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Clay Minerals (1990) 25, 93-98

CRYSTALLOCHEMICAL C L A S S I F I C A T I O N S OF
PHYLLOSILICATES BASED ON THE UNIFIED
S Y S T E M OF P R O J E C T I O N OF C H E M I C A L
COMPOSITION:
III. T H E S E R P E N T I N E - K A O L I N GROUP

A. W l E W I O R A

Institute of Geological Sciences, Polish Academy of Sciences, AI. Zwirki i Wigury 93, 02-089 Warsaw, Poland

(Received 15 February 1989; revised 20 July 1989)

A BST R A C T : A unified system of projection of chemical composition, prepared initially for


micas and chlorites, has been applied to minerals of the serpentine-kaolinite group. It has been
shown that the chemical composition in the projection field is controlled by the formula, the unit
of which is: (R~u§Ry3+%)(Si~2_ x)Alx)O5(OH)4, where u + y + z = 3, z = y - x. Using projection
fields for different chemical systems it has been shown that among the most important end-
members are kaolinite minerals, true serpentines, berthierine, brindleyite, amesite, cronstedtite,
greenalite, nepouite and their analogues having different substitutions in the octahedral sheets.

CRYSTALLOCHEMICAL CLASSIFICATION
As shown for micas (Part I) and chlorites (Part II), the chemical composition and its relation
to structure may be represented using the vector concept. If significant chemical
composition, as given by the crystallochemical formula, is assigned to a definite point located
at the intersections of isolines, this concept becomes also a useful basis for crystallochemical
classification of minerals characterized by the 7 A repeat unit, i.e. the serpentine-kaolin
group.
As for micas and chlorites, the projection field contains isolines:

IR2+ - sum of divalent cations, Mg, Fe 2+, Ni and M n per three octahedral positions;
IR 3§ - sum of trivalent cations, AI, Fe 3§ and Cr per three octahedral positions;
ID - n u m b e r of vacant sites per three octahedral positions;
[Si(4- x) - n u m b e r of Si per two tetrahedral positions, where x is the n u m b e r of trivalent
cations substituting for Si.

The nodes at the intersections of the following isolines:

IR 2+ = 3, [R 3+ = 0, IG = 0, ISi = 2
IR 2+--2, [R 3 + = 1 , ID=0, ISi=l
[R 2+ = 0, [R 3+ = 2, I[] = 1, ISi = 2
are chosen as three corners delimiting the projection field for the serpentine-kaolin minerals
(Fig. 1).
A layer of serpentine and kaolin contains one tetrahedral and one octahedral sheet as
compared to two of each in a layer of chlorite, so the crystallochemical formula unit is:
(R~ + Ry3+ Dz) (Si~2_ x)Alx)Os (OH)4, where u + y + z = 3, z = y - x. A composition projecting
in any point of the field is controlled by this formula.
9 1990 The Mineralogical Society
94 A. Wiewi6ra

SERPENTINES-- KAOLINS

~ dioctahedraI ~ trioctahedral ~
Rz*=O Re*=1 RZ*=2 RZ*=3

/ o=o.s / o=o
4R~'o)Si2 / R3~..SI 2 / /

,/
.=. _ ~ - 9 /(R~)CSil~R3& )

L/ Si=l--:R~'Ra*)(SiR 3.)
Fie. 1. Projection field for the condensed chemical composition of 1:1 phyllosilicates.
Composition isolines: R2+-Mg, Fe 2+, Ni, Mn, Zn; Ra+-A1, Fe3+, Cr; D-vacancies.

The projection field is divided along the isoline ID = 0.5 into two parts. They correspond to
the trioctahedral subgroup, the serpentines, and the dioctahedral subgroup, the kaolins.
Further differentiation must be carried out within certain chemical systems. Kaolins are
aluminium silicates but serpentines are magnesium or iron (rarely nickel or manganese)
silicates, alumino-silicates or ferrosilicates. The chemical composition of the most frequent
serpentines and kaolins may be enclosed in the polyhedron (Fig. 2) belonging to the
A1-Mg-Fe2+-E~ system of the composition of the octahedral sheet. The bottom, the right wall
(Fig. 3), and the top (Fig. 4) of this polyhedron are good two-dimensional approximations of
this system and are convenient to represent end-member compositions of such minerals, like
lizardite and other Mg-serpentines, berthierine, amesite, greenalite and kaolins. For
cronstedtite, another polyhedron must be constructed, the top of which is presented in Fig. 5.
Kaolins are characterized by a simple and uniform chemical composition such as that
represented in the left-hand comer of the triangle in Figs. 1-6. In contrast to most other
phyllosilicates, they are free of isomorphous substitutions. Some authors claim to find
substitutions in octahedral or tetrahedral sites, related to big cations in the interlayer space,
but fully documented substitution in kaolin polymorphs has been described only in
Cr-halloysite by Maksimovi6 & White (1973). Structural layers with Fe 3+ in octahedra that
might build theoretical Fe*-kaolinite (left-hand comer in Fig. 5) exist only in chapmanite and
bismutoferrite, due to the stabilizing effect of the interlayer Sb and/or Bi (Zhoukhlistov &
Zvyagin, 1977).
End-member serpentines with such cations as Ni, Zn and Mn usually constitute solid-
solution series with those serpentines presented in Fig. 2, e.g. nepouite is the Ni analogue of
lizardite, and zinalsite and kellyite are the Zn and Mn analogues of amesite. Other Ni-, Zn-

* In this work such a prefix indicates the predominant octahedral cation. It should not be confused with
exchangeable interlayer cation not considered here.
Classification of phyllosilicates--serpentine-kaolin group 95

M g - Ni --At- n - S E R P E N T I N E S - KAOLINITES
Ni=3
~=o
9 /N~sSi2
NI=2 +~NEPOUITE

At 1 /

~L"+-L -L - -/- - - ~ " ~ L ~ M (s'="'o~)


Ni=O Jl / \ ~ . / ' f / Ni-BE+RTHIERINE

AI2o Si2~ / I/~,;E/71 / JMg3S+2 . .

Mg=0\ ~ I /-""~': "t~Ni2A+li'iSiAtJ/ t


S =:o
(Mgi,7~$AI Do.25)|S~.5AI.~10:5) ~ / S i = 1 . 5
. '~M'g--:B'-N~L'
ff, ~'YiTE"---/~Mgm-~O.5)(Si,sAIo.5)
~ \'--~. / +M;:;~+;;.,~.,.~
Mg'=l ~ V / -

(Mg2At)(SiAl)",,~ Si=l
AMESITE / - -

a=O/,
Mg=2/
AI=I
FIG. 2. Composition polyhedron for 1:1 phyllosilicates with Mg, Fe 2+, AI and [] in octahedra.

Mg_ At_o- SE RPENTINES-KAOLINS A.


/_ 0+.,..0., ,.+o<,.,.0., I
M =0 Mg_l Mg 2 " Mg-:3~"'"-'--~,Oct.+ fNTIN
~,l:~+, , At:~ I Al:~ o ~'~+;--I~o s
\1.=:1 I tf:~ tP =' /." ~'+~ ,
~i "~ . l " v ,,_ ~," 1.~o.-, "-,-'2
. . . . -'kk(Al2rl)Si2 ] I A I Mg+~'l/ ~ / "~'=Z 1,,. I~'e2~3

Si I.(5
M-g .....

X II I / I /'/ ~(~eL+..

~ :'=~;i~ " ~/,/r~-~s:~,,,,.


~4 MESI ~'s

FIG. 3. Projection field for phyllosilicates with Mg, AI and [], (a bottom) and with Mg, Fe z+ and
A1 (a side wall of Fig. 2).
96
A. Wiewi6ra
Fe2+-AI-o-SERPENTINES-KAOLINS

, ~ di~ D/~ tri~ j I

Fe2%0 Fe2*_-1 Fe>_-2 FEZ*=3


AI=2 o 1 At=l AI=0
I,-- I I i?=o

(Fe~;sAl%2r)(Si' ~los),/( Fe~.~Alos)(Si,,a[o5)

Si=l 'N~/(Fe~"AI)(SiAI)
F@2t-AMESITE
FIG. 4. Projection field for 1: 1 phyllosilicates with Fe2+, Al and [] in octahedra.
Fe2"-- Fe3 " - o--SERPENTINES--KAOLINS

]. dioctahedral ~ trioctahedra[~
Fe2*=0 Fe2*= 1 Fe2*= 2 Fe2+=3
Fe3.=2
\lO=l. I F~:I
/ O=Z. I F,3.=0 .
~'O=,.i
~. /(Fern) Si z / Fe~*Siz' /

Sil --W(Fe~Fe3*)(Si Fe3")


CRONSTEDTITE
FIG. 5. Projection field for 1: 1 phyllosilicates with Fe 2+, Fe3§ and t~ in octahedra.

and/or Mn-serpentines are brindleyite, baumite, and caryopilite, respectively; tosalite is


regarded as manganoan greenalite (Bayliss, 1981). From among the three specified elements
the most important seems to be Ni. A polyhedron is then constructed for the system
Mg-Ni-AI-~, representing the composition of the octahedral sheet (Fig. 6). Apart from the
known end-members of the trioctahedral minerals such as lizardite, amesite, nepouite and
brindleyite, the Ni analogue of amesite is placed under the name Ni-amesite, as nimesite has
Classification of phyllosilicates--serpentine-kaolin group 97
Mg-- FeZ'--AI-n-SE RPE NTINES -- KAOLIN S
Fe%3

LITE

Fe

(Ai 201)Si 2 LSi=2


NAOLINITE]/ ITE

a=1
Mg=(

Ato.5)

o=O/I AM';'SJTE
Mg=2 l
AI=I
FIG. 6. Composition polyhedron for 1: 1 phyllosilicates with Mg, Ni, A1, and [] in octahedra.

been rejected by the Nomenclature Committee of the I M A (Maksimovi6 & Bish, 1978) on the
basis that it is too similar to nimite (Ni-chlorite).
Biindleyite, a nickeloan aluminous serpentine mineral (Nil.ysA1L,0[]0.25)(Sil.sA10.5)O 5(OH)4
(Maksimovi6 & Bish, 1978) is not an analogue of berthierine as postulated by these authors. It
occupies a distinct position in the projection field (Fig. 3); it is then a definite species having
its own crystallochemical characteristics different from berthierine. The difference is in the
octahedral vacancies, and twice the content of octahedral A1 as compared to berthierine,
apart from the Ni content. It is justified to leave the name brindleyite for the nickeloan
brindleyite, as it has been approved by the I M A Commission on New Minerals and Mineral
Names. Therefore its Mg-variety will be distinguished by a prefix, Mg-brindleyite, similarly
to Mg-berthierine which was originally iron bearing.
Odinite, a newly reported clay mineral (Bailey, 1988) has 'the structure based on 1:1
serpentine-like layer that is intermediate between dioctahedral and trioctahedral'. In odinite,
octahedral cations range from 2.3-2.54 per three sites for ten samples. Evidently the unstable
chemical composition makes it impossible to project the

(Fe3~8 Mg0.v7A10.56Fe02+8Ti0.02Mn0.0,)2.4n0.6(Si,.79A10.2~)Os (OH)4


crystallochemical formula for the purest sample in one point of the projection field, as the
formula does not fulfil the condition z = y - x (compare D0.6 and z = 1 . 3 6 - 0.21 --- 1.15).
However, points which are obtained from projection using orthogonal and oblique
coordinates indicate that the structure of odinite is dioctahedral.
98 A. Wiewi6ra
The classification presented for the serpentines includes several important compositional
.joins. Among the most important, participating in solid-solutions are:

Rz3+SizOs(OH)4 - - s e r p e n t i n e , greenalite, nepouite


(Re. 2+ 3+
5 m~. 5)(S i 1.5R~.5
3+)05(OH)4 --berthierine
u2+
~ 1 . 7 5 u3+
XXl.0 []0.25)(Sil.sR~+)Os(OH),__brindleyite
(R~.~R3+) (SIR3 +)O5 (OH)4 - - a m e s i t e , cronstedtite

The listed names of distinctly different mineral species should be considered as the
pre-eminent representatives of the trioctahedral subgroup of 1 : 1 minerals.
It is very significant that all the sensu stricto serpentines are located at/or close to isoline
I[] = 0 intersecting IMg = 3 (Figs. 1-6). This indicates the tendency to fill all the octahedra in
the structures with the comparable big cations. The net result is a bigger unit mesh of the
octahedral than the tetrahedral sheet. This reflects in an unusual morphology from the
normal planar type prevailing in lizardite, via alternating waves of antigorite, to cylindrical
rolls of chrysotile.

ACKNOWLEDGMENTS
Sincere thanks are due to Dr. Mackenzie and Prof. Bailey for critical reading and corrections in all three parts
of the manuscript, and to Prof. Dr. J. M. Serratosa of the Institute of Material Sciencein Madrid for providing
assistance for drawing reproducible figures. This work was fulfilled within project CPBP 03.04.

REFERENCES
BArnEYS.W. (1988) Odinite, a new dioctahedral-trioctahedral Fe3+-rich 1:1 clay mineral. Clay Miner. 23,
237 247.
BAYUSSP. (1981) Unit cell data of serpentine group minerals. Mineral. Mag. 44, 153-156.
MAKSIMOVICA.P. & WHITEJ.L. (1973) Infrared study of chromium-bearing halloysites.Proc. Int. Clay Conf.
Madrid, 61-73.
MAKSIMOVI~Z. & BISH D. (1978) Brindleyite, a nickel-rich aluminous serpentine mineral analogous to
berthierine. Am. Miner. 63, 484-489.
ZHOUKHLISTOVA.P. & ZVYAGINB.B. (1977) Crystal structure determination of chapmanite and bismutoferrite
by high-voltage electron diffraction. Kristallographiya 22, 731-738 (in Russian).