Clay Minerals (1968) 7, 295.

A STUDY OF CLAY MINERALS IN PODZOL

SOILS IN NEW BRUNSWICK, EASTERN CANADA

H. K O D A M A AND J. E. B R Y D O N

Soil Research Institute, Department o/ Agriculture,

Ottawa, Ontario, Canada

(Received 26 September 1967)

A B S T R A C T : Clays from the Ae and C horizons of five Podzol soil series

in New Brunswick were examined by X-ray, chemical and infrared absorption
methods. ALl the experimental evidence indicated that the Ae horizons contained
predominantly a dioctahedral randomly interstrafified mica-vermiculite--smectlte
clay, whereas the C horizons contained abundant dioctahedral mica (illite) and
trioctahedral chlorite. Since no trace of chlorite as a separate phase or as one
component of the interstratified structure was found in the Ae horizons, it was
concluded that, while the inherited chlorite was decomposed in all of the Ae
horizons, mica was differentially hydrated giving an interstratified structure.
Fourier transforms of the three-component interstratified clay revealed different
ratios of hydrated layers (vermiculite and smectite) to non-hydrated layers and
different stacking sequences. The proportion of hydrated layers and randomness
of stacking was related to the degree of weathering as measured by the accumula-
tion of TiO 2 in the Ae horizon and it was suggested that they may be related to
the degree of podzolization.

INTRODUCTION
M i n e r a l o g i c a l studies on soils in eastern C a n a d a have shown that in general illite
is the p r e d o m i n a n t c l a y m i n e r a l with chlorite a n d vermiculite present in lesser
a m o u n t s ( F o r m a n & B r y d o n , 1961). In the course of investigating P o d z o l soils f r o m
N e w Brunswick, it was f o u n d that illite a n d chlorite were a b u n d a n t in C horizons, t h a t
chlorite h a d d i s a p p e a r e d f r o m the A e h o r i z o n a n d that a smectite-like interstratified
clay was a m a j o r c o m p o n e n t m i n e r a l in A e horizons (of. B r y d o n , K o d a m a & R o s s ,
1968). It was thought that a m o r e d e t a i l e d s t u d y of the clay m i n e r a l s w o u l d e l u c i d a t e
the w e a t h e r i n g m e c h a n i s m s which s e e m e d to prevail o n the basis of the a b o v e d a t a .

EXPERIMENTAL METHOD
Materials and sample preparation
S a m p l e s were collected f r o m the A e a n d C horizons of each of five P o d z o l soil
296 H. Kodama and J. E. Brydon
series in N e w Brunswick.* A s u m m a r y of the soil samples, their p a r e n t m a t e r i a l s
a n d underlying b e d r o c k is given in T a b l e 1.
P o r t i o n s of the a i r - d r i e d , less t h a n 2 m m s a m p l e s were t i t r a t e d to p H 3"5 with
1 N HC1 to r e m o v e c a r b o n a t e s a n d t r e a t e d with H202 to d e s t r o y organic m a t t e r .
A f t e r w a s h i n g the s a m p l e s with water, they were f r a c t i o n a t e d b y a c o m b i n a t i o n
of s e d i m e n t a t i o n a n d c e n t r i f u g a t i o n into three f r a c t i o n s : fine silt ( 5 - 2 t~), coarse
clay (2-0-2 ~) a n d fine c l a y ( < 0 " 2 t~). T h e samples were c o n c e n t r a t e d b y floccula-
t i o n with acidified CaC12 solution, then w a s h e d free of c h l o r i d e with w a t e r a n d
ethyl a l c o h o l a n d freeze-dried.

TABLE 1. Description of the soil samples

Sample Soil Sample Underlying

No. Horizon series location rock Remarks

SMJ 1 Ae Kedgewick Near Kedgewick Limestone, Bisequa Podzol developed

47 ~40' 67~ 23' shale on an ablation moraine
SMJ 2 C Restigouche Co. (Ordovician) SMJ 1 (Ae) is from the
upper A horizon*

SMJ 3 Ae Monquart Near Carlingford Quartzite, An Orthic Podzol devel-

46 ~ 46' 67~ 46' argiUite, oped on an ablation
SMJ 4 C Victoria Co. shale moraine ~"

SMJ 5 Ae Baker Brooke Shale An Orthic Podzol formed

Glazier 47 ~ 18' 68 ~ 35' argillite, on water deposited
SMJ 6 C Madawaska Co. phyllite materials*

SMJ 7 Ae Lorne Parish Argillite, An Orthic Podzol formed

Serpentine 47 ~ 05' 67~ 00' quartizite on an ablation moraine*
SMJ 8 C Victoria Co. schist,
some volcanics
(Ordovician)

SMJ 9 Ae 47 ~ 00' 67 ~ 00' Granite, An Orthic Podzol formed

Tuadook basalt, on a ground moraine*
SMJ 10 C rhyolite

*Langmaid (1967). ~Millette & Langmaid (1963).

Analytical techniques
X - r a y analysis was c a r r i e d o u t with a Philips diffractometer using Fe-filtered
C o - r a d i a t i o n (Co Ka. X = 1"7902 A) on n o n - o r i e n t e d a n d oriented specimens. T h e
o r i e n t e d specimens were p r e p a r e d b y allowing 1 m l of the suspension containing
20 m g of s a m p l e to settle a n d d r y on a 37"5 m m x 25 m m glass slide. C l a y m i n e r a l s
were identified b y i n t e r p r e t a t i o n s f r o m X - r a y e x p e r i m e n t a l results on the oriented
* From K. K. Langmaid, Fredericton, N.B.
 Clay minerals in Podzol soils 297
specimens under various conditions included glycerolation, heating, extremely dry
(<3% relative humidity) and humid (95% relative humidity) conditions. In some
phases of the investigation, X-ray diffraction patterns were recorded while the
specimens were maintained at approximately 100~ C to characterize the hydrated
phyllosilicate layers.
Since it is difficult to identify kaolinite in the presence of chlorite by X-ray
examination an infrared absorption technique was used (Kodama & Oinuma, 1963).
The absorption spectra were obtained with a Beckman IR 12 infrared spectrophoto-
meter using samples prepared as a mull in Nujol and mounted between NaC1 plates.
Chemical analysis was performed using the X-ray spectrochemical method
developed by Kodama, Brydon & Stone (1967). Free iron oxide analysis was made
by the method described by Mehra & Jackson (1960). After treatment, extractable
AI was determined colorimetrically (Robertson, 1950).

Diagnostic criteria ]or clay minerals

10.4 clay mica (illite). A 10 A basal spacing and its integral series of higher
order reflections (00l) do not shift upon either solvation with glycerol or heating
at 550 ~ C. Some information about its chemical structure is provided by the position
of the 060 reflection and the intensity ratio 1(001)/1(002) (Brown, 1955).
Chlorite. An integral series of peaks associated with the largest basal spacing of
14 A does not expand by glycerol sorption and does not shift upon heating at
550 ~ C. The intensity ratio of the basal reflections may be used to define a species
of chlorite minerals (Brindley & GiUery, 1956).
Vermiculite and smectite. Neither of these minerals was present as an independent
mineral constituent of soils in the present study, but structures equivalent to those
of both minerals occurred as components in various types of interstratifications.
Although those layers may not be identical with typical vermiculite or smectite, it
is useful to distinguish them conventionally on the following basis: vermiculite
maintains its 14 A basal spacing upon solvation with glycerol and under high
relative humidity, whereas smectite (Ca-form) exhibits an expansion of its basal
spacing (15 A at room relative humidity---40-50% R.H.) to about 18 A under high
humidity or glycerolation. Both of them collapse to 10 A upon heating to 550 ~ C,
which is obviously different from chlorite which remains unchanged at that temp-
perature.
Interstratified minerals. There were several types of interstratified minerals in these
clays. Most of them showed an intermediate d-spacing indicating a hybrid nature
with no long-spacing periodicity. They consisted of two or three component layers
of mica-, vermiculite-, chlorite- and smectite-like layers. The determination of types
of interstratifications was based on a combination of the characteristics of each
component-layer that was mentioned in preceding sections. Brief criteria are
tabulated in Table 2. Interstratified mixtures of the three components, mica-
vermiculite-smectite were the only predominant and the most significant materials.
Their detailed analyses are described in a later section of this paper.
298 H. Kodama and J. E. Brydon
T,~Lr~ 2. Criteria used for determination of types of non-regular interstratifications indicated by
the first-order basal spacing (A) following different treatments

Type of Glycerol Humid Air-dry Very dry 110~ C 550~C

interstratification* 95 % RH 45 % RH 3 % RH

Mica-vermiculite 1 I 10-14 10-11 "5 10-11 "5 10

Mica-chlorite 1" I 10-14 I 1" 10-14
Mica-smectite 10or 18 Expansion 10-15'5 10-11'5 10-11"5 10
Vermiculite--chlorite 1 I" 14 11"5-14 11"5-14 10-14
Vermiculite--smectite 14-18 Expansion 14-15.4 11.5 11.5 10
Chlorite--smectite 14-18 Expansion 14-15"4 1 1 . 5 - 1 4 11.5-14 10-14
Mica-vermiculite--chlorite I" i 10-14 Contraction Contraction 10-14
Mica-vermiculite--smectite Expansion Expansion 10-15"4 Contraction Contraction 10
Vermiculite-chlorite-
smectite Expansion Expansion 14-15-4 Contraction Contraction 10-14

Expansion and contraction mean shift of the original first-order reflection (air dry) towards
large and small spacing sides respectively.
* As Ca-saturated specimen.
Indicates that the basal spacing is unchanged from air-dry.

Kaolinite. In the present study, kaolinite was only a minor constituent of the
clays. Because of its association with chlorite in most cases, the infrared absorption
technique was applied. Kaolinite can be identified by the presence of an absorption
peak at 3700 cm -1 in the absence of brucite (Oinuma & Kodama, 1967) and is
detectable down to a few per cent of total clay (Kodama & Oinuma, 1963).

RESULTS AND DISCUSSION

Mica and chlorite
Both of these minerals were present abundantly in C horizons. The micas were
aluminous and of a dioctahedral-type, since the intensity ratios 1(001)/1(002) were
less than 4 and 060 reflections appeared at 1"50 A.
The chlorite minerals showed that their odd order reflections were weaker than
the even order reflections. The ratios 1(002)/1(001) of the chlorites were between
3 and 4, which indicated that they were of a trioctahedral-type. A further con-
firmation was made by the evidence that the ratios 1(003)/1(002) were less than 1,
since a dioctahedral chlorite should have the intensity ratio of more than 1"5 (Hayashi
& Oinuma, 1964; Eggleston & Bailey, 1967).

lnterstratified mica-vermiculite-smectite clays

The three-component interstratified clays were abundant in the three fractions
of the Ae horizons of all soils. They showed a large broad peak with single or
double maxima ranging between 11 and 13-5 A at room temperature and 45% R.H.
Generally the magnitude of the spacing depended upon the size fraction, that is,
 Clay minerals in Podzol soils 299
the larger spacing appeared in the finer fraction. Upon solvation with glycerol, the
broad peak was split into fairly well defined peaks which were shifted to larger
spacings. The spacings of the shifted peaks were either one of 12, 13"8 and 17"6 A
depending on the position of the original spacing. In addition to this, a separate
peak appeared in most cases at approximately 10 A. Similar results were obtained
from Ca-saturated samples after removal of free iron by the dithionite--citrate treat-
ment, excepting that the treatment caused a slightly larger spacing in both the air-dry
and glycerolated specimens. When the untreated air-dry samples were heated to
550 ~ C, the large broad peak collapsed completely to 10 A. Powder patterns of
the nonoriented specimens showed the presence of a reflection at 1"50 A.
This behaviour indicated that the interstratified clays contained mica-like and
smectite-like layers but not chlorite-like layers. However, the basal peak positions
of glycerolated samples could not be interpreted from the published data on two-
component mica-smectite interstratification (MacEwan, Ruiz & Brown, 1961;

d-spacing (~)
3-3 3"5 4 5 6 "7 8 9 I0 14 I8

(a)

(b)

Co)

(d)

(e)

35 30 25 20 t5 lO 5
Degrees, 28 CoKc~

FiG. 1. X-ray diffraction patterns of oriented specimen of the minus 0.2/~ fraction from
sample SMJ 1. (a) is untreated air-dry specimen; (b) is glycerol-saturated specimen;
(c) is the specimen under 95 % relative humidity condition; (d) is the specimen kept
at I I0~ C; (e) is the specimen after heating at 550~
300 H. Kodama and J. E. Brydon
d- spocing (~)
3"53'.5 4 5 6 7 8 9 IO I418

(o)
J
! -
(b)
lj
(c)

(e)
J
35
!,__, I, ,I I, t,
50 25 20 15 I0 5
Degrees, 28 CoKa

FIG. 2. X-ray diffraction patterns of oriented specimen of the minus 0'2 t~ fraction
from sample SMJ 9. (a) is untreated air-dry specimen; (b) is glycerol-saturated specimen ;
(c) is the specimen under 95 % relative humidity condition; (d) is the specimen kept
at 110~C; (e) is the specimen after heating at 550~C.

Cesari, Morelli & Favretto, 1965; Reynolds, 1967). This suggested that the material
consisted of a multi-component interstratification and that the direct method of
MacEwan (1956) could be used to interpret the X-ray diffraction data. For this
purpose the minus 0'2 t~ size fractions were most suitable, because of a high con-
centration of the interstratified clays.
A m o n g the five samples from the Ae horizons, SMJ 1 and SMJ 9 seemed to
exhibit extremes of behaviour on the basis of the X-ray diffraction data (Figs 1
and 2). The same relation was also observed in the coarser fractions. The first-order
basal reflection of-SMJ 1 appeared at 12"5 A in the air-dry condition and moved to
13-3 A upon glycerolation whereas that of SMJ 9 appeared at 13"3 A in the air-dry
condition and the reflection was split into two peaks at 13.8 and 17.6 A after
glycerol-sorption. The other samples showed characteristics intermediate between
the above two. Therefore the Fourier transform analyses were made on the two
samples using air-dry specimens.
 Clay minerals in Podzol soils 301
Basal reflection data were obtained using oriented specimens under varying
conditions of slit widths and scale factors in order to record each basal reflection
adequately. The peak area was measured by means of a planimeter and expressed
in arbitrary units. Peak areas for the various operational conditions were compared
on the basis of the 1~ slit and the x 20000 c/min scale factor with which the
diffraction pattern for SMJ 1 was taken. The compiled intensity data are listed in
Table 3 with the record of diffraction angles and d-spacings. After the correction

TABLE 3. X-ray diffraction data (air-dry) for the minus 0-2/~ size fraction samples
o f S M J 1 and SMJ 9 at room temperature and 40-50% R H

20 (deg.) d(A) I
(arbitrary units)

SMJ 1 8"2 12"5 1547

20"7 4"97 157
31 '3 3"32 297
41-0 2"55 21
53 "2 1 "997 80

SMJ 9 7"7 13"32 1547

20"7 4'97 45
31'2 3"32 74
40"7 2"55 3
53"2 1.997 6

for Lorentz-polarization factors, the integrated intensities were converted to Fourier

coefficients using conventional layer structure factors published by Cole & Lancucki
(1966) for hydrous dioctahedral mica type layers. In the absence of definite chemical
formulae of the interstratified components, no absorption correction was made. In
order to check the effect of absorption on the intensity data, using a hypothetical
composition and the sample thickness of 0-003 cm, the absorption correction was
calculated. The correction increased the intensity of the highest order reflection
by about 20%. In the present case, however, because intensities of the higher orders
were very weak, the revised values of Pa, PB and Pe did not differ by more than 2%.
The Fourier transforms (Fig. 3) were calculated by means of an IBM 1620 com-
puter. Both of the transforms showed three fundamental components with spacings
of 10(A), 13-6 (B) and 15.8(C) A. Since chlorite had been found to be absent, the
three fundamental components were assigned to mica-like, vermiculite-like and
smectite-like layers, respectively. A further support of the assignment may be given
by the evidence that high humidity caused an expansion of the first-order reflection and
that the extremely dry condition, which was obtained by maintaining the temperature
at I10 ~ C, shifted the reflection towards a spacing between 10 and 11.5 A (Figs
1 and 2). Lists of assignments for peaks on the Fourier transforms are given in
Table 4 with a comparison of the observed peak heights with the calculated ones.
302 H. Kodama and J. E. Brydon
to <
m+ _~ t~o <
+: t

<% to ,~ (a)

W (R)

~ u to
(b)

+.

,,,,,,,,I, ...... ,,I ......... l,,,,,,,,,l,, .......

0 I0 20 30 40 50
R (~)
FIG. 3. Fourier transforms of basal reflections of untreated air-dry intcrstratified
mica-vermiculite--smectite clays. (a) Sample SMJ 1; (b) sample SMJ 9.

The comparison indicated a good agreement between the observed and calculated
peak heights. The probability coefficients were then deduced from the observed
data of peak heights and are listed in Table 5. The mixing ratios of the three
components (mica-vermiculite-smectite) were 0-53:0"27:0"20 for sample SMJ 1
and 0.40:0.38:0-22 for sample SMJ 9, as obtained directly from probability
coefficients for the three fundamental components. In sample SMJ 1, the mica layers
had a tendency to pile together to produce a zonal structure [P,ta (0.74) > PX (0"53)],
but not in sample SMJ 9 (PaA < P,t). Both Fourier transforms (Fig. 3) showed a
prominent combination peak at 40 A consisting of contributions from both
AAAA-type and ABC-type layer successions. The latter type of succession includes
six orderings such as ABC, ACB, BAC, BCA, CAB and CBA. In sample SMJ 1,
the calculated height ratio of the 40 A peak is 0-37, of which only two-fifths belongs
 Clay minerals in Podzol soils 303
TABLE4. Comparison of observed peak heights on Fourier transform with calculated peak
heights for untreated samples of SMJ 1 and SMJ 9

SMJ 1 SM.I 9

Spacing Calculated Observed Spacing Calculated Observed

(A) Peak height height (A) Peak height height

10.0 A 0.53 0.53 10.1 A 0.40 0"40

13.6 B 0.27 0.27 13.6 B 0.38 0.38
15.9 C 0-20 0.20 15-8 C 0.22 0.22
20"0 AA 0.39 0.39 20.0 AA 0.14 0-14
23.6 AB 0-28 0-28 23-8 AB 0.21 0-21
26"0 AC 0-35 0"35 26"1 AC 0"39 0.39
29.9 AAA 0-29} 0"38 29"9 {AAA 0'05/ 0"37
BC 0"09 BC 0"30 J
33-7 AAB 0"2i 0"19
36.0 AAC 0.22 0"35 36"2 AAC 0"30 0.11
39.9 AAAA
ABC 0"22 t 0"46 40"0 { AAAA 0.02 0"59
0-15 J ABC 0"37,
43 "6 {AAAB 0-19} 0-14 43.5 {AAAB 0.04} 0"15
BBC 0"01 BBC 0"05
46-0 AAAC 0"20 0-25
[ AAAAA 0"16 / 0"51 50.0 { AAAAA 0.01} 0"35
49-6
t AABC 0"19 J AABC 0"30

TABLE5. Probability coefficients deducted from Fourier trans-

forms of calcium saturated clays SMJ I and SMJ 9

SMJ 1 SMJ 9

PA 0"53
--'~ P~, = 0-40
Pa = 0.27 Ps = 0.38
Pc = 0.20 Pc = 0.22
PAA = 0"74 PAA = 0"35
PAB = 0"16 PAB = 0"10
PAC = 0"10 Pgc = 0"55
PBA = 0"74 PBA = 0"45
PBs = 0 Pss = 0
Psc = 0-26 PBc = 0"55
PeA ---- 0"90 PCA = 0"77
PcB = 0"10 PcB = 0"23
Pcc = 0 Pet = 0

to the c o n t r i b u t i o n from a n A B C - t y p e layer succession (Table 4). While, in the case

of the sample SMP 9, the calculated height ratio of the c o r r e s p o n d i n g peak is 0.39
almost all of which, 0"37, contributes to the p r o b a b i l i t y that the A B C - t y p e layer
succession occurs (Table 4). I t could, therefore, be c o n c l u d e d that the three-
c o m p o n e n t layers of SMJ 9 were m o r e r a n d o m l y interstratified t h a n those of SMJ 1.
304 H. Kodama and J. E. Brydon
Mineral associations
Table 6 summarizes the clay mineral assemblages in the soils with a semi-
quantitative estimation of each clay mineral. In the C horizons, the coexistence of

mica with chlorite was characteristic. Chlorite tended to be less concentrated in

the fine fraction and substituted by several types of interstratified clays in which

TABLE 6. Clay mineral associations of the soils

Interstratified clay minerals

Soil Hori- Fraction Chlorite Mica Kaolinite
type zon M--Ch V-Ch Ch-S M-V-S M-V-Ch

Kedge- Ae 5-2/~ -- * . . . . **
wick 2-0.2/~ -- * . . . . ***
<0.2/z -- ** . . . . *** --
5-2 ~ ** ** -- -- * -- -- --
2-0.2/~ * *** tr * . . . .
< 0"2/~ -- *** tr * -- -- -- *

Monquart Ae 5 - 2 t~ -- ** . . . . **
2-0"2 ~ -- * . . . . ***
< 0"2/,~ -- ** . . . . ***
C 5 - 2 tz ** *** * . . . . .
2-0'2/z * *** * . . . . *
<0"2/~ -- *** tr . . . . **

Glasier Ae 5-2/* -- ** . . . . ** --
2-0"2/~ -- * . . . . *** --
<0"2t* -- * tr -- -- -- *** --
C 5-2/z *** ** . . . . . .
2 - 0 ' 2 t~ ** ** . . . . . .
<0'2~ * *** . . . . . .

Serpen- Ae 5 - 2 tz -- ** . . . . **
fine 2 - 0 - 2 tz -- * tr -- -- -- *** --
<0'2/~ -- * tr -- -- -- *** --
C 5-2 ~ ** ** * * . . . .
2-0-2/~ ** ** * -- * ** -- --
<0'2 p, -- *** * -- -- *** -- --

Tuadook Ae 5-2~ -- tr tr -- -- --

2-0.2 -- tr * - - i - -

<0.2a -- tr
C 5.2tz
2-0.2
<0.2 tz

*** Abundant M: Mica

* * Moderate V: Vermiculite
* Minor Ch: Chlorite
tr Trace S: Smectite
 Clay minerals in Podzol soils 305
chlorite was one component. This may suggest a gradual weathering of chlorite to
its derivatives in the C horizons. In the Ae horizons, the interstratified mica-
vermiculite-smectite clays were predominant whereas chlorite had disappeared
completely. Mica was another component mineral in the Ae horizon but its quantity
was moderate to trace. Kaolinite occurred occasionally as a small quantity in both
Ae and C horizons. It occurred only as a trace in the Kedgewick C horizon and
was present in minor amounts in the Monquart, Serpentine and Tuadook. There
was a decrease in kaolinite content from the C to the Ae horizon of the Kedgewick,
Monquart and Serpentine.
These clay minerals were generally accompanied by quartz and feldspar, and
their quantities decreased with decreasing size of fraction. Further information about
the feldspar minerals was obtained by X-ray diffraction data for non-oriented
and (111) reflection at 3"77 A. Assuming the absence of unmixing of peristerite-type
powder samples of the 5-2 t~ fractions. Powder patterns of all five silt fractions gave
a single (20[) reflection at 4"03 A and the separation of (1i1) reflection at 3"87 A
according to Smith's diagram (1956), the measure 20 (111)-20 (1~ 1) of those samples
corresponded to plagioclase with the composition in the region An2o-Ana0. Because
of the assumption, the identification of the plagioclase species is inconclusive. A
minor quantity of an amphibole mineral is present in the 5-2 /~ fraction of C
horizons of Serpentine and Tuadook.

Chemical composition
The total chemical composition of the respective 2-0.2 ~ samples only is reported
in Table 7, because the composition of the 5-2 ~ fraction was affected by the
primary minerals present and there was insutlicient material in some of the <0"2 t~
fractions for analysis.
The difference in chemical composition (Table 7) between the Ae and C horizons
supports the foregoing finding that there is a clear distinction in mineral associations
between the two horizons. The amounts of Al203, total FezO3, MnO, MgO, K~.O
and NazO decreased from the C to the Ae horizon although not to the same degree.
The change is obviously due to leaching of certain elements associated with a
selective mineral alteration from the C to the Ae horizon. The increase in C a t
content in the Ae horizon was caused by saturation of the samples with calcium
prior to chemical analysis. Therefore, the apparent increase in C a t suggested that
the soil samples from the Ae horizon, where the three-component interstratified
clays occur, had a higher cation-exchange capacity which would be expected from
the vermiculite and smectite component layers of the interstratified clays. The
amounts of SiOz and Tit2 increased from the C to the Ae horizon. Although small
amounts of Ti may substitute for Al and Fe in silicates, most of the Tit2 content
is attributed to clay-sized titanium oxide minerals (Jackson, 1964) which are
relatively resistant to weathering. Therefore, the ratio of the Tit2 in the Ae horizon
to that in the C horizon may be used as an indicator of the degree of weathering.
The ratios ranged between 1"26 for Kedgewick and 2-97 for Tuadook.
306 H. Kodama and 3". E. Brydon

~ ~

~ g

t~

~ e

e,n e~

eq ~ cq e~ ~ ~ eq ~ eq

f~

el o~

.o
 Clay minerals in Podzol soils 307
The free iron oxide content of the Ae horizons are low as compared to the
C horizons (Table 7) or to Podzol Bf horizons (McKeague & Day, 1966). High
amounts of ignition losses of the samples from the Ae horizon are due to combustion
of organic matter remaining from the H~O2 treatment, which has been confirmed
by the presence of an exothermic reaction at about 350 ~ C in unpublished d.t.a.
curves.

Weathering reactions
In the Podzol soils investigated here, micas and chlorites were the principal
minerals in the C horizon although chlorite in some cases had already been altered to
its intergrades of various types. During weathering in the Ae horizon, the chlorites
seemed to have been decomposed because there was no evidence of a trioctahedral
alteration product and the magnesium and iron contents were low. Recent laboratory
experiments on the acid dissolution of Mg-chlorite also have shown decomposition
to an amorphous state with no evidence of a preferential degradation of the
lattice (Ross, 1967a, b). On the other hand, the micas were degraded, resulting in
interstratified mica-vermiculite-smectite clays. Similar reactions have been recog-
nized in soils and have been summarized recently (Jackson, 1965). However, a
further differentiation of the mineralogy of Podzol Ae horizons is noted.
According to the TiO2 content ratio, the degree of weathering decreases in the
following sequence : Tuadook > Serpentine > Glasier > Monquart > Kedgewick.
The same sequence is shown by the X-ray data for the three-component interstratified
clays of every fraction from the Ae horizon. For instance the main peaks of the
clays in the minus 0-2 ~ fraction after glycerol sorption were 17"6 and 13-8 A for
Tuadook, 17-4, 13-7 and 10 A for Serpentine, 17"1, 13-5 and 10 A for Galiser, 13.7 and
10 A for Monquart, and 13-3 and 10 A for Kedgewick. Since a large number of
hydrated layers in the interstratified clays is reflected in a series of larger spacings, the
above sequence agrees with the degree of hydration as well as with the degree of
weathering. In fact, the ratio of hydrated component layers to non-hydrated (mica-
like) component layers of Tuadook (1-5) is higher than that of Kedgewick (0"9). In
addition, the mica component layers of the interstratified clay of Kedgewick are
segregated to maintain a zonal structure, whereas the interstratified clay of Tuadook
has a more homogeneous distribution of each component layer. The presence of
a zonal structure indicates that the interstratified clay is a weathering product of
mica by a selective hydration alteration which is still in a relatively earlier stage. A
continuation of the selective alteration of mica would result in a higher ratio of
hydrated component layers to mica layers and more homogeneous distribution of
every component layer to make a stable structure. An example of the latter case can be
seen in the interstratified clay of Tuadook. The data and this interpretation suggested
that the micas became altered along preferential weathering planes (Jackson et al.,
1952) according to a mechanism similar to that proposed by Sudo, Hayashi &
308 H. Kodama and J. E. Brydon
Shimoda (1962). Thus the mineral weathering observed in these soils may be
expressed schematically as follows based upon the degree of weathering:

Degree of weathering in Podzols

) Increase

Interstratified mica-vermiculite--smectite(probably (8), (9))

Low proportion of / High proportion of

/-----+ hydrated layers. Mica hydrated layers.
/ layers segregated ~ Homogeneous distri-
Mica (7) / bution of layers
(illite) - - \
\
\ ) Degradedmica

Interstratified )
Intergrade with mica-like ) Amorphous residue
Chlorite (4) ~ (8), (9) hydrated layers

where the bracketed numbers, represent weathering indexes as proposed by Jackson

et al. (1948) and Jackson (1964).
It is also proposed that these results and this weathering sequence refect the
degree of podzolization. Although neither the morphology nor the chemical properties
of the five soil profiles have been included in this paper, the Kedgewick, a Bisequa
Podzol represents a poorly developed or 'youthful' Podzol whereas the others are
well developed. The TiO2 contents and the nature of the interstratified clay minerals
in the Kedgewick reflect the early stage of mica weathering in the equation above.
On the other hand, the data for the well-developed Tuadook reflect the later stage
of mica weathering in the above equation. The other soils seem to occupy an
intermediate position and it may be that the mineralogical data might be used to
subdivide further the well-developed Podzols.

CONCLUSIONS
The Ae horizons of the five soil series contained predominantly a dioctahedral
randomly interstratified mica-vermiculite-smectite clay. Variations in the nature
of the clays appeared to conform with the differences in degree of weathering.
While the inherited chlorite was decomposed in all of the Ae horizons, mica was
differently hydrated and transformed into an interstratified structure in which the
manner of interstratification indicated the degree of weathering.
According to Allen & Johns (1960) the major clay minerals in bed rocks at
three localities of New Brunswick are hydrous mica and chlorite. Well-ordered
mica and chlorite were found in the clay fraction of many of the C horizons of the
soils reported by Brydon et al. (1968). These similarities suggest that mineral
 Clay minerals in Podzol soils 309
association of the C horizon has been inherited from the source rock or sediment.
I n the present investigation, there were no large differences a m o n g the clays of
the five soil series. However, in terms of TiO.~ contents a n d the n a t u r e of the
t h r e e - c o m p o n e n t interstratified clays, podzolization in the T u a d o o k is considered
to be more a d v a n c e d t h a n in the Kedgewick a n d the other series m a y be in a n
intermediate stage.

ACKNOWLEDGMENTS
The authors wish to thank Mr K. K. Langmaid for collecting the samples, Drs J. A. McKeague
and G. J. Ross for reviewing this manuscript, Dr K. H. MacKay for calculating by an IBM
computer, and Messrs N. M. Miles, B. C. Stone and L. M. Patry for their technical assistance.

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