THE HYDROTHERMAL AND HYDROTHERMAL-

M E T A S O M A T I C F O R M A T I O N OF K A O L I N A N D
A G E N E T I C C L A S S I F I C A T I O N OF C L A Y R O C K S
By M. A. KASHKAI
Academy of Sciences, Baku, Azerbaljan S.S.R.
[Received 27th March, 1958]
ABSTRACT
A genetic classification of clay rocks is given in which five main types are
recognized. In this classification minerals of the kaolin group formed
directly from hydrothermal solutions, along with sulphides, sulphates,
and pneumatogenic minerals, are separated from the same minerals
formed by the hydrothermal-metasomatic action of gases and vapours on
aluminosilicate rocks. Some data oll the occurrence of these two types
in Azerbaijan are recorded. The origin of the bentonitic clays ("gilabi")
of Azerbaljan is also discussed; the geology of the deposits indicates
cycles of volcanic activity and long-range transport of volcanic ash.

Some twenty to thirty years ago researches in the U.S.S.R. o n

rocks altered by hydrothermal action and by contact metasomatism
resulted in the discovery of minerals of the kaolin group and of clay
rocks which had been formed directly from hydrothermal solutions
along with sulphides, sulphates, and pneumatogenic minerals; at
the same time minerals of the kaolin group originating from the
hydrothermal-metasomatic alteration of igneous, sedimentary, and
metamorphic rocks were also recognized.
Although no comprehensive discussion has yet been attempted,
the literature contains many descriptions of clay rocks formed b y
hydrothermal action. Thus, Ries et al. (1922) believe the kaolin
veins in N o r t h Carolina, where the kaolinite envelops irregular quartz
grains (Bayley, 1920, 1925), to be formed by the alteration of the
aluminosilicate minerals in pegmatite veins, Ross and Kerr (1931)
refer to minerals of the kaolin group in the interstices of ore-bearing
quartz veins, and Tarr and Keller (1937) record several occurrences
in Missouri of kaolin minerals formed from s o l u t i o n - - a concept in
accord with earlier observations in the U.S.S.R. (Beljankin and
Iwanowa, 1935; Smolyaninov, 1936; see also Kashkai, 1939a,
1939/)). The Cornwall deposits, where kaolinite occurs along with
pneumatolytic minerals, are also of interest in this connection.
There is thus ample evidence of the formation of kaolinite under
hydrothermal conditions.
44
 ORIGIN AND CLASSIFICATION OF CLAY ROCKS 45
While the hydrothermal type is formed directly from solution, the
hydrothermal-metasomatic type is formed by the action of sulphurous
gases or carbon dioxide, gas-water solutions, and thermal waters
generally on aluminosilicate rock. Such kaolins frequently form
commercial deposits, as in the Little Caucasus (e.g., Chardakhly,
Azerbaijan). From~the literature it w o u l d appear that th e deposits
near Karlovy Vary (Carlsbad), Czechoslovakia, (e.g., Zeitlin, etc.)
are also of this type, but the author's inspection of these deposits
suggests that these kaolins should be regarded as the products of
ancient surface weathering of granites in peneplained regions.
As a result of the above considerations and other studies on clay
rocks the classification in Table 1 is suggested. Five types, some of
which are further subdivided, are recognized.
There is much literature on the last three types. Clay rocks of
the crust of weathering have been the subject of investigation in the
U.S.S.R. for many years (see, e.g., Ginzburg, 1912, 1915; Polynov,
1934; Petrov, 1948) and clays of sedimentary origin have been
studied both by geologists and by pedologists--for example, in the
oil-bearing areas of Azerbaijan, by Kashkai and Evseev (1943),
Pustovalov et al. (1944), Sultanov (1949), Khalifa-Zade (1953),
Seidov (1956), Aliev and Akaeva (1957), Kossovskaya (1957), etc.
Adsorptive clays of the Caucasus have been described by Blagodarov
(1934), Kashkai and Sultanov (1945), Vezir-Zade (1946), Zulfugarov
and Efendiev (1948), Sultanov (1949), and Kashkai, Efendiev and
Kerimov (1957). Recent sediments in oceans and seas in and around
the U.S.S.R. have also been studied by many geologists--see, for
example, the investigations on Caspian Sea sediments by Kashkai
and Suleimanov (1950), Suleimanov and Pashaly (1953) and Klenova
and Yastrebova (1956).
As regards the first type in Table 1, minerals of the kaolin group of
ihydrothermal origin are found in the paragenesis of alunites, pyro-
phyllites, barites and sulphides. In an alunite mass, such as that at
Zaglik in the Dashkesan ore region of the Little Caucasus, they form
lenses or veins up to 1-2 m thick. They are massive and are either
white or have violet, pink or green tints. The kaolinite of such
deposits is extremely pure and approaches the theoretical chemical
composition--it is indeed comparable in composition and in optical
and X-ray characteristics with synthetic kaolinites (van Nieuwenburg
and Pieters, 1929; Permyakov, 1931; Noll, 1932, 1934; Norton,
1939, etc.) prepared at about 300~ under pressures of up to 300
atmospheres. Chemical analyses of hydrothermal kaolinites from
46 M. A. KASHKAI

TABLE 1--Genetic classification o f clay rocks.

Type [
No. Genetic type Origin M o d e o f Occurrence

1 (a) Kaolinites and Directly from hydro- Veins, lenses, inclus-

kaolin group minerals
o f hydrothermal ori-
gin.
(b) Kaolin group min-
erals in fissures.
thermal solutions, ions.
along with sulphi-
des, sulphates,
pneumatogenic and
other minerals.
Precipitation from Thin (down to fila-
vadose waters. mentary) fissure
forms.

Kaolins and kaolin By the action o f sul- Along tectonically

group minerals o f hy-
drothermal - metaso-
matic origin.
phurous gases, COe, dislocated zones; or
gas-water solutions whole massifs a n d
and thermal waters rock masses sub-
on aluminosilicate iected to hydrother-
rocks. mal-metasomatic
alteration.

3 Adsorptive clays Through the din- Bands (thick or thin)

(washing and bleach- genesis o f volcanic in s e d i m e n t a r y
ing): ash. rocks.
(a) Bentonitic ('gilabi,'
'kil,' 'keffekilite'*)--
active after chemical
pretreatment.
(b) Floridinic* (' gum-
brin ')--active in nat-
ural state.

Clays and clay rocks in T h r o u g h the weath- A t t h e peripheral re-

the crust o f weather-
ing:
(a) Kaolins and kaolin
g r o u p minerals.
(b) Nontronites, nickel
ores, etc.
(c) Laterites and ochres
ering of: gions o f igneous,
sedimentary, and
aluminosilicate metamorphic rocks,
rocks; usually in pene-
ultrabasic rocks; plain regions, and
at depths o f 0-50 m.
various rocks, main-
ly basic.

Clays o f sedimentary
origin:
(a) Ancient marine. By settling on the Beds o f different geo-
b o t t o m o f oceans, logical age.
(b) Recent marine. seas and certain Bottom deposits.
rivers.
(e) Continental. By mechanical wea- Mantle forms.
thering o f rocks
and redeposition.
*The nomenclature here is somewhat confusing: keffekill is generally regarded as sepiolite al-
though it may originally have referred to a smectitie clay (see R, KJrwan, Elements of Mineralogy,
Elmsly, London, 2nd Ed., 1794, voL 1, p. 144, and G. P. C. Chambers, Silic'. Industr., 1959, 24, 181>
and it is interesting to note that M. H. Hey (An Index of Mineral Speeies and Varieties Arranged
Chemically, British Museum, London, 2nd Ed., 1955) distinguishes keffekill from keffekilite; floridir~
also does not seem to be used here as a synonym for palygorskite but appears rather to indicate a
natural earth of unspecified mineral composition used for ell deeolorizing (see R. H. S. Robertson,
Clay Min. Bull., 1950, 1, 125).--Ed.
 ORIGIN AND CLASSIFICATION OF CLAY ROCKS 47

d e p o s i t s in A z e r b a i j a n are given in T a b l e 2, while X - r a y p o w d e r d a t a

a r e q u o t e d in T a b l e 3 a n d a differential t h e r m a l curve is shown in
Fig. 1 (Curve A). The refractive indices o f the Z a g l i k m a t e r i a l are
y 1.567, a 1.561, with 9 ' - a 0-006. A n analysis o f a snow-white
halloysite f r o m t h i n fissures in the alunitized r o c k at Z a g l i k is also
given in T a b l e 1, a n d a differential t h e r m a l curve s h o w n as Curve B
in Fig. 1.

TABLE 2--Chemical analyses of kaolins of hydrothermal and hydrothermal-

metasomatic origin from Azerbai'an.

Hydrothermal-
Hydrothermal metasomatic
2 3 4 5
SiO2 45-54 43 '20 45.30 45.50 56-10 47.23
TiO 2 0.00 0.00 0"00 0.00 0.70 0.00
A1208 39.50 38-26 39.15 39 "99 27-44 38.29
Fe20 3 0"06 0-00 0-03 0'10 2.58 0"75
FeO 0"00 0.00 0.00 0"00 0.29 0"00
CaO 0"00 0 -22 0.04 0"15 0.74 0"49
MgO 0"06 tr. 0.05 0"18 0'01 tr.
MnO 0"00 n.d. 0.00 0 "00 n.d. n.d.
Na~O 0"00 n.d. 0-00 0"00 0,25 n.d.
K20 tr. n.d. 0-00 0 "00 0-22 n.d.
H20 -}- 14.44 14.28 14.20 14'32 9.96 12-73
H20 - 0-22 4.48 0.18 0'15 1.85 0'90
COz 0-07 0.17 n.d. n.d. n.d. n.d.
SO,~ n.d. n.d. ll.d. n.d. 0.51 n.d.
P205 n.d. n.d. n.d. n.d. tr. n.d.
Total 99:89 100.61 98.95 100.39 100.65 100.39

1. Kaolinite, Zaglik alunite deposit.

2. Halloysite, Zaglik alunite deposit.
3. Kaolinite from a lens in Karamurad kaolin deposit.
4. Kaolinite from a vein in Chovdar baryte deposit.
5. Kaolinized quartz porphyry, Chardakhly kaolin deposit.
6. Snow-white pseudomorphs of kaolinite after plagioclase, Chardakhly kaolin
deposit

K a o l i n s o f h y d r o t h e r m a l - m e t a s o m a t i c origin are genetically

a s s o c i a t e d with the effect o f s u l p h u r o u s a n d c a r b o n d i o x i d e s o l u t i o n s
o n aluminosilicate rocks. I n this instance the k a o l i n i z a t i o n process
p r o c e e d e d a l o n g t e c t o n i c fractures a n d i n v o l v e d large massifs, the
o r i g i n a l structure o f w h i c h d e t e r m i n e s the m o r p h o l o g y o f the deposit.
T h e r e are a n u m b e r o f deposits o f this t y p e in t h e Little Caucasus,
w h e r e q u a r t z p o r p h y r i e s o f M i d d l e Jurassic age were a l t e r e d into
48 M.A. KASHKAI

kaolins with residual porphyritic quartz and pseudomorphs of pure

kaolinite after felspar* (see analysis in Table 2). The refractive
indices of the kaolinite in these PSeudomorphs are V 1-568, a 1.562,
with 7 - a 0-006; a differential thermal curve is shown in Fig. 1
(Curve C).
TABLE 3--X-ray powder data for clays from Azerbaijan.

Montmorillonite Kaolinite
d G) I d (A) ~ d (A) I
7.709 8 4"45 10
7.074 10 4"34 6
4-499-~ [3-35 1 (qtz.)]
3.954f 5d 3"34 2
3.08 89
3.581 10 3-03 10
2.758 10 2.556
2.590~ 2-534 10
2.508f 5d 2-491 5
2.379 1 2.272 5
2.338 8 2.24 2
2-303 1 2-16 2
2-208 2 1.839 2
1.992 5 1 '689
1.840 2 1 "658 7
1-790 1 1.652 6
1.663 5 1.536 3
1.622 1 1-489 10
1-59O 2 1 "486 8
1.543 I 1.288 6
1.491 8 1 "284 3
1.461 2 1-239 6
1-433 2 1.235 3
1 "374 2 0.974 4
1 "339 3 0'973 1
1-307 5
1-285 3
1.238 3
1 "192 2
1 "128 2
1-095 2
1. Hydrothermal kaolinite from the Zaglik alunite deposit.
2. Bentonitic clay (Tertiary) from the Khurdalan deposit, Apsheron Peninsula.

Tuffites, t u f f a c e o u s s a n d s t o n e s , a n d t u f f b r e c c i a s o f t h e Z a g l i k
d e p o s i t h a v e also b e e n s u b j e c t e d t o h y d r o t h e r m a l - m e t a s o m a t i c
a l t e r a t i o n , t h e p r o c e s s o c c u r r i n g in t h e f o U o w i n g s e q u e n c e : a l u n i t i z a -
tion--pyro phyllitization--kaolinization.
* At the periphery of the quartz-porphyry mass, the ancient crust of weathering
can at times be observed.
 ORIGIN AND CLASSIFICATIONOF CLAY ROCKS 49

In all such deposits relict textures and structures of the original

rock can be observed both macroscopically and microscopically.
Under the microscope it can be seen that the dark-coloured com-
ponents of the rock are also kaolinized, the coloration is due to iron
oxides (and titania) released during the alteration of the rock. In
the Chardakhly deposit the
quartz grains display resorbed
and corroded edges typical of
quartz-porphyries.
Bentonitic and floridinic*
clays, formed by the diagenesis
of volcanic ash, are widely
developed in volcanic areas,
occurring in Upper Cretaceous
and Tertiary deposits in the
Caucasus. Ten or more ben-
tonitic clay beds ("gilabi") have
been recognized in Tertiary
deposits in the oil-bearing
regions of Azerbaijan. These
600 650 82#
clays were formed from volcanic
ash transported from the
,~67 685 volcanic vents in the Little
Caucasus for distances of up
to hundreds of kilometres to
FIG. 1--Differential thermal curves for regions where the conditions
clays from Azerbaijan: A--kaolinite,
Zaglik deposit, Little Caucasus; B-- were favourable for the form-
halloysite, Zaglik deposit, Little Cau- ation of bentonitic clays.
casus; C--kaolinite, Chardakhly de- During this process the heavy
posit, Little Caucasus; D--montmoril- minerals separated at an early
lonite (Cretaceous), Khanlar deposit, stage of transportation. The
Little Caucasus; E--montmorillonite
(Tertiary), Khurdalar~deposit, Apsheron field relationships indicate
Peninsula; F monothermke, Zykh de- cycles of volcanic activity.
posit, Apsheron Peninsula. The light fraction of the ben-
tonitic clays (which comprises
96-98 per cent. of the rock) consists of montmorillonite (up to 70 per
cent., or more), kaolinite, volcanic glass fragments (up to 7 per cent.,
or more), quartz, felspars, gypsum, and carbonates, while the heavy
fraction (only a few per cent. of the rock) contains biotite, chlorite,

* See footnote to Table 1.

50 M. A. KASHKA1

amphiboles, pyroxenes, epidote, garnets, zircon, apatite, limonite,

ilmenite, and magnetite.
The X-ray powder data in Table 3 for a sample from the Khur-
dalan deposit in the Apsheron Peninsula indicate a mixture of
montmorillonite with some kaolinite. The chemical composition
of these clays is in the range SiO2 45-65, A120~ 12-22, CaO 2-7, MgO
2-4, H20 14-15, with SiOz : Al~O3 3-7. Curves D and E, Fig. 1,
are typical differential thermal curves.
The physical and chemical properties of these clays depend upon
both the mineralogical composition and the extent of microaggre-
gation. They acquire the main properties of an activated oil-
decolorizing or bleaching clay on treatment with 20 per cent. sul-
phuric acid.

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