5 hr , mercur y remaine dwel l abov e th e limi t o f 0.0 5 ppb , an daluminu mexceede dth e 100-pp b leve l considere ddeleteriou s t o growt han dsurviva l o f fish

. Cadmiu mwa s ove r th e trou t

standar do f

0. 4 t o 1. 2 pp b fo r

177 5 h r an dexceede d th e maximu mlimi t

fo r othe r aquati c specie s ( 4 t o 1 2 ppb ) fo r 105 023 6 BIRG E t o 143 5 hr

. O n th e basi s o f th e Environmenta l Protectio n Agency' s (EPA ) applicatio n facto r (0.01 ) an dth e trout , toad , an dgoldfis h embryo—larva l LC S 0 values , nicke l an dzin c concentration s exceede d recommende dlevel s fo r al l tes t specie s throug h177 5 hr , an dsilve r wa s abov e acceptabl e limit s fo r 105 0 t o 126 6 hr

. Copper , withan applicatio n facto r

o f 0.1 , exceede dcalculate dconcentration s fo r trou t an dtoa dthroug h100 0 t o 1500 h r bu t wa s ove r

th e goldfis h limi t fo r onl y 2 2 hr

. Usin g embryo—larva l rathe r tha n adul t

LC S O value s resulte din more stringen t limit s for

Ag, Cu, Ni , andZn. However , freshwate r

standard s shoul dpermi t adequat e protectio n fo r sensitiv e life-cycl e stages
. Excep t fo r copper , th e suggeste dEP A applicatio n factor s appeare dacceptabl e fo r embryo—larva l stages
. O n th e basi s o f

dat ai n Tabl e 2 , 0.0 1 t o 0.0 5 o f LC 5 0 determination s gav e value s that

generall y fel l withi n o r near 95 % confidenc e limit s fo r LC , 's

. I n compariso n wit hth e EP A valu e o f 0.1 , amor e suitabl e applicatio n facto r

fo r coppe r wa s foun dt o b e 0.0 5 fo r goldfis han d trou t an d0.0 1 fo r

th e toad

. Sinc e combine dtoxicologica l effect s o f comple x suite s o f

trac e metal s ar e difficul t

t o quantif y b y existin g hazard-assessmen t criteria , direc t bioassa y monitorin g wa s use dt o provid e furthe r characteriza

tio n o f as heffluent

. A s noted , afte r 103 3 h r o f continuou s elution , undilute das heffluen t

produce d100 % mortalit y o f sunfis heggs , an d surviva l o f

goldfis hegg s wa s reduce dt o 57 % whe n exposur e wa s initiate da t

177 5 hr

. A 0. 1 dilutio n produce da n approximat e LC 5 0 fo r sunfish , an d0.0 1 gav e essentiall y control-leve l surviva l fo r bot h species

. Whe nmedia n surviva l wa s obtained , concentration s o f al l monitore dmetal s excep t aluminu mwer e a t

o r belo w goldfis hLC j values , an daluminu mwa s presen t a t abou t th e LC 5 0 leve l (Tabl e 2)

. Effluen t dilution s tha t

gav e control-leve l surviva l di dno t contai n an y monitore dmetal s a t

concentration s exceedin g goldfis hLC ] values

. Althoug has heffluen t

wa s no t analyze dfo r

al l possibl e toxicants , result s obtaine db y direc t effluen t

monitorin g wer e i n goo d agreemen t

wit hth e independen t embryo—larva l bioassay s fo r coa l elements

. Also , trac e metal s presen t a t o r belo w th e probi t

LC i ' s di d no t exer t an y over t

synergisti c effects

. I n addition , result s indicat e tha t continuous-flo w embryo—larva l tes t system s ar e highl y suitabl e fo r i n sit u toxicologica l monitorin g o f comple x coa l effluents

. Althoug hno t

intende dt o serv e i n lie u o f actua l fiel dstudies , simulate das hpond s ca n b e use dt o characteriz e aqueou s leachin g processe s an dt o evaluat e as heffluent s fo r potentia l environmenta l hazards

. Tes t

parameter s ca n b e manipulate dindividuall y t o deter

min e effect s o nmeta l elutio n rates , an dsuc hmode l system s ca n b e particularl y usefu l i ncomparin g as hresidue s o f coa l fro mdifferen tAQUATI C TOXICOLOG YO F TRAC E ELEMENT S 23 7 formations

. Th e chemica l compositio n o f botto man dfl y as hi s highl y variable , dependin g o n th e sourc e o f th e coal used , combus

tio n conditions , an dsuc hfactor s a s th e efficienc y o f emissio n - contro l equipmen t

(Moulton , 1973 ; Chu , Nicholas , an dRuane , 1975 ; Cooper , 1975)

. I n additio n t o difference s i n as hcomposition , numerou s physica l an dchemica l factor s ma y affec t th e leachin g o f trac e element s an dth e fina l compositio n o f ash-pon dwater
. Thes e factor s includ e th e quantit y o f wate r use dfo r

sluicing ; it s tempera

ture , pH , an dhardness ; an dvariou s performanc e characteristic s o f th e settlin g pond

. A s note db y Chu , Nicholas , an dRuan e (1975) , th e effect s o f

suc hvariable s o n th e qualit y o f ash-pon deffluent s ar e no t sufficientl y understood

. I t i s known , however , tha t anumbe r

o f coal-derive dinorgani c element s reac happreciabl e concentration s i n ash-pon dwaters
. Sinc e 1973 , TV A ha s analyze dfo r 1 7 trac e element s i nquarterl y gra b sample s fro mbotto mash , fl y ash , an d combine das hponds , an dth e result s hav e bee n summarize db y Ch u an dco-worker s (Chu , Nicholas , an dRuane , 1975 ; Chu , Krenkel , an d Ruane , 1976)

. Discharge s fro mfly-as hpond s wer e reporte dt o contai n u p t o 7. 3 pp mAl , 0. 3 pp mBa , 0.0 4 pp mCd , 0. 1 pp mCr , 0. 3 pp mCu , 0.0 8 pp mPb , 13. 4 pp mMn , 1. 1 pp mNi , an d1. 5 pp m Zn

. Range s fo r

anumbe r

o f thes e metal s ar e summarize di n Tabl e 4

. Othe r investigator s als o hav e considere dvariou s problem s associate dwit hfly-as hdisposal (Guthrie , Cherry , an dRodgers , 1974 ; Theis , 1975 : Hollan de t al. , 1975)

. Thei s (1975 ) indicate dtha t th e productio n o f

meta l leachate s an dalteration s o f p H an ddissolve d oxyge n ma y affec t

receivin g waters
. H e als o demonstrate dsignifican t releas e rate s fo r

trac e metal s whe n fl y as hwa s disperse di n distille d water
. Hollan de t

al

. (1975 ) investigate dth e environmenta l effect s o f trac e element s i n th e pon ddisposa l o f as han dflue-ga s desulfuriza

tio n sludge

. Sample s o f as han dsludg e fro mfiv e generatin g station s wer e studie db y simulate dponding

. I n general , concentration s o f aqueou s leachate s wer e low , bu t Ba , B , Cr , Hg , an dS e exceede dEP A guideline s fo r

publi c wate r

supplies

. However , thes e investigator s di d no t compar e thei r

finding s wit hEP A standard s fo r freshwate r

biota , whic hgenerall y ar e mor e stringent , an dthe y di dno t conside r

th e combine dtoxi c effect s o f th e resultin g meta l mixtures

. Guthrie , Cherry , an dRodger s (1974 ) evaluate dth e impac t o n biot ai n water s receivin g ash-basi n effluen t fro macoal-fire dpowe r plant

. Bacterial , plant , an danima l diversitie s wer e reduce da t site s affecte d b y as heffluents

. Abioti c wate r parameter s affecte db y ash-basi n effluent s include dtemperature , turbidity , dissolve doxygen , an dpH

. Concentration s o f

coal-as hleachate s (e.g. , Cd , Cr

. Cu , Hg , an dZn ) wer e lowes t

i neffluen t

water , somewha t

greate r i naquati c biota , an d23 8 BIRG E 

### highes t i n benthos

. Thi s indicate daccumulatio no f thes e toxicant s i n biomas s an dbotto msediment

. Th e result s give nher e sho w clearl y tha t asubstantia l numbe r

o f mino r an dtrac e element s o f coal an dfl y as har e highl y toxi c t o aquati c organisms

. Man y are leachabl e fro mashresidue s at concen tration s tha t

prov e lethal t o fis han damphibianembryo—larva l stage s an dothe r

organisms

. Sinc e annua l coa l utilizatio ni n th e Unite d State s ma y reac h1 billio nton s o r mor e i n th e near

futur e (Vaugha n e t al. , 1975) , i t

remain s essentia

l to characteriz e mor e full y th e toxi c propertie s o f

coal-derive dcontaminants , ascertai n thei r releas e rates , an ddetermin e thei r

pathway s o f

exchang e withi nan dultimat e effect s upo n aquati c ecosystems
. ACKNOWLEDGMENT S 

### I shoul dlik e t o acknowledg e effort s devote dt o bioassay evaluatio nb y A

. G

. Westerma nan dJ

. A

. Blac k an dcontribution s b y R

. A

. Freemanan dJ

. E

. Hudso nt o th e fly-ash-leachin g studies

. I a m mos t gratefu l t o B

. A

. Rame y fo r preparatio no f

th e manuscrip t

an d figures

. Th e researc hreporte dher e wa s supporte db y th e Institut e fo r Minin g an dMineral s Research , Lexington , Kentuck y (gran t numbe r 7576-EZ)

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