Clay Minerals (1993) 28, 13-24

This paper is dedicated to Professor Lisa Heller-Kallai on the occasion of her 65th birthday.

P R E P A R A T I O N A N D P R O P E R T I E S OF A B A S I C L E A D
CARBONATE-- MONTMORILLONITE COMPLEX

S. T S U T S U M I , A. YAMAZAKI*,M. UEHARAAND R. O T S U K A *

Institute of Earth Science, School of Education, Waseda University, 1-6-1 Nishiwaseda, Shinjuku-ku,
Tokyo 169-50, and *Department of Mineral Resources Engineering, School of Science and Engineering,
Waseda University, 3-4-10hkubo, Shinjuku-ku, Tokyo 169, Japan

(Received 30 September 1991; revised 27 January 1992)

A B S T R A C T: A basiclead carbonate-montmorillonitecomplexwas prepared by treating a natural

montmorillonitehydrothermally for 120 h at 250~ with lead powder, dry ice and lead nitrate
solution.The productis a non-swellingmaterialshowingwell-outlined,hexagonal,thin plates <1/~m
in size; the symmetryis pseudo-orthorhombic,a = 5.141(7) A, b = 9.005(5) A, c = 17-420(4)A, and
Z = 2. The X-raypowder pattern is characterized by a 17.4 A reflectionand an integralseries to the
14th order. The TG-DTA curves of this 17 A-mineral showed one endotherm around 400~
accompanied by weight loss and two exthotherms at about 680 and 780~ By applying high-
temperature X-ray diffractometry (XRD) and infrared (IR) spectroscopy, it was found that the
endotherm is due to decomposition of carbonate hydroxide in the interlayer, while the two
exthotherms are caused by crystallizationof a hexagonalphase of PbA12Si208and by the conversion
of this phase into lead feldspar, respectively. The crystal structure of the 17 A-mineral was
determinedand refinedas a 2:1 dioctahedralsmectiteinterlayeredwith a hydrocerussite-likelayerby
a one-dimensionalFourier synthesismethod.

Hayase et al. (1978) studied a Pb-rich, clay-like material occurring in the oxidation zone of
P b - Z n - C u deposits of the Cruz del Sur Mine, Argentina, and described this material as a
new mineral species, surite. The mineral has the structure of a 2: l layer-silicate similar to
dioctahedral smectite intercalated with a cerussite-like layer. Little is known about the
genesis and crystal structure of this mineral, but synthesis of surite has been attempted in
various ways for many years. In the course of the synthetic study, a product having a basal
reflection of - 1 7 A (hereafter, abbreviated to 17 A-mineral) was obtained. The detailed
study indicated that this material was a clay-inorganic complex, the structure of which was
based on a basic lead carbonate intercalated with a 2:1 silicate layer of montmorillonite.
This paper describes (i) the preparation of the 17 A-mineral; (ii) its properties which
were characterized by X-ray powder diffractometry, transmission electron microscopy
(TEM), thermal analysis and I R absorption spectroscopy; and (iii) its crystal structure as
revealed by a one-dimensional Fourier synthesis method.

EXPERIMENTAL

Sample preparation

The starting material was natural montmorillonite, purified from Aterazawa bentonite,
Yamagata Pref., Japan ( K u n i m i n e Co., Ltd.). Impurities such as quartz and feldspar were

9 1993 The MineralogicalSociety

14 S. Tsutsumi et al.

removed by the hydraulic elutriation technique. Hydrothermal experiments were

performed using a Morey-type bomb, containing a Teflon bottle --60 ml in volume.
Initially, 360 mg of starting material and 1160 mg of lead powder (corresponding to
4.0 • 103 mEq/100 g of starting material) (Junsei Chemical Co., Ltd) were placed in the
Teflon bottle, and then 35 ml of 0.5 N Pb(NO3)2 solution adjusted at pH = 1 by dilute nitric
acid, were added. After the suspension had been stirred well, --800 mg of dry ice was put in
the bottle to provide CO2, and the bottle was sealed immediately. The mixture was
hydrothermally treated for 120 h at 250~ in an electric furnace. The product was then
centrifugally separated from the solution and washed five times with distilled water. Finally,
impure products such as cerussite and hydrocerussite were removed by the hydraulic
elutriation technique.

Analytical methods
X-ray powder diffraction was carried out with a Rigaku Geigerflex R A D - R C using
graphite monochromatized Cu-K0lradiation (55 kV, 200 mA). Each reflection of the 17 ~ -
mineral was indexed and the unit-cell parameters were calculated using the program by
Appleman & Evans (1973) modified and improved for a NEC PC9801 personal computer
by the authors. High-temperature X-ray powder diffraction was carried out using a Rigaku
Giegerflex RAD-IC with a high temperature attachment, using Ni-filtered Cu-Ko:radiation
(40 kV, 20mA).
In order to investigate the fundamental layer structure of the 17/~-mineral, interlayer
materials were removed by the following acid treatment: the 17 A-mineral was treated with
0.75% HC1 at room temperature for five days and then washed with distilled water; the
residue was then dispersed in 1 N NaC1 solution and stirred with a magnetic stirrer for 24 h
after which the product was centrifugally separated from the solution, washed five times
with distilled water, and the exchangeable cations in the interlayer were completely
exchanged by Na ions.
Transmission electron micrographs were taken with a Philips CM30 at an accelerating
voltage of 300 kV.
Chemical analysis was carried out by using an energy-dispersive analysis system (Tracor
Northern TN5400 EDS) installed in an electron probe microanalyser (JEOL JXA733) using
an accelerating voltage of 15 kV and a beam current of 4.00 • 10 10 A. The CO2 content
was determined by using a H I T A C H I Type 163 gas chromatograph equipped with a high-
temperature dissolution attachment. The water content was obtained by subtracting the
CO2 content from the weight loss between room temperature and 1000~ determined by
thermogravimetry. The measured values of the elements, except CO2 and H20, were
corrected by the Z A F correction method.
The T G - D T A curves were recorded with a Rigaku Thermoflex 8076 at a heating rate of
10 K/min in static air, N2 and CO2 with a flow rate of 100 ml/min.
The I R spectra were recorded with a JASCO FT-IR-8000 spectrometer, using the KBr
disk method.

RESULTS AND DISCUSSION

X R D and E M Data
The XRD data for the 17 A-mineral formed during the hydrothermal treatment are given
in Table 1. Assuming that the symmetry of 17 ]k-mineral was pseudo-orthorhombic
 Basic lead carbonate--montmorillonite complex 15

TABLE 1. X-ray powder diffractiondata for the 17 A-mineral.

dobs/A dcalc/A hkl 1/lo*

17.40 17-42 00 1 100

8.722 8-710 002 5
5.836 5-807 003 8
4.416 4.428 10 2 5
4.363 4.355 004 6
3.489 3-484 005 13
3.131 3-130 024 8
2.899 2.903 006 38
2.591 2.592 13 0 8
2.490 2-489 007 13
2.242 2-240 10 7 5
2.175 2.178 008 5
1-934 1-936 009 2
1.865 1-864 14 4 5
1.743 1-742 0 0 10 4
1-693 1.694 240 5
1-583 1-584 0 0 11 4
1-500 1-501 060 3
1.449 1.452 0 0 12 4
1.339 1.340 0 0 13 2
1-245 1.244 0 0 14 3
1.243 1-242 264 3

* Relative intensitiesobtained by applyingthe slit correction.

(/3 = 90.0~ the unit-cell parameters obtained were a = 5.141(7) A, b = 9.005(5) A and
c = 17-420(4) A. In the diffraction pattern, the basal reflections corresponding to a spacing
of 17-4 A up to the fourteenth order were observed, and the d-spacing of the 060 reflection
was 1.500 A. This suggests that the structure of the 17 A-mineral can be regarded as based
on dioctahedral smectite. T r e a t m e n t with ethylene glycol did not cause discernible change
in the intensities and spacings of the overall peaks, and swelling character was not observed.
The X R D pattern of the residue obtained with the series of acid treatments described
showed a basal reflection corresponding to a spacing of 12.47 A , clearly expanding to
17-2 A after treatment with ethylene glycol (Fig. 1). These properties agree with those of a
Na form of montmorillonite. Hence, it is suggested that the structure of the 17 A-mineral
can be regarded as based on the 2:1 silicate layer of dioctahedral smectite.
Figure 2 shows well-outlined, hexagonal thin plates <1 /tm in size, which are very
different in morphology from c o m m o n montmorillonite, which consists of irregular-shaped
or curled thin plates. The well-defined shape of the 17 A-mineral is similar to that of a basic
lead carbonate (Cowley, 1956). Hence, the T E M observation suggests that the morphology
of the 17 A-mineral is strongly controlled by that of the interlayer material.

Chemical composition and structural formula

F r o m the chemical analysis listed in Table 2 of the 17 A-mineral and the residue after
treatment with HCI, the chemical composition of the 17 A-mineral can be regarded as a 2:1
dioctahedral smectite interlayered with basic lead carbonate.
16 S. Tsutsumi et al.

I dO01=17.40~ I~
, il
J! i, ~- Ca) I
I--~ w ~L..I o-I I

dOOl= 12.,47A (b)

rl2
<~

doot= 17.2A (C)

2 10 20 30 40 50 60 70
20 (Cu-Ka)/degree
FIG. 1. X-ray diffraction patterns of (a) 17 A-mineral; (b) residue obtained from the 17 A-mineral
powder pretreated with 0-75% HCI and Na-exchanged; (c) residue treated with ethylene glycol.

FIG. 2. Transmission electron micrograph of the 17 A-mineral.

 Basic lead carbonate--montmorillonite complex 17

TABLE2. Chemicalcompositionsand formulaeof the 17/i-mineral

(1), and residue obtained from the 17/i-mineral powder pre-
treated with 0-75% HCI and Na-exchanged (2).

(1) (2)

SiO2 20.62 56-18

A1203 8-67 20.49
Fe203 1-07 2.48
MgO 0.55 1-66
CaO trace trace
Na20 trace 2-72
K20 trace trace
PbO 58.21 trace
CO2 7.45 --
H2O+ 3.18 4.22
H20- 0.25 12.25
Total 100-00 100.00

Composition per formula unit containingO10(OH)2

Si 3-81 3.95
Altet 0"19 0"05
Aloct 1"70 1"65
Fe 0-15 0-13
Mg 0-15 0.17

Interlayer composition
Ca - -
Na - 0.37
K -- --

Pb 2-90 --
CO 3 1"88 --

OH 1.92 --
H20 0.15 2-87

A n interlayer negative charge was assumed to be close to - 0 . 3 7 , obtained for the

structural formula of the Na-exchanged residue after HC1 treatment corresponding to a Na
form of montmorillonite, as shown in (2) of Table 2. Based on this assumption, the
following structural formula was obtained for the 2:1 layer of the 1 7 / i - m i n e r a l :

(Si3.81Alo.19)(All.voFeo.15Mgo.15)Olo(OH)2

The interlayer negative charge from this formula is - 0 . 3 4 , very close to - 0 . 3 7 . The
a m o u n t of tetrahedral A1 in the residue was very small compared with that of the 17 A-
mineral, as shown in Table 2. This was presumably because some A1 ions had been
dissolved by acid treatment. Based upon the interlayer charge of 0.34, the amounts of Pb
and CO3 in the interlayer were calculated as 2.90 and 1.88, respectively. If the basic lead
carbonate in the interlayer has a composition similar to that of hydrocerussite
(Pb3(CO3)2(OH)2) and Pb 2+ compensates for the negative layer charge of - 0 - 3 4 , then the
chemical composition of the interlayer substance can be estimated as
Pb2.90(CO3)t.82(OH)l.s2, in good agreement with the results of the chemical analysis in
18 S. T s u t s u m i et al.

Table 2. Excess 0.15H20 may be ascribed to adsorption water. Hence, the structural
formula of the 17 A-mineral in a half unit-cell can be represented as follows:

Pb2-90(CO3) 1.82(OH) 1.82(Si3.81A10.19)(Ala.70Feo. 15Mgo.15)O10(OH)2

TG-DTA curves

Figure 3 shows the T G - D T A curves of the 17 A-mineral in various atmospheres (a-c),

the montmorillonite used as the starting material (f), basic lead carbonate (d), and the
mixture of montmorillonite and basic lead carbonate, prepared so as to have the same
composition as the 17 A-mineral (e). In static air, the D T A curve of the 17 A-mineral has
an endothermic peak at 400~ and two exothermic peaks, one at - 6 8 0 ~ and the other
around 780~ These peak temperatures were almost unchanged in N2 gas flow, while the

TG

~t I

(c)

~ (d)

(0
I I [ I 1 I I I I
1O0 300 500 700 900

oC
FIG.3. TG-DTA curves. (a)-(c): 17 A-mineral; (d): basic lead carbonate; (e): mixed powder of basic
lead carbonate and montmorillonite; (f): montmorillonite.
 Basic lead carbonate--montmorillonite complex 19

• ~ ~,r R T

~ ,~,,,,,,]! 275 ~

3oo ~

~I'~..~,,,~.,,,.~~.1
k~ 450 ~
0 ~
P p
p o
t ~ ,,.~,;~ p 675 C

k_~.~ ~, . ~ ~ ~,,,~~,. '

LL
~LL L r iL~l L o

I [ I I I I

2 10 20 30 40 50 60 70
20 (Cu-Ka)/degree
FIG. 4. X-ray diffraction patterns of the 17 A-mineral at various temperatures. P: PbA12Si208;
L: lead feldspar.

endotherm around 400~ became slightly sharper and 15~ higher, and the temperature of
the exotherm around 680~ lowered by 15~ in CO2 gas flow. As the endotherm around
400~ was accompanied by a loss in weight, this suggested that it was caused by
decomposition of carbonate hydroxide situated in the interlayer. This endotherm, however,
was nearly 50~ higher than the endotherm at 360~ due to decomposition of basic lead
carbonate, as shown by curve (d) in Fig. 3.
20 S. Tsutsumi et al.
18
00000000
17

16
?,
0000000000
15

14 I I I I I

0 200 400 600

oC
Fro. 5. Values of the 001 reflections for the 17 A-mineral as a function of temperature.

The T G - D T A curves of the mixture of montmorillonite and basic lead carbonate showed
several endotherms accompanied by weight loss (curve (e), Fig. 3), Of these, two
endotherms, near 100~ and around 680~ were due to dehydration of montmorillonite
(curve (f), Fig. 3). In addition, a two-step endotherm followed by a sharp endotherm
around 350~ were caused by decomposition of basic lead carbonate (curve (d), Fig. 3). The
T G - D T A curves of the 17 k-mineral were quite different from those of the mixture, despite
their similar chemical compositions. This indicates that the 17 ,~-mineral is not a simple
mechanical mixture of montmorillonite and basic lead carbonate, but has the above-
mentioned interlayered structure.

High-temperature X-ray powder diffractometry

Figures 4 and 5 show the high-temperature XRD patterns of the 17 A-mineral, and
d(001) as a function of temperature, respectively. Heating below 275~ did not cause
appreciable changes in the XRD patterns. The basal spacing began to contract due to the
release of both H 2 0 and CO2 from the interlayer at 300~ and d(001) decreased to - 1 5
at 325~ The 001 reflection of this heated product at 350~ did not expand with ethylene
glycol treatment. All of the reflections began to weaken at 450~ and disappeared at 600~
A hexagonal phase of PbAlzSi2Os (Sorrell, 1962; JCPDS 14-326; P in Fig. 4) crystallized at
675~ and the intensities reached the maximum at 700~ The reflections of lead feldspar
(PbA12Si208, L in Fig. 4) appeared at 725~ and those of the hexagonal phase disappeared
at 750~ These results indicate that the exotherms around 680 and 780~ were caused by
the crystallization of a hexagonal phase of PbA12SizOs, and by the conversion of this phase
into lead feldspar, respectively.

Infrared absorption spectra

Figure 6 shows the Fourier-transformed IR absorption spectra of the 17 A-mineral
heated at the temperatures indicated for 30 min. The absorption bands at 1385, 855 and
685 cm -1 were assigned to v3, v2 and v4 of CO3, and the bands at 1000, 525 and 470 cm ~ to
the 2:1 layer-silicates. Further, the 3620 cm 1 band was assigned to an O H group of the
layer-silicate, while the 3560 cm 1 band was assigned to that of the hydrocerussite-like
layer. The IR spectrum of the 17 k-mineral showed no discernible changes in intensities
and wave numbers between room temperature and 200~ The 3560 cm 1 band
 Basic lead carbonate--montmorillonite complex 21

became broad at 300~ and disappeared at 400~ whereas the band assigned to CO3 became
weak and broad at 400~ and disappeared completely at 600~ suggesting that the basic
lead carbonate layer of the 17 A-mineral dehydrated prior to the decomposition of
carbonate. This thermal behaviour agrees well with those obtained by several workers
(Kotama et al., 1969; White, 1974; Ball & Casson, 1977; Flemming et al., 1984) for basic
lead carbonate. The bands due to the 2:1 silicate layer became broad at 600~ at which
temperature the overall X-ray reflections disappeared (Fig. 4), showing distintegration of
the 2:1 layer.

400 ~

IIIllllll I I I I I t t i"'-. ~ I I L .

4000 3000 2000 1000 500

Wave Number/cm- 1
FIc. 6. Infrared absorption spectra for the 17 A-mineralat various temperatures.
22 S. Tsutsumi et al.

Structural formula and structure model

The properties of the 17 A-mineral suggest that the mineral can be regarded as composed
of a 2:1 layer of a dioctahedral smectite with a hydrocerussite-like interlayer. Based on this
assumption, the crystal structure of the 17 A-mineral was examined by the one-dimensional
Fourier synthesis method.
Assuming that the symmetry of basic lead carbonate is hexagonal, the cell parameters are
considered to be a = 9.06 A and c = 8.27 A (1/3 unit-cell of hydrocerussite, Cowley, 1956;
Katz & Reed, 1957). As d(001) of the 17 A-mineral is 17.4 A and the thickness of the 2:1
layer along the c-axis is approximately 9.5 A, it is considered that a reasonable model of the
crystal structure is a hydrocerussite-like layer intercalating with a 2:1 layer of montmorillo-
nite in the same c-axis direction.
On the basis of the above model, X-ray integrated intensities of the basal reflections from
the first to the twelfth order were calculated in different cases where z parameters of ion
planes and also ion contents in each plane were sightly different. Figure 7 shows the best fit
between the observed and calculated one-dimensional electron density distribution curves
which were obtained by a Fourier synthesis method, and the refined structural model of the
17 A-mineral is also shown with atomic parameters. Table 3 shows the comparison of
F(00i)obs with F(00l)cal c and gives R = 0.126, revealing that the structure model is
reasonable. The Pb planes occur at two levels: one is located in the middle of the basic lead
carbonate layer (z = 8-70), and the other is between the CO3 and O H planes (z = 5.94). The
distribution of Pb ions between the inner and outer Pb planes is obtained as
Pb*0.91Pbl.99(OH)l.82(CO3)l.82, where Pb* is defined as Pb ions on the inner plane (z =
8.70). The ideal structural formula of a basic lead carbonate is Pb*Pb2(OH)2(CO3)2.
Hence, the interlayer cationic charge of about + 0-34 for the 17 A-mineral is produced from
Pb ions on the outer plane (z = 5.94).
The z parameters shown in Fig. 7 indicate that the distance between the basal oxygen
plane of the 2:1 silicate layer and CO3 plane is - 2 . 1 3 A. This distance seems to be short

o.<
o

2
.............) (000
........
..~:: _. . . . . . . . . . . ~
1.04
2.68
AI,Fe,Mg
O,OH
Si,A!
O
---- 4 ~ - ~ ~
............ -- 3.26

....... ~ . . . . L -- 5.39 C03

6
8 o o iii
o o o 594
---7.71

. . . . o "o o ' o L" 8.70

ELECTRON DENSITY
~ o.~oo.~oo~o o~ o.-o C 0 3
I J
o OH
9 Pb
Fro. 7. One-dimensional Fourier synthesis of electron density normal to ab plane (left)--solid line
calculated, dotted line observed--and structural model (right) for the 17 A-mineral.
 Basic lead carbonate--montmorillonite c o m p l e x 23

TABLE3. Observed and calculated structural factors of 00l reflections for the 17/~-mineral.

00l dool/A l/ Io IF]obs Fcalc*

1 17.40 100-00 31-38 -43.62

2 8-722 5-79 15.13 - 5-63
3 5-836 10.92 31.27 44.03
4 4.363 5.88 31-01 - 16.45
5 3.489 7.58 44.61 -52-68
6 2.899 59-70 153.08 152.77
7 2-490 10.00 74-26 -73.91
8 2.175 0.60 21-26 -20.60
9 1.934 0.32 17.84 14.01
10 1.743 0-83 32.60 -29-13
11 1-583 0-85 37.15 -28.86
12 1-449 4.38 94-01 93-89

* obtained from the final z parameters (Fig. 7)

c o n s i d e r i n g t h e v a n d e r W a a l s r a d i u s o f t h e s e m o l e c u l e s , b u t is slightly l o n g c o m p a r e d w i t h
t h e i o n i c r a d i u s . B e c a u s e t h e p e a k o f e i t h e r a n e l e c t r o n d e n s i t y o r F o u r i e r w a v e is
d i s c e r n i b l e at z = 4, i o n s o f e i t h e r H + o r H 3 0 + m a y lie b e t w e e n t h e C O 3 p l a n e a n d t h e b a s a l
o x y g e n p l a n e o f t h e 2 : 1 silicate layer.
A c c o r d i n g to H a y a s e et al. (1978), sufite is m o n o c l i n i c , a = 5.22 A , b = 8 . 9 7 / k , c = 16-3/k,
fl = 96.1~ t h e c h e m i c a l f o r m u l a is Pb(Pb,Ca)l.17(CO3)2(A1,Fe,Mg)2(Si3.67A10.33)O10
( O H ) 2 . F u r t h e r m o r e , t h e c r y s t a l s t r u c t u r e o f s u r i t e is b a s e d u p o n a c e r u s s i t e - l i k e l a y e r
i n t e r c a l a t e d w i t h a 2 : 1 silicate l a y e r s i m i l a r to d i o c t a h e d r a l s m e c t i t e as d e d u c e d f r o m t h e
one-dimensional Fourier synthesis method. This suggests that the interlayer material of the
1 7 / k - m i n e r a l h a s a q u i t e d i f f e r e n t s t r u c t u r e f r o m t h a t o f s u r i t e , a n d t h e s e t w o species a r e
quite distinct from each other.

ACKNOWLEDGMENTS
The authors would like to thank Dr. A. Tsunashima, National Institute for Resources and Environment, and Prof.
S. Yamanaka, Hiroshima University, for their helpful comments. We are also indebted to Dr. M. Shiraishi,
National Research Institute for Resources and Environment, for permission to use the Institute's CM30
transmission electron microscope. This study was partially supported by a Waseda University Grant for Special
Research Projects (63B-5).

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No. 216 188, National Technical Information Services, Springfield.
BALL M.C. & CASSONM.J. (1977) Thermal studies on lead(II) salts-II, J. Inorg. Nucl. Chem. 39, 1949-1951.
COWLEYJ.M. (1956) Electron-diffraction study of the structure of basic lead carbonate, 2PbCO3.Pb(OH)2. Acta
Cryst. 9, 391-396.
FLEMMIN~N.J., LOPATAV.L, SANIPEW B.L. & TAYLORP. (1984) Thermal decomposition of basic lead carbonates:
A comparison of hydrocerussite and plumbonacraite. Thermochim. Acta. 81, 1-8.
HAYASEK., DRISTASJ.A., TSUTSUM1S., OTSUKAR., TANABES., SUDOT. & NISHIYAMAT. (1978) Surite, a new Pb-
rich layer silicate mineral. Am. Miner. 63, 1175-1181.
KATZ G. & REED L. (1957) The unit cell and space group of basic lead carbonate. Acta Cryst. 10, 142.
24 S. Tsutsumi et al.

KOTAMAR., NISHI Y. & KANO M. (1969) Thermal decomposition of lead hydroxide carbonate. Nippon Kagaku
Zasshi, 90, 30-34.
SORRELLC.A. (1962) Solid state formation of barium, strontium and lead feldspars in clay-sulfate mixture. Am.
Miner. 47, 291-309.
WHITE W.B. (1974) Carbonate. Pp. 227-284 in: The Infrared Spectra of Minerals (V.C. Farmer, editor),
Mineralogical Society, London.