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IN SITU I N F R A R E D SPECIATION OF A D S O R B E D C A R B O N A T E
O N A L U M I N U M A N D IRON OXIDES
CHUNMING SU~ AND DONALD L. SUAREZ
USDA-ARS, U.S. Salinity Laboratory, 450 West Big Springs Road, Riverside, California 92507-4617
Abstract--Surface adsorption mechanisms of dissolved inorganic carbon species on soil minerals are not
well understood. Traditional infrared (IR) study of adsorbed species of inorganic carbon using air-dried
samples may not reveal true species in the solid/water interface in suspension. The ptu'pose of this study
was to obtain information on interracial carbonate speciation between solid and aqueous phases. The
interaction of bicarbonate and carbonate ions with X-ray amorphous (am) A1 and Fe oxides, gibbsite (~/AI(OH)3 ) and goethite (a-FeOOH) was examined by electrophoresis and in situ attenuated total reflectance
Fourier transform infrared (ATR-FTIR) spectroscopy. The presence of carbonate lowered the electrophoretic mobility and decreased the point of zero charge (PZC) of all minerals, implying specific adsorption.
Inner-sphere complexation of bicarbonate and carbonate was supported by a lowering in the anion symmetry due to the interaction with A1 and Fe oxide surfaces. Only complexed monodentate carbonate was
identified in am-Al(OH)3/aqueous solution at pH 4.1-7.8 when the solid was reacted with either N a n C O 3
or N a 2 C O 3 solutions. Am-AI(OH)3 was transformed to a crystalline sodium aluminum hydroxy carbonate,
dawsonite [NaAl(CO3)(OH)2], and bayerite (ct-AI(OH)3) after reacting with 1.0 M Na2CO3 for 24 h.
Gibbsite adsorbed much less carbonate than am-AI(OH)3 such that adsorbed carbonate on gibbsite gave
weak IR absorption. It is probable that monodentate carbonate is also the complexed species on gibbsite.
Evidence suggesting the presence of both surface complexed bicarbonate and carbonate species in the
interfacial region of am-Fe(OH)3 in suspension and the dependence of their relative distribution on solution pH is shown. Only monodentate carbonate was found in the interracial region of goethite in 1.0
M NaHCO3. A ligand exchange reaction was proposed to describe the interaction of bicarbonate and
carbonate with the surface functional groups of A1 and Fe oxides.
Key Words----Attenuated Total Reflectance-Fourier Transform Infrared, Carbonate Adsorption, Electrophoretic Mobility, Infrared, Point of Zero Charge, Point of Zero Net Proton Charge, X-ray Diffraction.
INTRODUCTION
Dissolved inorganic carbon species such a s H 2 C O 3 ~
H C O 3- and CO32- are ubiquitous in natural waters and
soil environments. Yet their interaction with soil minerals such as A1 and F e oxides are not well understood.
Information is lacking on in s i t u speciation o f inorganic carbon species at the molecular level on soil
mineral surfaces in aqueous suspension. An understanding o f carbonate species adsorption mechanisms
has practical applications in soil science, g e o c h e m i s t r y
and for the global carbon cycle.
Schulthess and M c C a r t h y (1990) studied competitive adsorption o f anions on an A1 oxide (~-A1203) and
obtained an affinity sequence of the anions for the oxide: O H - > CO32- > acetate > C1-. T h e y stated that
these ions adsorb competitively on the same A1 sites,
but not necessarily by the same mechanisms. C o m petitive adsorption also has been o b s e r v e d between
CrO42- and dissolved CO2(g ) on amorphous Fe hydroxide (Zachara et al. 1987) and on goethite (Van
G e e n et al. 1994). In addition to surface adsorption,
carbonate can also f o r m discrete solid phases with A1
such as dawsonite [NaAI(CO3)(OH)2]. The m a x i m u m
I" Present address: U.S. Environmental Protection Agency,
National Risk Management Research Laboratory, 919 Kerr
Research Drive, Ada, Oklahoma 74820.
Copyright 9 1997, The Clay Minerals Society
814
815
ing results in a more concentrated solution (higher ionic strength), and increasing alkalinity (with drying)
shifts the pH to greater values. Both increased ionic
strength and increased pH (constant HzCO3 concentration and increased alkalinity) result in an increase in
the CO32- concentration relative to the HCO 3- concentration in solution. Because of these limitations it is
preferred to utilize in situ examination in aqueous suspension for bicarbonate and carbonate adsorption with
techniques such as ATR-FTIR spectroscopy.
The objectives of this study were to determine the
bonding mechanisms of bicarbonate and carbonate
with A1 and Fe oxides and to elucidate the structure
of surface-adsorbed species. We also seek to determine
the relationship between the solution and interfacial
species distribution.
MATERIALS AND METHODS
Synthetic X-ray amorphous A1 hydroxide [amAI(OH)3 ] and Fe hydroxide [am-Fe(OH)3] (hereafter
called oxides) were prepared by the method of Su and
Suarez (1995). A well-crystallized gibbsite (C-730)
described by Kittrick (1966) was utilized. Synthetic
goethite (et-FeOOH) was prepared with an OH/Fe molar ratio of 9.0 by the method of Schwertmann and
Cornell (1991) using 1 M Fe(NO3) 3 and 5 M KOH.
The suspension was incubated at 70 ~ for 60 h and
centrifuged. The solids were resuspended in deionized
water and the suspension pH was adjusted to 6.5 with
HC1 before centrifugation. The solids were washed repeatedly with deionized water until the supernatant
electrical conductivity was <0.003 dS m -1. The crystals were dried at 70 ~ and gently ground.
The EM was determined for all minerals by microelectrophoresis using a Zeta-Meter 3.0 system (Zeta
Meter, Long Island City, New York; mention of trade
names is for the benefit of the reader only and does
not indicate endorsement by the USEPA and USDA).
Suspensions containing 0.2 g L -1 solid in 0.01 M NaC1
were acidified to pH 3 with HC1 and titrated with 0.01
M NaOH (CO2-free) or 0.0033 M Na2CO 3 to various
pHs for EM determination. The PZC was obtained by
direct observation or interpolating the data to zero mobility.
For the ATR-F-TIR spectroscopic study, mineral suspensions (usually 100 g L -1 unless indicated otherwise) were prepared by adding the equivalent of 2 g
of solids to 20 mL of CO2-free water, 0.01, 0.1 and
1.0 M analytical grade Na/-ICO3 or 0.01, 011 and 1.0
M Na2CO 3 (Mallinckrodt, Paris, Kentucky) dissolved
in CO2-free water. The experiment was performed in
the laboratory atmosphere. The CO2-free water was
prepared by boiling deionized water. The suspensions
were shaken end-to-end for 24 h and centrifuged. Fifteen milliliters of the supernatant was removed and 3.5
mL of it was used as a "reference" for FTIR analysis.
The solid was resuspended in the remaining 5 mL of
816
Su and Suarez
....)
Figure 1. Electrophoretic mobility of A1 and Fe oxides in 0.01 M NaC1 titrated with 0.01 M NaOH and 0.003 M N a 2 C O 3.
Initial solid concentration was 0.2 g L 1. The PZC~ stands for PZC of adsorbents titrated with 0.0033 M Na2CO3.
817
~I ._o.oo~_~o~_.~~_ I
-~,,
?,,,,I
-3
10
11
10
11
3
!
-1
~,I
-3
,,-1
I..11
m
0
4
3
~J
Am_Fe(0H)
1==4
0
O
D.,
0
-1
-2
PZC
C
-3
3
E..,
rJ
8.5
PZC c =
7.2
10
11
b.q
~ - ~
-2
PZCc
-1
--3
.,,~,~
=
~,~-~
8.0
10
pH
11
818
Su and Suarez
1360 1)2
NaI-ICO3
1)2
310
8t:
an
I_.
O
m
.o
1)4
1)4 1605
1.0 M , p H 7.9 1)1
1668 f i
1010
1)6
843
1360
M, pH 8.
0.01 M, pH 8.2
I
1200
1600
800
819
1)3
1383
Na2CO3
1.0
r
C
!--
.g2
<
1.0 M, pH 11.2
~)2
1680 1559
887
1395
0.1 M, pH 11.0
0.01 M, pH 10.8
I
1200
1600
800
820
Su and Suarez
Am_Al(OH)1484
3 / r ~ 1420
0.4
tO
,.Q 0.3
i._
- NaHCO3
/1028
992
11.0M,pH7.8
1495 1420
f"-"No.1 M ,
p H 4.!
O
.Q
<t
0.2 -
0.01 M, pH
o,
0.0
1600
,
1200
800
3.0 and 3.3 (Hsu and Bates 1964; Hsu 1967). Apparently, CO32 and OH compete for A1 in am-AI(OH)3
to form these 2 solid phases, as they do for A1 in
aqueous solutions of A1C13. Scholtz et al. (1984)found
dawsonite in addition to amorphous carbonate-containing A1 hydroxide when an A1C13 solution was titrated to pH 7.5-9.5 by separate solutions of NaHCO3
and Na2CO 3.
In comparison with am-Al(OH) 3, gibbsite was less
reactive with N a n C O 3 and N a z C O 3 a s shown by their
lower amounts of adsorption. The amount of adsorbed
C on gibbsite was 0.001, 0.030, 0.10 and 0.27 mol
kg -1 in water (equilibrium pH 4.7), 0.01 (pH 8.0), 0.1
(pH 8.6) and 1.0 M NaHCO 3 (pH 8.3), respectively.
No detectable IR absorption bands were found for either carbonate or bicarbonate species in the interracial
region for aqueous concentrations of less than 0.1 M.
The v3 vibration for CO32- did not split in gibbsite
reacted with 1.0 M N a n C O 3 and Na2CO 3 (spectra not
shown).
Characterization of Carbonate/Fe Oxide Surface
Complexes
The v4 vibration doublet at approximately 1670 and
1590 cm -1 for the protonated complex, ---Fe-O-COOH,
were observed in am-Fe(OH)3/aqueous solution of wa-
821
0.5
Am-AI(OH) 3
0.4
Na2CO3
972
ID
r
C
J~
0.3-
1490 1420
i_
U~
x~
< 0.20.1-
0.0
1600
1200
800
W a v e n u m b e r s (cm "1)
Figure 5. ATR-FTIR difference spectra of am-Al(OH)3 as a function of Na2CO 3 concentration. Solid concentration in the
ATR reservoir was 400 g L -1. The amount of adsorbed C on am-Al(OH)3 was 0.058 and 0.52 tool kg 1 in 0.01 and 0.1 M
Na2CO 3, respectively.
tration into the F e oxides. T h e I R b a n d intensity increases due to the resulting d e e p e r penetration. Second, am-Fe(OH)3 had the h i g h e s t surface area o f the
a d s o r b e n t s studied [250 m 2 g 1 as c o m p a r e d to 128,
7.8 and 21.8 m 2 g 1 for am-Al(OH)3, gibbsite and goe-
Table 1. Infrared absorption bands of bicarbonate and carbonate ions in aqueous solution (free state), on mineral surfaces
(adsorbed form) and in dawsonite (structural form).
Frequency, cmAnion
Free bicarbonate
Free carbonate
Monodentate carbonatet
[Co(NH3)5CO3]C1
Bidentate carbonatet
[Co(NH3)4CO3]C1
Symmetry
C~
D3h
vt
v~
v~
va
1010
1065
1360
887
1310
1062
877
1448
1354
1043
865
1590
1282
1495
1484
1490
1560
1420
1477
1487
1474
1485
1410
1420
1420
1420
1388
1028
1095
1050
1070
1020
1070
1020
950
944
1668
1605
1667
1585
1674
1586
1383
1359
1335
1358
1336
1335
822
2500
a
fl
Dawsonite
v i b r a t i o n o f the u n c o m p l e x e d b i c a r b o n a t e a n i o n i n
aqueous s o l u t i o n (Table 1), s u g g e s t i n g a d e c r e a s e i n
the s y m m e t r y of the surface c o m p l e x e d b i c a r b o n a t e .
In addition, the vl v i b r a t i o n shifted f r o m 1010 in solution to 1050 c m -] in am-Fe(OH)3 r e a c t e d w i t h 0.01
M N a H C O 3. T h e v 3 splitting for s u r f a c e - c o m p l e x e d
c a r b o n a t e w a s o b s e r v e d in all a m - F e ( O H ) 3 / a q u e o u s
solution s y s t e m s a n d the f r e q u e n c y d i f f e r e n c e b e t w e e n
the d o u b l e t s i n c r e a s e d w i t h i n c r e a s i n g initial c o n c e n tration o f b o t h N a H C O 3 a n d Na2CO3, i n d i c a t i n g inc r e a s e d distortion o f CO32 o n the surface. T h e m a g n i t u d e o f t h e splitting suggests m o n o d e n t a t e c a r b o n a t e
c o m p l e x e d to the am-Fe(OH)3 surface. T h e vl vibration for c a r b o n a t e o n l y slightly shifted u p w a r d f r o m
1065 for the free species to 1070 c m -~ for the surfacec o m p l e x e d species. T h e b a n d n e a r 9 5 0 c m -~ m a y b e
a c o m b i n a t i o n o f v 6 v i b r a t i o n for HCO3-, a n d v 2 vib r a t i o n for CO32- o n the surface (Figure 9). Failure to
o b s e r v e b i c a r b o n a t e i n a n I R study o f c a r b o n a t e interaction w i t h a freshly p r e p a r e d F e o x i d e b y H a r r i s o n
a n d B e r k h e i s e r (1982) is p r o b a b l y d u e to the air-drying a n d e v a c u a t i o n of their s a m p l e s , w h i c h i n c r e a s e s
the pH, r e s u l t i n g i n m o r e c a r b o n a t e relative to bicarb o n a t e in the system. A p p a r e n t l y , the in situ A T R F T I R m e t h o d o v e r c o m e s this p r o b l e m a n d is able to
detect b i c a r b o n a t e surface c o m p l e x a t i o n .
Formation
2000
b: 1 . 0 g a m - A l ( 0 H ) s +
2 0 m L IM NaeC0 s
1w
e,. 9
Su and Suarez
c;,~.
1505
555
I
10
20
30
40
50
Degrees
50
(20)
thite, respectively], r e s u l t i n g in h i g h e r I R a b s o r p t i o n
for c a r b o n a t e species. It is a p p a r e n t that o n l y qualitative i n f o r m a t i o n o n c a r b o n a t e s p e c i a t i o n in the interfacial r e g i o n c a n b e o b t a i n e d f r o m this study.
T h e r e is a slightly larger splitting o f the v4 v i b r a t i o n
o f the interfacial b i c a r b o n a t e t h a n the splitting o f v 4
O.q
0.06
Am-AI(OH) 3
1.0M, Na2CO 3 pH 11.2
1560
955
1387
I
(9
(J
C
(0
J~
1096
im
0
U)
.Q
100gL -1
<
560
I
1600
1389
~.~50
~ /
! v1020
g L"1
800
1200
Wavenumbers
(cm "1)
Figure 7. ATR-FTIR difference spectra of mineral solids after 1.0 (top spectrum) and 0.5 g (bottom spectrum) of amAI(OH) 3 reacted with 20 mL of 1.0 M Na2CO 3 for 24 h. Solid concentration in the ATR reservoir was 100 g L -I for the top
spectrum and 50 g L -1 for the bottom spectrum. The amount of sorbed C on am-AI(OH) 3 was 8.7 and 7.4 mol kg -1 for the
top and bottom spectra, respectively.
Am'Fe(OH) 3
NaHCO3
1487
/'X
0.4
/
823
1335
~381~1.0M,
p H 8.0
0.3-
s
0
<1: 0.2-
0,1 m
1600
1200
800
W a v e n u m b e r s (cm "1)
Figure 8. ATR-FrIR difference spectra of am-Fe(OH)3 as a function of NaHCO3 concentration. Solid concentration in the
ATR reservoir was 400 g L -1. The amount of adsorbed C on am-Fe(OH)3 was 0.053, 0.074, 0.38, and 1,1 mol kg -1 in
deionized water, 0.01, 0.I and 1.0 M NaHCO3, respectively,
[1]
[2]
[3]
and on am-Fe(OH)3:
~Fe-OH2 + HCO3- = =-Fe-O-COOH + H20
at pH 3.5-6.2
[4]
[5]
824
Su and Suarez
1336
Am-Fe(OH) 3
Na2CO3
~.OM, pH 10.5
0.4O
e~
1474~1348
'
e~
t...
O
0~
e~
<
1586
/'~
1358
~ . ~
1600
1020
971
800
1200
= ~Fe-O-CO2- + H +
[6]
T h e a p p a r e n t p K (the p H at w h i c h the c o n c e n t r a t i o n
o f the 2 surface species in e q u i l i b r i u m is equal) for
this r e a c t i o n is p o s s i b l y b e t w e e n 4 a n d 6.
In s u m m a r y , similar to p h o s p h a t e a n d borate, carb o n a t e l o w e r e d the electrophoretic m o b i l i t y a n d dec r e a s e d the P Z C o f A1 a n d Fe oxides. T h e surfacec o m p l e x e d m o n o d e n t a t e c a r b o n a t e was the o n l y identified interracial species i n a m - A l ( O H ) J a q u e o u s solution at p H 4 . 1 - 7 . 8 . A discrete c r y s t a l l i n e solid phase,
d a w s o n i t e , f o r m e d w i t h traces o f b a y e r i t e w h e n amA I ( O H ) 3 w a s reacted w i t h 1.0 M Na2CO 3. G i b b s i t e ads o r b e d m u c h less c a r b o n a t e t h a n am-AI(OH)3 d u e to
l i m i t e d f u n c t i o n a l g r o u p s o n the surface. P r o b a b l y carb o n a t e is also the c o m p l e x e d species o n gibbsite. B o t h
surface c o m p l e x e d b i c a r b o n a t e a n d c a r b o n a t e species
w e r e f o u n d in the interracial r e g i o n o f the a m Fe(OH)3-water system, d e p e n d i n g o n solution pH.
M o n o d e n t a t e c a r b o n a t e w a s identified o n g o e t h i t e in
1.0 M N a n C O 3 s u s p e n s i o n s .
A T R - F T I R s p e c t r o s c o p y h a s b e e n s h o w n as a useful
t e c h n i q u e to yield qualitative if n o t s e m i q u a n t i t a t i v e
i n f o r m a t i o n o n the c h e m i c a l structure o f specifically
a d s o r b e d anions, p r o v i d i n g i n c r e a s e d u n d e r s t a n d i n g o f
825