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Removal of heavy metals from industrial wastewaters can be accomplished through various treatment options, including
such unit operations as chemical precipitation, coagulation, complexation, activated carbon adsorption, ion exchange,
solvent extraction, foam flotation, electrodeposition, cementation, and membrane operations. This paper describes these
various treatment strategies and methodologies employed for heavy metal removal. Comparison of their applications in
industry are addressed. Advantages and disadvantages are addressed for each treatment scheme.
INTRODUCTION bath. The spent process waters u s u a l l y con-
t a i n h i g h c o n c e n t r a t i o n s o f ammonia o r cyanide
Growing concern f o r t h e presence and con- which may i n t e r f e r e w i t h t h e removal o f the
t a m i n a t i o n o f heavy metals i n our water sup- heavy metals by hydroxide p r e c i p i t a t i o n .
p l i e s has s t e a d i l y increased over t h e l a s t few Generally, t h e waste problems are r e l a t e d t o
years. Elements such as mercury and cadmium t h e t r a n s f e r o f d i s s o l v e d metal from p l a t i n g
e x h i b i t human t o x i c i t y a t extremely low con- baths o r m e t a l surface c l e a n i n g baths by drag
c e n t r a t i o n s . The elements s i l v e r , chromium, out.
lead, copper, and z i n c a l s o e x h i b i t t o x i c pro-
p e r t i e s t o humans although t h e c o n c e n t r a t i o n s A number o f s p e c i a l i z e d processes have
a r e orders o f magnitude h i g h e r than t h a t r e - been developed f o r t h e removal o f metals from
q u i r e d f o r Cd o r Hg t o x i c i t y . The most pub- waste discharges. These u n i t operations i n -
l i c i z e d case o f i n d u s t r i a l heavy metal p o l l u - c l ude: chemical precipitation (18,67,85,87,111,124),
t i o n i n v o l v e d t h e discharge o f t h e c a t a l y s t coagulation/flocculation (38,431,ion exchange/
methylated mercury c h l o r i d e i n t o Minamato Bay, solvent extraction (36.44,76,93), cement-
Japan, from a p l a s t i c manufacturing f a c t o r y . a t i o n (41,681, complexation (66,99,1511,e l e c t r o -
Microorganisms converted t h e sedimented com- chemical operations (391, b i o l o g i c a l operations
pound t o monomethyl-mercury, which l e d t o an (27,301, a d s o r p t i o n (11,60,77,110), evaporation
enrichment o f t h i s t o x i c metal i n f i s h con- (1131,filtration (401, and membrane processes
sumed by l o c a l people, causing severe c h r o n i c (23,291.A number o f authors have presented
mercury p o i s o n i n g diseases . (31. Removal s o r summaries on various techniques a v a i l a b l e f o r
r e d u c t i o n s o f t o t a l heavy metal c o n c e n t r a t i o n s heavy metal removal from s o l u t i o n .
below 10 mg/l a r e u s u a l l y desirable p r i o r t o
any wastewater treatment o p e r a t i o n s i n c e many
heavy metals, adversely a f f e c t b i o l o g i c a l o x i - The purpose o f t h i s paper i s t o review
d a t i o n processes, (Z,27,113), such as trickling t h e processes c u r r e n t l y a v a i l able f o r waste-
f i l t e r s , a c t i v a t e d sludge, and anaerobic d i - waters laden w i t h heavy metals. The removal
ges t i on. e f f i c i e n c i e s and r e s i d u a l heavy metal con-
c e n t r a t i o n s r e p o r t e d i n t h e l i t e r a t u r e are
Metal processing, metal f i n i s h i n g , and summarized i n t h i s paper and w e l l as r e l a t e d
t h e p l a t i n g i n d u s t r i e s a r e obvious sources of c o s t i n f o r m a t i o n . This paper c o u l d n o t pos-
these heavy metals. The n a t u r e o f t h e waste s i b l y i n c l u d e a l l t h e research and a p p l i c a -
d i r e c t l y r e f l e c t s t h e p a r t i c u l a r combination t i o n s o f heavy metal removal from wastewaters;
o f metals and manufacturing processes used by r a t h e r t h i s paper seeks t o h i g h l i g h t many o f
a g i v e n p l a n t . For example, p l a t i n g i s com- the s i g n i f i c a n t contributions t o the f i e l d
monly done i n e i t h e r an ammonia o r a cyanide d u r i n g t h e p a s t twenty years.
165
166 Separation of Heavy Metals AlChE SYMPOSIUM SERIES
precipitation of heavy metals (45) : soluble tions of Se, Cd, and Zn were 9,2, and 5 mg/l,
sulfide precipitation (SSP) and insoluble s u l - respectively. A t pH 10.5, the residual Cd
fide precipitation ( I S P ) , the difference being and Zn concentrations decreased t o 0.6 and
on how the sulfide ion i s introduced i n t o the 1.1 mg/l, respectively. The s e t t l i n g r a t e
wastewater. In the SSP process, sulfide i s of the sludges was a function of pH and the
added in the form of a water soluble sulfide suifide dose. Poor s e t t l i n g velocities re-
reagent such as sodium sulfide (Na S ) or sulted from hydroxide precipitation and excess
sodium hydrosulfide. I n the ISP pfocess, a sulfide precipitation. The s e t t l i n g rate
slightly soluble ferrous sulfide (FeS) slurry with 0 . 6 ~was twice t h a t obtained by hydroxide
i s added t o the wastewater t o supply the precipitation. Bhattacharyya e t a l . (21) ob-
needed sulfide ions needed t o precipitate the served essentially complete removal of zinc
heavy metals. Since most of the heavy metals using sulfide precipitation ( 1 . 0 ~ )for pH > 4.
have sulfides less soluble than ferrous sul- Measurements taken on H2S loss (as gas) showed
fide, they will precipitate a s metal sulfides. H S loss was negligible due t o the preference
Advantages of the ISP process include the f$r the metal sulfide reaction over the
absence of any6detect$gle H S gas and re- H -S- reaction. The f a c t t h a t nickel pre-
duction of Cr t o Cr . D?sadvantages of cipitation with sulfide was found to be a
the process include considerably larger t h a n s t r o n g function of reaction time for pH < 10
stoichiometric reagent consumption and 1 arge i n open systems was attributed to nickel
quantities of sludge being generated due t o dissolution causing the formation of Ni(SOH)2
the ferrous hydroxide formation, In the SSP and NiSO i n the presence of oxygen. Using
process, the high sulfide concentration often sulfide ffrecipitation, residual concentrations
causes rapid precipitation of metal sulfides less t h a n 0.1 mg/l for Cu, Cd, Pb, and Zn
(high nucleation rates) resulting in small can be achieved(l8) for the pH range of 4-12.
particulate fines and hydrated colloidal The combined hydroxide-sulfide treatment a t
particles. This causes poor s e t t l i n g and pH 8-9 was shown effective for removal of
f i l t e r i n g of the flocs. In the presence of As, Zn, Cd, Pb, Cu, Hg, and Fe in both
chelating agents, hydroxide precipitation of synthetic wastewaters and for full-scale
heavy metals i s n o t possible even a t high pH. operation of wastewaters a t the Boliden Metal1
With sulfide precipitation, heavy metal removal Corporation, Skelleftehamn, Sweden. Even
i s possible even with chelants present, a l - with sulfide overdoses a t low pH, no H2S gas
t h o u g h the heavy metal precipitation i s in- loss was observed.
fluenced by the presence of chelating agents.
In the absence of chelating agents, l i t t l e Fender e t a l . (49) studied sulfide pre-
metal hydroxide precipitation occurs f o r pH < 6. cipi tation for zinc-1 aden foundry wastewaters.
An excellent description and review of the The wastewater pH was adjusted with 1 ime t o
sulfide precipitation processes has been pro- pH's ranging from 8.5 t o 11.0. Ferrous sul-
vi ded by EPA (45). fide (750 mg/l) was added t o each sample.
The residual lead and iron concentrations
Bhattacharyya e t a l . (17) found sulfide were consistently less t h a n 0.1 mg/l for
precipitation using Na2S to be highly effective i n i t i a l wastewater concentrations of 0.1 and
for removal of Cd, Zn, Cu, Pb, As, and Se from 21.1 mg/l, respectively. The zinc concentra-
complex wastewaters. The separation character- tion decreased from 775 mg/l t o 1.7-3.7 mg/l;
i s t i c s were evaluated using a dilute synthetic however t h i s removal was s t i l l inadequate.
wastewater and an actual copper smelting p l a n t Two stage hydroxi de/sul f i de prec i pi t a t i on
wastewater. Overall separation and precipi- was investigated. The best treatment occurred
t a t e s e t t l i n g rates were optimum for under- for lime treatment a t pH 9.6 t o which 20 mg/l
stoichiometric addition of sulfide (-0.60 x FeS was added t o the supernatant, resulting
theoretical stoichiometric sul fide requi rement) i n a final f i l t e r e d effluent concentration
and pH > 8.0. For the copper smelting plant of 0.05 mg/l Zn.
wastewater, removal of Cd, Zn, and Cu exceeded
99%, w i t h the removals of As and Se being 98% A full scale SSP treatment plant(l33)was
and > 92%, respectively. The residual con- constructed by the U.S. Army a t the Belvoir
centrations achieved f o r Cd, Cu, and Zn were Research and Development Center in Fort
consistently in the range of 0.05-0.10 mg/l. Belvoir. Virainia. becomina oDerationa1 in
Using only hydroxide treatment, the s e t t l i n g February 1985. Safety f e a h es of the plant
rates and metal separations were considerably included: neutralization of the wastewater
lower t h a n t h a t obtained by sulfide precipi- pH prior t o sulfide a d d i t i o n automatic con-
t a t i o n . The Zn, Cd, and Se removals were much t r o l of the sulfide feed via a specific ion
poorer, even a t pH 10.5, using hydroxide t r e a t - probe, ferrous sulfate addi t on t o remove
ment. A t pH 8.5, the residual metal concentra- the excess sulfide, hydrogen peroxide oxidatioi
No. 243,Vol. 81 169
Coagul a t i o n / f l o c c u l a t i o n has been known .For treatment o f base metal mine drainage,
capable o f removing heavy metals from s o l u t i o n . (64),use o f an a n i o n i c polymeric f l o c c u l a n t
Coagulation r e f e r s t o t h e charge n e u t r a l i z a t i o n provided greater c l a r i f i e r operational re-
o f t h e p a r t i c l e s . F l o c c u l a t i o n i n v o l v e s slow 1ia b i 1it y and reduced mean metal concentrations
m i x i n g t o promote the agglomeration o f t h e i n t h e o v e r f l o w . Polymer a d d i t i o n s u b s t a n t i a l -
d e s t a b i l i z e d p a r t i c l e s . EPA (43) i n v e s t i g a t e d l y improved t h e sludge s e t t l i n g characteristics
the use o f l i m e s o f t e n i n g and c o a g u l a t i o n Aulenbach e t a1 .(6) observed t h a t a d d i t i o n
( u s i n g f e r r i c s u l f a t e o r a&m) f y i remyyal +6 o f alum o r sodium aluminate a t dosages t h a t
o f such heavy metals as Pb , Cd , C r , C r , e f f e c t i v e l y remove phosphorus i s b e n e f i c i a l
e t c . While l i m e s o f t e n i n g achieved removals i n t h e removal o f Cu, C r , and Pb from waste-
o f g r e a t e r than 98% i n t h e pH range o f 8.5-11.3 waters. Chromium removal i s enhanced by
f o r cadmium, cadmium removals by f e r r i c s u l f a t e sodium aluminate a d d i t i o n , b u t i s u n a f f e c t e d
and alum c o a g u l a t i o n were lower than t h a t of by alum a d d i t i o n . Both aluminum s a l t s i n -
l i m e s o f t e n i n g and were shown t o depend on crease t h e removal o f 1ead. N i 1ssy$lOtj) itj-
pH. Cadmium removals increased w i t h i n c r e a s i n g veS.igaty$ the+remov$i o f &++, Cu Cr ,
pH. F e r r i c s u l f a t e c o a g u l a t i o n o f a r i v e r Hg , Cd , Zn , N i ' , Co , and As'5 by
water c o n t a i n i n g 0.3 mg/l Cd showed removal aluminum s u l f a t e and calcium hydroxide t r e a t -
t o increase from 20% a t pH 7.2 t o above 90% ment. Orthophosphate had no i n f l u e n c e upon
a t pH 2 8. Alum c o a g u l a t i o n r e s u l t s a l s o i n - t h e p r e c i p i t a t i o n . The concentrations of Pb,
creased w i t h i n c r e a s i n g pH; however above pH 8, Cu, Cr, Hg, Cd, and As were reduced t o low
removals may depend on t h e raw water t u r b i d i t y . l e v e l s by b o t h p r e c i p i t a n t s , w h i l e Zn, N i ,
Both f e r r i c s u l f a t e and alum c o a g u l a t i o n and Co were p r e c i p i t a t e d o n l y f o r pH 9.5.
achieved g r e a t e r than 97% removal o f l e a d from The p r e c i p i t a t i o n o f Cu and Pb were severely
a r i v e r water c o n t a i n i n g 0.15 mg/l Pb i n t h e i n h i b i t e d by t h e presence o f NTA a t pH 1 9 . 0 .
pH range o f 6-10. Experiments on w e l l waters
under s i m i l a r c o n d i t i o n s had removal r a t e s by FLOTATION
f e r r i c s u l f a t e and a1 um c o a g u l a t i o n o f >97%
and 80-90%, r e s p e c t i v e l y . When t h e l e a d con- Foam f l o t a t i o n depends on t h e use o f a
c e n t r a t i o n was increased t o 10 mg/l, f e r r i c s u r f a c t a n t t h a t causes a nonsurface a c t i v e
s u l f a t e c o a g u l a t i o n again achieved removals m a t e r i a l t o become surface a c t i v e forming
i n excess o f 95% whereas alum coagulaJAon a product t h a t i s removed by b u b b l i n g a gas
achieved o n l y -80% removal. Using C r waters, through the b u l k s o l u t i o n t o form a foam.
f e r r i c s u l f a t e achieved the b e s t r e s u l t s , r e - The use o f foam f l o t a t i o n techniques f o r r e -
moving -35% a t pQ65.5 on a r i v e r water c o n t a i n - moval o f heavy metals has been w e l l studied.
i n g 0.15 mg/l C r . Alum c o a g u l a t i o n c o u l d (32,52,142,155). With dilute wastewaters containing
do no b e t t e r than 10% removal throughout t h e heavy metals i n t h e p a r t s per b i l l i o n o r p a r t s
e n t i r e pH range.+3pH has o n l y a s l i g h t e f f e c t per m i l l i o n ranges, foam f l o t a t i o n o f f e r s
qn removal o f C r by alum and i r o n coagula- several d i s t i n c t advantages:
t i o n . F e r r i $ 3 s u l f a t e c o a g d l a t i o n achieved simplicity
Pycellent C r removals, i n excess of 98%, f l e x i b i l i t y and e f f e c t i v e n e s s o f o p e r a t i o n .
Tnroughout t h e pH range o f 6.5-9.3. Alum l i m i t e d space requirements due t o r a p i d
oagulation, although l e s s e f f e c t i v e , o b t a i n e d reactions.
rziiovals exceeding 90% f o r t h e pH range 6.7- p r o d u c t i o n o f small, concentrated volumes
5 Above pH 8.5, removals began t o decrease; of sludge.
3 t pH 9 . 2 t h e remyyal had decreased t o 78%.
moderate c o s t s comparable t o t h a t o f l i m e
F o r an i n i t i a l C r c o n c e n t r a t i o n o f 10 mg/l,
No. 243,Vol. 81 173
precipitation. 2. I n c r e a s i n g t h e l e n g t h o f the s u r f a c t a n t
9 low c o s t s i n terms o f l a b o r , equipment, hydrocarbon t a i l decreases t h e b u l k
energy, and chemical s . l i q u i d concentration o f surfactant re-
capable o f a p p l i c a t i o n on small i n t e r m e d i a t e q u i r e d t o produce f l o t a t i o n .
and l a r g e scales. 3. I n c r e a s i n g p a r t i c l e s i z e increases f l o t a -
capabi 1it y o f reducing t h e contaminant con- tion efficiency.
c e n t r a t i o n s w e l l below t h e standards 4. I n c r e a s i n g temperature increases t h e r e -
e s t a b l i s h e d by r e g u l a t o r y agencies q u i r e d s u r f a c t a n t concentration.
d i s t i l 1a t i o n processes. i s expected t o be a f u n c t i o n o f : m ? t d l - l i g a n d
c h a p f i + $ i s t r i b y t h o r ( f o r example ML ,
P a t t e r s o n and M i n e a r ( l l 3 ) p o i n t o u t t h a t MH L -
' MOHL - ) ; f r e e metal and f r e e
e v a p o r a t i o n i s a w e l l - e s t a b l i s h e d technology l i g a n d charges; t h e pH o f t h e carbon s u r f a c e
f o r r e c o v e r i n g p l a t i n g chemicals and water from and t h e p o l a r i t y o f l i g % % molecules. The
p l a t i n g waste e f f l u e n t s . Commericial u n i t s pH w i l l a f f e c t t h e charge d i s t r i b u t i o n o f
have been b u i l t f o r h a n d l i n g zinc, copper, t h e v a r i o u s species as w e l l as t h e hydroxo
n i c k e l , chromium, and o t h e r metal p l a t i n g baths. group d i s t r i b u t i o n a t t h e a c t i v a t e d carbon
Disadvantages o f e v a p o r a t i o n / d i s t i l l a t i o n surface. J e v t i t c h and Bhattacharyya (69)
processes i n c l u d e : e s t a b l i s h e d t h e a d s o r p t i o n c a p a c i t i e s o f com-
plexed heavy metal i o n s by a c t i v a t e d carbons
Relatively high capital costs. under e q u i l i b r i u m c o n d i t i o n s . An e x t e n s i v e
R e l a t i v e l y high operational costs ( p a r t i c u - experimental i n v e s t i g a t i o n was conducted w i t h
l a r l y f o r vacuum systems.)
D i s t i l l a t i o n processes are energy i n t e n s i v e . a c t i v a t e d carbons t o establish2$he a$$or;;$p"
capaci5jes o f heavy metals (Cd , N i , Y
The economics o f d i s t i l l a t i o n imposes a
and Zn ) i n t h e presence o f complexing agents
c o n s t r a i n t on t h e s i z e range o f these systems.
(EDTA, t r i e t h y l e n e t e t r a m i n e (TRIEN), c i t r a t e ,
These systems are complex, r e q u i r i n g t r a i n e d e t c ) . Adsorption e q u i l i b r i a a r e e x p l a i n e d
personnel t o operate and m a i n t a i n them.
by species charges and carbon s u r f a c e charge
c h a r a c t e r i s t i c s . I n t h e pH range 7.5-8.0,
ADSORPTION
t h e a c t i v e s i t e s a r e p o s i t i y f l y charged. The
a d s o r p t i o n c a p a c i t i e s o f Cd (and o t h e r heavy
Due t o t h e h i s t o r i c a l development and use
m e t a l s ) , f r e e ligands, and cadmium-ligands
o f a c t i v a t e d carbon i n water and wastewater
were a l s o a f u n c t i o n o f feed metal concentra-
treatment, most o f t h e a p p l i c a t i o n s and research
t i o n , t y p e s o f l i g a n d s , molar r a t i o o f l i g a n d /
e f f o r t on a c t i v a t e d carbon have been o r i e n t e d
metal, and pH. Complete m e t a l - l i g a n d species
towards o r g a n i c s removal (63). Research e f f o r t s
d i s t r i b u t i o n s were c a l c u l a t e d by computer
on i n o r g a n i c s removal by a c t i v a t e d carbon,
solutions o f multiple reaction equilibria.
s p e c i f i c a l l y m e t a l l i c ions, have been markedly
For an e q u i l i b r i u m cadmium c o n c e n t r a t i o n o f
1 i m i t e d . Huang(63) p r o v i d e s an excel l e n t r e v i e w
0.1 mM (pH 7.5-8.0), t h e sequence i n adsorp-
o f i n o r g a n i c s removal by a c t i v a t e d carbon by
t i o n c a p a c i t y f o r cadmium c h e l a t e s i s ,Q ,-c,
c o n s i d e r i n g such f a c t o r s as s u r f a c e p r o p e r t i e s
(and t h e i r measurement) and a d s o r p t i o n charac- > QCD-citrate > QCd-TRIEN > QCd-tartrate.
t e r i s t i c s o f c a t i o n i c and a n i o n i c species o n t o
a c t i v a t e d carbon surfaces. I m p o r t a n t p h y s i c a l - Huang e t a1 . evaluated t h e a c t i v a t e d
chemical p r o p e r t i e s a f f e c t i n g i n o r g a n i c e l e c t r o - carbon a d s o r p t i o n process f o r removal o f
l y t e a d s o r p t i o n i n c l u d e : s p e c i f i c s u r f a c e area, Co(I1) from s o l u t i o n w i t h s p e c i a l emphasis
pore s t r u c t u r e , e l e c t r o p h o r e t i c p r o p e r t i e s , p l a c e d on t h e e f f e c t of v a r i o u s organic sub-
and s u r f a c e a c i d i t y . stances on Co(I1) removal. T h e i r r e s u l t s
showed Co( 11) was removed by a d s o r p t i o n r a t h e r
Very l i t t l e has been r e p o r t e d on t h e use than be p r e c i p i t a t i o n alone. Fourteen types
o f a c t i v a t e d carbon f o r removal o f i n o r g a n i c s o f a c t i v a t e d carbon were evaluated f o r t h e i r
f r o m wastewaters. A c t i v a t e d carbon was r e - Co(I1) removal c a p a b i l i t i e s . Two a c t i v a t e d
p o r t e d t o be a p o t e n t i a l adsorbent f o r heavy carbons, Nuclar SA and Nuchar SN, gave s i m i l a r
metal removal (4,35). Salvaged automobile t i r e s h i g h metal removal c a p a c i t i e s (removals
a r e capable o f removing t r a c e metals (A1 , Hg, approached loo%, depending on t h e s o l u t i o n pH).
Ni, Cd, C r , Co, Cu, Fe, Pb, Mn, Ag, and Zn) The Co(I1) removal percentage decreased w i t h
from s o l u t i o n due t o v a r i o u s m a t e r i a l s p r e s e n t i n c r e a s i n g s u r f a c e l o a d i n g s . The authors
i n t h e t i r e s , such as s u l f u r , carbon black, showed t h a t t h e presence o f o r g a n i c a c i d r e -
f i l l e r s , s y n t h e t i c rubber, a n t i o x i d a n t s , e t c . s u l t s i n f i v e d i f f e r e n t cases o f e f f e c t s i n
(103-05).Saito(134)2sed a c t i v a t e d carbon and s u l - Co(I1) a d s o r p t i o n : 1. anion induced c a t i o n
f o n a t e d coal f o r removal o f Cu, Cd, and Fe f r m adsorption, 2. complexes n o t adsorbable ( o r
wastewaters. Removals exceeding 98% were c o m p e t i t i v e anion a d s o r p t i o n ) , 3. complexes
achieved f o r c u p e r i c i o n s t r e a t e d w i t h s u l f o - adsorbable ( o r non-competitive anion a d s o r p t i o n ) ,
nated coal a f t e r a one-stage e x t r a c t i o n . For 4. anion-induced c a t i o n a d s o r p t i o n and com-
an i n i t i a l copper c o n c e n t r a t i o n o f 312 mg/l, plexes n o t adsorbable, and 5 . anion-induced
t h e r e s i d u a l copper c o n c e n t r a t i o n was reduced c a t i o n a d s o r p t i o n and cumplexes adsorbable.
t o 0.08 mg/l a f t e r a two-stage e x t r a c t i o n . Depending on the extenL o f complex formation
S i g n i f i c a n t removals were achieved l i k e w i s e and t h e a d s o r b a b i l i t y o f t h e complexed Co(I1)
w i t h a c t i v a t e d carbon. The e x t e n t of heavy and o f t h e l i g a n d , i t w a s p o s s i b l e t o d i f -
metal a d s o r p t i o n on a s p e c i f i c t y p e o f carbon f e r e n t i a t e f o u r d i f f e r e n t e f f e c t groups:
182 Separation of Heavy Metals AlChE SYMPOSIUM SERIES
C
100
100
mg/l. Fe/Ni = 0
nig/l. Fe/Ni = 0.5
mg/l, Fe/Ni = 1.0
94
Table 1. (cont.)
Technology Hetal(s) pH I n i t i a l Metal, Residual Etetal Removal Coiinlents Reference
Einploved Concentration Concentration E f f i c i e n c y .%
Table 1 (cont.)
Technology Metal(s) pH I n i t i a l Metal Residual Metal Reilloval Comnennts Reference
Employed Concent r a t i o n * Concentration* E f f i c i e n c y ,%
29.30.33,
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86( 24) : 1 7 6 , 7 5 7 ~ (1977r;-
~
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