I RRE VE RS I B I L I T Y OF S UL F AT E S ORP T I ON ON

GOETHI TE AND HEMATI TE

LAURIE J. TURNER* and JAMES R. KRAMER
Department of Geology, McMaster University, 1280 Main Street West, Hamilton, Ontario,
Canada L8S 4M1
(Received January 28, 199i; revised July 2, 199I)
Abstract. Sulfate ion adsorption and desorption experiments carried out on synthetic goethite and hematite
and natural hematite show adsorption to be a highly irreversible reaction. All oxides showed an increase
in sulfate ion adsorption with decrease in pH. Only a small fraction of sorbed sulfate was desorbable
after 48 hr, and only at a pH of 3. Extreme irreversibility of sulfate sorption on these common soil
minerals suggests that adsorbed sulfate is more immobile in watersheds than previously considered
and that recovery models which inherently assume reversibility may need to be modified.
1. Int roduct i on
The Direct Delayed Response Program (DDRP) has been employed to assess the
long term effect of acid deposition. Indeed much of the Acid Rain literature
conclusions are geared towards a saturation-desorption phenomenon. Inherent in
the models (i.e. MAGI C) is the assumption of reversibility of sulfate adsorption
(Cosby et al . , 1986; Hornberger et al . , 1986), even though some literature suggests
that sulfate sorption is more irreversible in nature.
Sulfate ion retention in a soil depends on environmental conditions and site reac-
tion characteristics, with oxyhydroxide and clay minerals being important soil con-
stituents. Definition of constituent sorption charateristics and consideration of factors
which influence sorption are prerequisite to the modeling of sulfate ion sorption
in soils. When the sorption process on individual soil constituents is ascertained,
then parallel effects in whole soil behavior may be estimated.
Natural whole soil samples are a complex mixture of surfaces with a variety
of organic and inorganic species in the soil solution. Many soils have been examined
for sorption characteristics (Kamprath et al . , 1956; Liu and Thomas, 1961; Chao
et al . , 1962; Chang and Thomas, 1963; Barrow, 1967; Bornemisza and Llanos,
1967; Hasan et al . , 1970; Sanders and Tinker, 1975; Couto et al . , 1979; Singh,
1984), but derivations of mechanisms from soil studies is difficult due to their complex
nature, and the inability to specify specific reactions with certainty. The sorption
mechanisms of the individual constituents can be interpreted with less ambiguity,
since specific mineral components and surfaces can be more thoroughly characterized.
Extrapolation of experimental results for individual surfaces must be done with
caution, however, because when placed back into the natural environment, con-
* Current address: 10 York Street, Dundas, Ontario, Canada L9H 1L2.
Water, Air, and Soil Pollution 63: 23-32, 1992.
9 1992 Kluwer Academic Publishers. Printed in the Netherlands.
24 LAURIE J. TURNER AND JAMES R. KRAMER
stituent behavi or may be modi fi ed by i nt eract i on with ot her subst rat e component s.
Ani on sor pt i on on oxyhydr oxi de minerals has been st udi ed fairly extensively
(Bowden e l a l . , 1973; Breuwsma and Lykl ema, 1973; Parfi t t and Russell, 1977;
Parfi t t and Smart , 1977, 1978; Sigg and St umm, 1981; Borggaard, 1983), but onl y
a few ( Ayl mor e e t a l . , 1967; Hi ngst on e t a l . , 1974; Russell e t a l . , 1974) have exami ned
desor pt i on also. Thi s paper present results of sor pt i on- desor pt i on studies on the
i ron oxide, hemat i t e, and hydroxi de, goethite. These i mpor t ant soil minerals are
easily pr epar ed and known to sorb sulfate.
2. Experimental Methods
PREPARATI ON OF MATERI ALS
Goet hi t e was pr epar ed by aging a sol ut i on of ferric ni t rat e, adj ust ed to pH 12,
at 60 ~ f or 24 hr (At ki nson e t a l . , 1968). Hemat i t e was pr epar ed by hydrol yzi ng
ferric ni t rat e at 100 ~ under reflux condi t i ons f or 18 d (Parks and DeBr uyn, 1962).
Precipitates were washed, filtered and vacuum dried. X- r ay di ffract i on analysis
( XRD) i ndi cat ed t hat the materials obt ai ned were goet hi t e in the first case, and
hemat i t e with a small amount of goet hi t e i mpur i t y in t he second case. A sample
of nat ur al hemat i t e was crushed and sieved. XRD analysis showed no crystalline
impurities.
The surface areas of synt het i c goet hi t e and hemat i t e, measur ed using the BET-
N2 adsor pt i on met hod ( Br unauer e t a l . , 1938), were 44.1 and 43.2 m 2 g l, respectively,
while the crushed nat ural hemat i t e sample was 12.0 m 2 g 1.
The pH of zero points of charge as det er mi ned by aci d/ base t i t rat i ons were
7.1, 8.0, and 8.8 (all + 0.05) f or goet hi t e, hemat i t e and nat ural hemat i t e, respectively.
All chemicals used were of anal yt i cal reagent grade.
SORPTI ON EXPERIMENTS
Ooet hi t e and hemat i t e samples (0.1 g) were mi xed with 25 t o 50 mL of K2NO3
medi a of 10 -2 t o 10 -4 M concent r at i on. These const ant i oni c st rengt h suspensions
were equi l i brat ed for 24 hr at a const ant pH value. Known amount s of sulfate
were added K2SO 4 to at t ai n initial sol ut i on concent r at i ons up to 5 mM. At pre-
set time intervals (0.5 to 48 hr), the pH was r ecor ded, and a sample of t he suspension
r emoved and filtered t hr ough 0.45 v.m Millipore filter paper. The filtrate was anal yzed
f or sulfate using i on chr omat ogr aphy.
DESORPTI ON EXPERIMENTS
Reversibility was exami ned by leaching in a const ant pH and ionic media. This
was achi eved by fi l t rat i on and resuspensi on of a sample to which a known amount
of sulfate had been sorbed. The ionic media and pH were the same as f or upt ake
studies, and the rat i o of solid t o sol ut i on was kept const ant . Aft er a react i on time
of 48 hr, the suspensi on was filtered and the filtrate exami ned for sulfate con-
IRREVERSIBILITY OF SULFATE SORPTION 25
i f )
i
O
E
O
Or)
O
E
=,,
11)
i f )
Q)
i
i f )
O
E
=k
300
250
200
150
100
A. Goethite
t
~ 0 0
rn 17
s 0 , ~
~ ~ 4 ' ~ 6
Equilibrium Solution Concentration (retool/I)
300
250
200
150
100
B. H e m a t i t e . ? J ................
s ~ - , , , , ~ 6
Equilibrium Solution Concentration (mmol/1)
300
C. Natural Hematite
250
200
150
100
50.
0
E(
p~3
~ ' ~ ~, ~ 6
uilibrium Solution Concentration (mmol/i)
p~5 pl~17 Des.9~, l!on
Fig. 1. Ads or pt i on i sot her ms for sulfate s or pt i on on (A) goet hi t e, (B) hemat i t e and (C) nat ur al hemat i t e
at r oom t emper at ur e for p H 3, 5 and 7. Des or pt i on dat a are i ndi cat ed by an ast eri sk.
26 L AUR I E J . T U R N E R A N D J AME S R. KRAME R
c e nt r a t i on. The ent i r e p r o c e d u r e was r e p e a t e d s ever al t i mes unt i l no a d d i t i o n a l
s ul f at e c o u l d be d e t e c t e d i n s ol ut i on. The v a r i o u s SO4 f r a c t i ons wer e s u mme d t o
d e t e r mi n e t he t ot a l d e s o r b a b l e f r a c t i on.
3. Resul t s a n d D i s c u s s i o n
SULFATE SORPTION
The s o r p t i o n pr oc e s s was i n i t i a t e d by a r a p i d r e a c t i o n ( ~1/ 2 hr ) f o l l o we d by a
l o n g e r s l ow one whi c h r e a c h e d a s t e a d y s t a t e o r a p p a r e n t e q u i l i b r i u m i n 24 hr .
3
2 . 5
E 2
" ~ 1 . 5
0
" J 1
0 . 5
0
A Hematite
. . . . . . . . . . s . . . . . . .
-1~ . . . . . . . . . . . . . . . . . . ~ ' "
. . . . . . . . . . . . . . . ~.:~:.-:
................................. = . ~ . ~ . . ~ ~ . - . . . . - . 9 . : . ~ 7 7 = ~ " * ' '
. . . . . . . . .. 0 . - . . - - - - ~ ' ' U "
I I I 1 I
1 . 5 2 2 . 5 3 3 . 5 4
Log Eqilibrium Sulfate Concentration, p m o l / I
2 . 5
B Goethite
D . . . . . . . . . . . . . . E3--' s . . . . . .
2 . . . . . . . . . . . . ~ - . . . . . E} . . . . . . . . . . . .
E . . . . . . - - . T
o , ~ " " ' " ~ o . . f o
0 . 5 t i t i i
1 1 . 5 2 2 . 5 3 3 . 5 4
Log Eqilibrium Sulfate Concentration, )Jmol/I
..~.. z~_ _~_ ~ " ~
Fig. 2. Freundlich plots for sulfate sorption on (A) hematite and (B) goethite at three pH levels. NH
= Natural hematite.
I R R E V E R S I B I L I T Y O F S U L F A T E S O R P T I O N 2 7
Th a t i s, n o f ur t he r c ha ng e s i n p H or s ul f at e c o n c e n t r a t i o n we r e o bs e r v e d af t er
24 hr. Thi s rapi d e qui l i br i um a t t a i n me n t is a c o m m o n p h e n o me n o n o f a n i o n s o r p t i o n
e x pe r i me nt s . In al l c as e s , t he o x i de s s o r be d i nc r e as i ng a mo u n t s o f s ul f at e as s o l u t i o n
p H wa s de c r e as e d. The a mo u n t s o r be d al s o i nc r e as e d wi t h s o l u t i o n s ul f at e c o n -
c e nt r a t i o n. The r e wa s n o ef f ect o f c ha ng i ng i o ni c s t r e ngt h o n a d s o r p t i o n f or he ma t i t e ,
but g o e t hi t e s o r p t i o n i nc r e as e d wi t h i nc r e as i ng i o n i c s t r e ngt h at a p H o f 5. Thi s
is i n c o nt r a s t t o t he o b s e r v a t i o n s o f Ba r r o w ( 1967) wh o n o t e d a de c r e as e i n s o r p t i o n
wi t h i nc r e a s i ng i o ni c s t r e ngt h up t o 0. 01 M, and n o ef f ect a b o v e t hi s c o n c e n t r a t i o n .
N o s o l i d c o n c e n t r a t i o n ef f ect was o bs e r v e d i n a ny o f t he s t udi es .
Fi gur e 1 s h o ws t he s ul f at e a d s o r p t i o n i s o t h e r ms o b t a i n e d f or t he t hr e e s a mpl e s
120
100
8O
E
6o
o
A Hematite / / . t . . . .
j . , "
9 , , "
~ , . ' "
/ ....*'"
J , , . , , . , .. ,o9149149 , ~ S ~
/ * / / ~ ~ ~,, " ~ S j "
40 , / . ...... . . . . . . ~
/ . / .- .... . . - "
2 0 ' . . . . . . . . . . . . 1~. . . . . . . . . . . . . . . . . . .
o . . . . : . . . . . . . . . . . . . . . . i , ,
0 1,000 2,000 3,000 4,000 5,000 6, 000
Eqilibrium Sulfate Concentration, ,umol/i
80
6O
E
40
o
/
/
1
. s
J
t
B Goethit~
/
/
/
/
i
/
r , 5 - " " /
/ ~ o O ~ 1 7 6 1 7 6
/ 4" o 1 ~ " ~
9 , j o . o ~
2 ..,, 1~ . . . . . . .
I I I 1
0 1,000 2, 000 3, 000 4, 000 5, 000 6, 000
Eqilibrium Sul f at e Concent rat i on, jJmol/I
F i g . 3. L a n g m u i r p l o t s f o r s u l f a t e s o r p t i o n o n ( A ) h e m a t i t e a n d ( B ) g o e t h i t e a t t h r e e p H l e v e l s . N H
= N a t u r a l h e m a t i t e .
28 L AURI E J , T U R N E R AND J AME S R. KR AME R
u n d e r s t udy. Th e p r e p a r e d goe t hi t e r e a c h e d an a p p a r e n t s o r p t i o n p l a t e a u at al l
p H l evel s. The n a t u r a l h e ma t i t e s a mp l e al s o r e a c h e d a s o r p t i o n ma x i mu m. The
s ynt he t i c h e ma t i t e , howe ve r , a p p r o a c h e d a s o r p t i o n ma x i mu m o n l y at p H 7. Th e
l owe r p H e x p e r i me n t s t e nd t o e xhi bi t a c o n t i n u i n g i nc r e a s e i n s ul f at e wi t h s ul f at e
i on c o n c e n t r a t i o n .
S o r p t i o n d a t a f or 24 hr e x p e r i me n t s wer e c o mp a r e d t o b o t h t he F r e u n d l i c h a n d
La n g mu i r t ype e q u a t i o n s ( Fi g u r e s 2 a nd 3). Fi t t e d p a r a me t e r s a n d t he g o o d n e s s -
of - f i t f or speci f i c p Hs a r e s u mma r i z e d i n Ta bl e I.
Coef f i ci ent s o f v a r i a t i o n i ndi c a t e t ha t f or p H 3 a n d 5 t he La n g mu i r f o r m of
e q u a t i o n is a be t t e r fi t t o t he e x p e r i me n t a l d a t a t h a n t he F r e u n d l i c h e q u a t i o n .
At p H 7, howe ve r , coef f i ci ent s of v a r i a t i o n f a vor t he F r e u n d l i c h e q u a t i o n even
t h o u g h t he c o r r e l a t i o n coef f i ci ent s a r e p o o r e r t h a n f or t he La n g mu i r fi t s. Ove r a l l ,
a d s o r p t i o n i s o t h e r ms f or t he oxi de s e x a mi n e d f ol l ow t he La n g mu i r e q u a t i o n
TABLE I
(a) Langmuir equation parameters for Oxide Samples, X / M - ( b C ) / ( K + C ) . The inverse linear form
was used for fitting, and the coefficient of variation (C.V.) is determined by ( X/ ( E( I ' - I ~ m) 2 / n ) ) / I ~ m where
12, Fro, and n are predicted uptake, mean difference between predicted uptake and experimental uptake
and number of samples, respectively. Sorption units are in txmol L -1 sulfate ion and ismol g-1 of solid
Oxide Correlation Coefficient Sorption Equilibrium
sample pH coefficient of variation maximum constant
Goethite 3 0.9999 0.5010 152.3 32.9
5 0.9992 0.5729 74.6 186.5
7 0.9980 0.5642 23.7 130.5
Hematite 3 0.9828 0.3625 278.4 408.3
5 0.9750 0.5430 82.4 603.6
7 0.9977 0.5799 20.2 127.6
Natural 3 0.9990 0.2931 45.9 173.1
hematite
(b) Freundlich equation parameters. Parameters are obtained from the linear logarithmic transformation
of the equation, X / M = k O/ P -. X / M is in ~mol g-~ and C in ~smol L -~
Oxide Correlation Coefficient
sample pH coefficient of variation p k
Goethite 3 0.9504 0.8357 0.1047 1.8
5 0.9567 0.5915 0.2160 1.1
7 0.9858 0.3465 0.4229 0.1
Hematite 3 0.9414 0.4435 0.1961 1.7
5 0.9433 0.5966 0.2237 0.8
7 0.9563 0.2294 0.4729 0.1
Natural 3 0.9794 0.9346 0.1222 1.2
hematite
IRREVERSIBILITY OF SULFATE SORPTION 29
reasonabl y well over all concent rat i on ranges studied,. The sorption maxi ma for
goethite listed in Table I agree fairly well with the observed maxi ma of 151.0,
72.9, and 20.8 p.mol g 1 for pH levels 3, 5 and 7, respectively. No maxi ma were
observed at pH 3 or 5 for the synthetic hemat i t e for the range of concent rat i ons
under st udy, however, a maxi mum of 17.6 tsmol g< observed at pH 7 is within
range of the calculated Langmui r maxi mum. For the nat ural hemat i t e sample, the
calculated adsorpt i on maxi mum is in fair agreement with the observed maxi mum
of 45 gmol g 1.
Other studies also indicate a Langmui r form of equat i on can be fitted to sulfate
adsorpt i on dat a, because a pl at eau or maxi mum is achieved. Hi ngst on et al. (1972)
report ed a sorpt i on maxi mum of 150 p.mol g-~ at pH 3 for a prepared goethite
sample. Parfitt and Smart (1977) det ermi ned the sorpt i on maxi mum for a prepared
goethite to be 75 p.mol g-1 and 125 ~xmol g-I for pH 5.1 and 3.4, respectively.
A maxi mum of 67 ~xmol g< was report ed by Ayl more et al. (1967) and 85 p.mol
g t by Pa r f t t and Smart (1978) for a prepared hemat i t e at pH 4.6 and 3.5, respectively.
Woot t on (1985) det ermi ned the apparent sorpt i on maxi mum for the same nat ural
hemat i t e sample used in this st udy to be 46 ~mol g ~ at pH 3.0.
The values for sorpt i on maxi mum report ed in the literature and here are normal i zed
to BET-N2 speci fc surface areas in Table II. Differences in maxi mum surface
sat urat i on are directly at t ri but abl e to variations in measured or calculated specific
surface area. Goet hi t e samples in this st udy exhibit hal f and hemat i t e samples about
twice the specific surface area of samples report ed in the literature. Ayl more et
a/. (1967), Hi ngst on el al. (1972) and Woot on (1985) used a BET-N2 met hod for
measuri ng specific surface area. Parfitt and Smart (1977, 1978) calculated the surface
area for their goethite and hemat i t e particles from phosphat e adsorpt i on data.
TABLE II
Exper i ment al a nd r epor t ed s or pt i on ma x i mu m f or oxi de s ampl es nor mal i zed to specific sur f ace ar eas
Ma x i mu m Ar e a Ma x i mu m
Sampl e p H fsmol g-~ m 2 g ~ p~mol m 2 Ref er ence
Goet hi t e 3 151.0 44.1 3.42 t hi s s t udy
3 150 81 1.85 Hi ngs t on e t a l . , 1972
3.4 125 90 1.39 Parfi t t a nd Smar t , 1977
5 72.9 44.1 1.65 t hi s s t udy
5 60 81 0. 74 Hi n g s t o n e t a l . , 1972
5.1 75 90 0.83 Par f i t t a nd Smar t , 1977
7 20.8 44.1 0. 47 t hi s s t udy
He ma t i t e
3.5 85 22 3.86 Par f i t t and Smar t , 1978
4. 6 67 26.7 2.50 Ayl mor e e t a l . , 1967
7 17.6 43.2 0.41 t hi s s t udy
Na t ur a l 3 45.0 12.0 3.72 t hi s s t udy
hemat i t e 3 46. 0 12.0 3.80 Woot on, 1985
30 LAURIE J . TURNER AND JAMES R. KRAMER
SULFATE DESORPTION
Sulfate sor pt i on is st r ongl y p H dependent and l argel y i rreversi bl e (Fi gure 4). The
sor pt i on p H also appear s t o cont r ol the desor pt i on. Sulfate sor bed at l ow p H was
general l y mor e desor babl e t han t hat at hi gher p H (0%) due t o bei ng less st rongl y
bound. I n fact, onl y t hose sor pt i on exper i ment s at p H 3 showed any measur abl e
desor pt i on. Onl y 41, 29, and 6.5% of sor bed sulfate is desor babl e at p H 3 f r om
goet hi t e, hemat i t e, and nat ur al hemat i t e, respectively.
(D
.Q 50
L _
o A
if}
40
a
10
0
2
3o
C O
o 20
d~
c -
O
13_
-o 70
c, 60
I1,=,
O
50
a .
40
3 0
= , "
O)
20
o 1 0 -
E
=1-" 0
2
G o e t h i t e
.!1
o~176176
~176 ~176176176176
o.~
~
, ~ 1 7 6 1 7 6 1 7 6 o~176176
~ . ~ 1 7 6 1 7 6 1 7 6
O ~176176176176176176176176176176176176176176176 . . . . . . ~176176176176176176176176176176176176
3 4 5 6 7
pH of Desorption
8
B
. . . l
~176
~ 1 7 6
o . " ~ , . ~
. . . : / " "
. . ' S " "
.o ~
o . ' . . o
....2 2 2 " "
.,..2 2 2 " " "
~ : : . . ' "
t - . . . . . . . + . . . . . : ' " ' ; . . . . . : ' " ' T ' " : " ' ' ~
3 4 5 6 7
pH of Desorption
H e . ~ t i t e N a t u r a l H e m a t i t e
. . . . . . . 0 . .
8
Fig. 4. pH dependence of sulfate desorption from goethite, hematite, and natural hematite. The sulfate
was sorbed at pH 3 in order to saturate the surface before desorption. (A) pH vs pecentage of sulfate
desorbed. (B) pH vs p, mol g i of sulfate desorbed.
I RREVERSI BI L1 TY OF S U L F A T E S ORP T I ON 31
Increasi ng amount s of sulfate were released as desor pt i on pH increased. Fi gure
4a shows t hat goet hi t e desorbs the largest percent age of sor bed sulfate, and nat ur al
hemat i t e the smallest. Fi gure 4b indicates t hat goet hi t e and hemat i t e act ual l y
desor bed about t he same absol ut e amount of sulfate (60 txmol g-X), whereas t he
nat ur al hemat i t e sample released much less (4 gmol g-l).
4. Implications For Modeling
In model i ng wat ershed r ecover y processes, the DDRP describes the dynami c response
of surface wat er chemi st ry as a f unct i on of rates of acidic deposi t i on and several
key soil processes. In part i cul ar, soil sulfate adsor pt i on is used as the cont rol l i ng
fact or of l ong t er m sulfate dynami cs (Cosby e t a l . , 1986; Hor nber ger e t a l . , 1986).
I nher ent in t he model is t he assumpt i on of reversibility of sulfate adsorpt i on;
equi l i bri um adsor pt i on and desorpt i on. The present work has shown sulfate
adsor pt i on on i ron oxides t o be f or the most par t irreversible, with desorpt i on
onl y occurri ng under specific condi t i ons. It is i mpor t ant to realize t hat i ron oxides
are not soils, but i mpor t ant soil minerals. In addi t i on to i ron oxides, ot her minerals
(such as al umi num oxides) pl ay an integral par t as substrates f or the adsor pt i on
of sulfate. I f al umi num oxides behave in the same manner as i ron oxides, we
hypot hesi ze t hat soil may behave as follows:
A soil with a measurabl e amount of sulfate sor pt i on capaci t y will follow the
DDRP model when amount s of acidic deposi t i on are increased. That is, i ncomi ng
sulfate will adsor b ont o soil oxides del ayi ng the equi l i brat i on of surface wat er
chemi st ry until the sor pt i on capaci t y is reached, aft er which hydr ol ogi c ret ent i on
will det er mi ne the remai ni ng t i me t o equilibrium. However , because of the irre-
versibility of sulfate sorpt i on, the system will not react as predi ct ed when acidic
deposi t i on is decreased.
A neut ral or alkaline soil is not likely to adsor b a large amount of sulfate. An
acidic soil, on t he ot her hand, will adsor b a l arger amount if sulfate and has the
best chance of desorbi ng some of t hat sulfate. Present dat a indicate t hat t he amount
desor bed will be small if the pH remai ns low and will onl y increase if the pH
is raised. I f a small amount of sulfate is desorbed, t here will be a time lag great er
t han t hat of hydr ol ogi c response time before equi l i bri um is again reached. However ,
if no sulfate is desor bed, as in the case of neut ral and alkaline soils, equi l i bri um
will be established accordi ng to hydr ol ogi c response time alone.
5. Summary
The sor pt i on and desor pt i on of sulfate ions on hemat i t e and goet hi t e have been
exami ned at equi l i bri um concent r at i ons up t o 5 mM SO4 =. Bot h sor pt i on and
desor pt i on are highly pH dependent . Sor pt i on increases with decreasing pH, as
seen in previ ous studies with i ron oxyhydr oxi des and soils, with the maxi mum
amount adsor bed (sat urat i on) occurri ng near a pH of 3. Previ ous studies with soils
i ndi cat e Langmui r behavi or (with its sor pt i on maxi mum) in some cases, and
32 LAURIE J. TURNER AND JAMES R. KRAMER
Freundl i ch behavi or (wi th no s orpt i on maxi mum present) i n others. Present sorpt i on
i sot herms are i n better agreement wi t h Langmui r behavi or. In this study, a s orpt i on
maxi mum or pl at eau is reached at all pH l evel s exami ned except f or syntheti c hemati te
whi ch reached maxi mum at pH 7 onl y. The s orpt i on maxi mums measured here
f or goet hi t e agree parti cul arl y wel l wi t h maxi ma f rom ot her studi es o f this mineral.
Soi l studi es i ndi cat e sorbed sulfate t o be parti al l y des orbabl e, wi t h amount s
desorbed dependent upon soi l properti es such a mi neral cont ent . In the present
study, Ayl mor e et a l . (1967) initial i ndi cat i on o f irreversibility o f sulfate sorpt i on
on iron oxyhydroxi de minerals is conf i rmed. Under present condi t i ons , onl y sulfate
sorbed at pH 3 is l abi l e, wi t h amount s desorbed i ncreasi ng wi t h the pH o f the
des orpt i on sol ut i on. A maxi mum o f 41, 29, and 6.5% o f t ot al sorbed sulfate can
be des orbed f rom goet hi t e, hemat i t e and natural hemat i t e, respecti vel y. Thi s lack
o f reversi bi l i ty has i mport ant i mpl i cat i ons f or model s whi ch si mul at e wat ershed
response t o changi ng i nputs o f aci di c sulfate deposi t i on. Sorpt i on ont o soi l mi neral s
is assumed t o be reversi bl e, and wat ershed recovery model s were f ormul at ed around
this assumption. In fact, sorpt i on ont o iron oxide minerals is not reversible, and
present model s must be modi f i ed t o reflect this irreversibility. Al l substrates ( i ncl udi ng
whol e soi l sampl es) need t o be i nvesti gated bef ore as s umpt i ons about soi l behavi or
can be assessed quanti tati vel y.
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