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Mineralogical Magazine, June 2007, Vol. 71(3), pp.

285–320

True and brittle micas: composition and solid-solution series


G. TISCHENDORF1, H.-J. FÖRSTER2,*, B. GOTTESMANN3 AND M. RIEDER4
1
Bautzner Strasse 16, D-02763 Zittau, Germany
2
Institute of Earth Sciences, University of Potsdam, P.O. Box 601553, D-14415 Potsdam, Germany
3
GeoForschungsZentrum Potsdam, Telegrafenberg, D-14473 Potsdam, Germany
4
Institute of Materials Chemistry, TU Ostrava, 17. listopadu 15/2172, CZ-708 33 Ostrava-Poruba, Czech Republic
[Received 8 May 2007; Accepted 11 September 2007]

ABSTR ACT

Micas incorporate a wide variety of elements in their crystal structures. Elements occurring in
significant concentrations in micas include: Si, IVAl, IVFe3+, B and Be in the tetrahedral sheet; Ti, VIAl,
VI
Fe3+, Mn3+, Cr, V, Fe2+, Mn2+, Mg and Li in the octahedral sheet; K, Na, Rb, Cs, NH4, Ca and Ba in
the interlayer; and O, OH, F, Cl and S as anions. Extensive substitutions within these groups of
elements form compositionally varied micas as members of different solid-solution series. The most
common true K micas (94% of almost 6750 mica analyses) belong to three dominant solid-solution
series (phlogopite–annite, siderophyllite polylithionite and muscovite celadonite). Their classification
parameters include: Mg/(Mg+Fetot) [=Mg#] for micas with VIR >2.5 a.p.f.u. and VIAl <0.5 a.p.f.u.;
Fetot/(Fetot+Li) [=Fe#] for micas with VIR >2.5 a.p.f.u. and VIAl >0.5 a.p.f.u.; and VIAl/(VIAl+Fetot+Mg)
[=Al#] for micas with VIR <2.5 a.p.f.u. The common true K micas plot predominantly within and
between these series and have Mg6Li <0.3 a.p.f.u. Tainiolite is a mica with Mg6Li >0.7 a.p.f.u., or,
for transitional stages, 0.3 0.7 a.p.f.u. Some true K mica end-members, especially phlogopite, annite
and muscovite, form binary solid solutions with non-K true micas and with brittle micas (6% of the
micas studied). Graphical presentation of true K micas using the coordinates Mg minus Li (= mgli) and
VI
Fetot+Mn+Ti minus VIAl (= feal) depends on their classification according to VIR and VIAl,
complemented with the 50/50 rule.

K EY WORDS : true micas, brittle micas, classification, solid-solution series, composition.

Introduction
Following an idea and proposal of Charles
MICAS are widespread in igneous, metamorphic Guidotti{, our colleague, friend and co-author of a
and sedimentary rocks. Their crystal structure recent paper on micas (Tischendorf et al., 2004),
accommodates a plethora of elements, leading to we present in this paper a survey and analysis of
a large and diverse mineral group. The composi- composition and solid solution in the mica group,
tional diversity of micas has led to numerous comprising trioctahedral and dioctahedral,
attempts at classification and graphical presenta- common and uncommon true K micas, other
tion (Foster, 1960a,b; Tröger, 1962; Rieder et al., alkali-element-bearing micas, and brittle micas.
1970, 1998; Koval et al., 1972; Gottesmann and The principles behind the subdivision, and the
Tischendorf, 1978; Černý and Burt, 1984; Monier graphical presentation adopted, follow the recom-
and Robert, 1986; Jolliff et al., 1987; Burt, 1991; mendations of the Mica Sub-committee of the
Tischendorf et al., 1997, 2004; Sun Shihua and International Mineralogical Association’s
Yu Jie, 1999, 2000). Commission on New Minerals, Nomenclature

* E-mail: forhj@gfz-potsdam.de
{
DOI: 10.1180/minmag.2007.071.3.285 Died 19 May 2005

# 2007 The Mineralogical Society


TISCHENDORF ET AL.

and Classification (IMA-CNMNC) (Rieder et al., (2) uncommon brittle micas (0.4%): contain V,
1998) and the IMA principles of mineral Be, Fe3+, Ti or S and O as major elements, in
classification. This paper treats the micas only in addition to Ca or Ba [in anandite, bityite,
terms of their compositions, an approach that chernykhite, oxykinoshitalite].
permits a quick and easy classification of any
mica. Common true K micas
Principles of classif|cation
Methods Our classification scheme uses four major,
This study is based on mica analyses obtained by octahedrally-coordinated cations (Mg, Fetot,
VI
different analytical methods (wet chemical, X-ray Al, Li) together with the existence of solid
fluorescence, electron- and ion-microprobe solutions. It considers only IMA-approved end-
analysis). Data sources not listed in the member names and strictly applies the 50/50 rule
References are given in previous publications (e.g. Nickel, 1992).
(e.g. Tischendorf et al., 1997, 1999, 2001a,b, The main parameters in this classification are
VI
2004) or are noted in Deer et al. (2003). R, VIAl and the product Mg6Li (all in a.p.f.u.).
The crystallo-chemical formulae were calcu- The value of VIR = 2.5 differentiates trioctahedral
lated on the basis of 22 cation charges, except for from dioctahedral micas. The limiting value
oxy-micas with 24 cation charges. The concentra- between micas of the phlogopite–annite and
tion of Li2O, if essential but not known, was siderophyllite–polylithionite series (VIAl = 0.5)
estimated using the empirical equations published results from the application of the 50/50 rule. The
by Tischendorf et al. (2004, their Appendix). same is valid for the parameter Mg6Li, which
separates tainiolite micas (Mg6Li >0.3) from all
other trioctahedral micas (Mg6Li <0.3).
Results
Compositionally, micas are subdivided into true (1) Phlogopite–annite series
micas, with monovalent cations in the interlayer, trioctahedral (VIR >2.5); VIAl <0.5; Mg6Li <0.3
and brittle micas containing divalent cations in the end-members: phlogopite KMg3[AlSi3O10](OH)2,
interlayer. Our evaluation of mica analyses yielded annite KFe2+ 3 [AlSi3O10](OH)2
the following quantitative subdivisions (in percen- classification according to the ratio Mg/
tages of the total population of ~6750 analyses). (Mg+Fetot) [= Mg#]
True micas (96.8% of all analyses) comprise: phlogopite: Mg# >0.5
(1) common true K micas (93.1%): [annite, annite: Mg# <0.5
celadonite, muscovite, phlogopite, polylithionite, (2) Siderophyllite polylithionite series
siderophyllite, tainiolite]; trioctahedral (VIR >2.5); VIAl >0.5; Mg6Li <0.3
(2) uncommon true K micas (1.6%): contain a e n d - m e m b e r s : s i d e r o p h y l l i t e K F e 22 + A l
minor element (Mn2+, Fe3+ or F) in an above- [Al2Si2O10](OH)2, polylithionite
average concentration [fluorannite, masutomilite, KLi2Al[Si4O10]F2;
montdorite, shirozulite, tetra-ferriannite, tetra- classification according to the ratio Fe tot /
ferriphlogopite], an uncommon element (Zn, V, (Fetot+Li) [= Fe#]
Cr, Mn3+ or B) as major element [in boromusco- siderophyllite: Fe# >0.5
vite, chromphyllite, hendricksite, roscoelite, polylithionite: Fe# <0.5
norrishite] or a common element in an uncommon (3) Tainiolite group
coordination (e.g. Na+ in shirokshinite); trioctahedral (VIR >2.5); Mg6Li for tainiolite
(3) uncommon true non-K micas (2.1%): sensu stricto >0.7, for tainiolitic micas 0.3 0.7
contain the monovalent cations Na, Rb, Cs or end-member: tainiolite KLiMg2[Si4O10]F2
NH4 as major element substituting for K [in (4) Muscovite celadonite series
aspidolite, ephesite, nanpingite, paragonite, preis- dioctahedral (VIR <2.5); Mg6Li <0.3
werkite, sokolovaite, tobelite]. end-members: muscovite KAl 2 &[AlSi 3 O 10 ]
Brittle micas (3.2% of all analyses) comprise: (OH)2, celadonite: KMgFe3+&[Si4O10](OH)2;
(1) common brittle micas (2.8%): contain Ca or classification according to VIAl/(VIAl+Fetot+Mg)
Ba as major cations proxying for K [in clintonite, [= Al#]
ferrokinoshitalite, ganterite, kinoshitalite, muscovite: Al# >0.5
margarite]; celadonite: Al# <0.5

286
CLASSIFICATION OF MICAS

Celadonites are further subdivided according to Li maximum in the frequency distribution of natural
et al. (1997) as confirmed by Rieder et al. (1998). muscovite compositions is close to the end-
member composition. Two frequency peaks
Distribution of natural compositions in the mgli feal occur in the phlogopite–annite series, and one
plot occurs in the siderophyllite–polylithionite join.
Mica compositions may be described in two- Very few compositions plot in the relatively large
dimensional triangular or three-dimensional plots areas in the Mg-Al sector (lower right) and in
(cf. Tischendorf et al., 2004, for a compilation). smaller areas in the Fe-Li sector (upper left) of the
We have proposed a simple two-dimensional plot. Figure 2 shows the numbers of cations per
presentation according to the occupancy of the formula unit for compositions in the phlogopite–
octahedral sheet, using the parameters Mg minus annite, siderophyllite–polylithionite and
Li (= mgli) and VIFetot+Mn+Ti minus VIAl (= muscovite–celadonite series. Figure 3 shows
feal) a.p.f.u. (Tischendorf et al., 1997, 2004). species resulting from the application of the
Figure 1 shows common true K micas, 50/50 rule. Joins combining related end-members
excluding only tainiolite and celadonite. The are displayed and so are the half-way divides.

FIG. 1. mgli/feal plot of ~6100 common true K-mica compositions (excluding tainiolite and celadonites). Mica end-
members, ideal members, and one theoretical component are indicated. Isolines show relative densities of
composition points (1, 5, 10, 20, 30%) normalized to the density maximum at mgli = 0.05 and feal = 1.70 (the most
frequent muscovite composition), which is taken as 100%. Abbreviations: ann annite, eas eastonite, hyp-mus
hyper-muscovite, mus muscovite, phl phlogopite, pol polylithionite, sid siderophyllite, trans-mus
transitional muscovite, tri trilithionite.

287
TISCHENDORF ET AL.

FIG. 2. Phlogopite annite and siderophyllite polylithionite series, and the muscovite portion of the muscov-
ite celadonite series plotted in the mgli/feal diagram. Mica end-members, ideal members, and one theoretical
component are indicated. The boundary between the first two series (VIAl = 0.5) and their boundary with muscovite
(VIR = 2.5) is marked by dashed lines. Note that two boundaries are shown in the transitional area between annite and
siderophyllite (both for VIAl = 0.5), one at VIR = 3.0, and another at VIR = 2.75. See Fig. 1 for abbreviations.

Compositional characteristics
phlogopites, 12% Ti-Fe-rich phlogopites, 5% Al-
In the following, we point out important Fe-rich phlogopites, 4% Ti-rich phlogopites (up to
compositional features of common true K micas 0.75 a.p.f.u. Ti), and 1% Al-rich phlogopites (up
in Fig. 4, some of which shed new light on the to 0.5 a.p.f.u. VIAl; for example Ferry, 1981)
relationships between common true K micas, (Appendices 1a and b). Few phlogopites have
uncommon true micas and brittle micas. Because larger Mn contents, but some (4%) contain
of the wide compositional variation of common considerable fluorine (>1 a.p.f.u.; Stoppa et al.,
true K mica species, we characterize varieties 1997, Motoyoshi and Hensen, 2001); the latter
according to their compositions (Appendices 1 5). should be termed F-rich phlogopite. Phlogopite
Phlogopite (1814 analyses): Many composi- enriched in Zn or V (up to 0.6 a.p.f.u.) is
tions (43%) have insufficient IVAl, suggesting that uncommon. The maximum contents (in a.p.f.u.)
Fe3+ and/or Ti4+ may be present in the tetrahedral are 0.20 for Cr, 0.12 for Cs, 0.04 for Ni and 0.07
sheet. Of these compositions, 28% are so close to for Rb. Barium behaves differently, because a
the end-member formula that they may be referred solid-solution series exists from phlogopite–
to as phlogopite sensu stricto; 50% are Fe-rich kinoshitalite (cf. Figs 11a and 12).

288
CLASSIFICATION OF MICAS

FIG. 3. Mica species in three dominant solid-solution series among common true K micas plotted in the mgli/feal
diagram. Mica end-members, ideal members, and one theoretical component are indicated. Boundaries between the
series are dashed, and between species are shown by dash-and-dot lines. Between annite and siderophyllite, for
VI
Al = 0.5, only the boundary at VIR = 2.75 is shown. Also inserted are lines joining mica end-members (dotted),
with 50/50 divides indicated. The arrow marks the direction towards celadonite (cel). Areas devoid of mica
compositions are not labelled. See Fig. 1 for abbreviations.

Annite (1376 analyses): in this group, 15% of (0.3 0.6 a.p.f.u.). Large concentrations of Ba
the samples analysed appear to have no VIAl. (0.3 0.5 a.p.f.u.) may be an indication of a
Only 7% refer to annite sensu stricto. Most solid-solution series between annite and ferroki-
annites (50%) are classified as Mg-rich annite, noshitalite (cf. Figs 11a and 12).
33% as Al-Mg-rich annite, 5% as Ti-Mg-rich Siderophyllite (748 analyses): most micas
annite (up to 0.65 a.p.f.u. Ti), and 3% as Al-rich (58%) classified in this group are Li-rich side-
annite. About 2% of the annite micas contain rophyllites (with F up to 1.8 a.p.f.u.), followed by
>0.3 a.p.f.u. Li and, therefore, represent Li- or Li- Mg-rich siderophyllite (25%), and siderophyllite
Al-rich annite (Appendices 2a and 2b). Li-rich sensu stricto (17%) (Appendices 3a and 3b).
annite is usually also enriched in F (up to However, compositions corresponding to ideal
1.4 a.p.f.u.; e.g. Kile and Foord, 1998). A few KFe2+2 Al[Al2Si2O10](OH)2 do not occur in nature
annites are Cl-rich (in the range 0.3 0.9 a.p.f.u.; (Fig. 24). Because Si4+ does not occur below
Oen and Lustenhouwer, 1992). Also uncommon 2.5 a.p.f.u. (except for micas with Ba2+ and/or
are annites containing large concentrations of Zn Ca 2+ and/or Fe 3+ >0.5 a.p.f.u. and/or Ti4+
(0.3 0.6 a. p . f.u.; Tr a c y , 1 9 91 ) o r M n >0.25 a.p.f.u.), the octahedral sheet must accom-

289
TISCHENDORF ET AL.

FIG. 4. Average values and 1s standard deviations (open squares and error bars) of common true K mica varieties in
the mgli/feal diagram (Appendices 1 4). The boundary between annite and siderophyllite is given for VIAl = 0.5 at
VI
R = 2.75. Boundaries between the series are dashed; boundaries between species are marked by dash-and-dot lines.
Mica end-members, ideal members, and one theoretical component are indicated. tai tainiolite. See Fig. 1 for
further abbreviations. Mica varieties are characterized by element prefixes, e.g. Ti-Fe means Ti-Fe-rich phlogopite.

modate more divalent (Mg2+) and univalent (Li+) Polylithionite (648 analyses): half of all
cations to balance charges. Therefore, a more polylithionites are polylithionite sensu stricto,
realistic composition would be KFe2+ 1.75Al0.75 the rest being Fe-rich polylithionite. About 80%
Li0.25Mg0.25[Si2.5Al1.5O10](OH)2 (for VIR = 3.0) of the compositions contain 1.0 2.0 a.p.f.u. F
or KFe 2+1.75 Al 0.75 & 0.25 Li 0.125 Mg 0.125 [Si 2.875 (Appendices 3a and 3b). The Rb concentration
Al1.125O10](OH)2 (for VIR = 2.75), respectively seldom exceeds 0.3 a.p.f.u., but one Rb-rich
(Appendix 3b, and Tischendorf et al., 2004). polylithionite (unnamed) contains 0.82 a.p.f.u.
Compositionally, siderophyllite is an atypical end- Rb (Černý et al., 2003). Concentrations of Cs in
member mica, because it plots in the centre of all polylithionite are usually large, and Cs-rich
K-mica compositions. It contains all the principal varieties (up to 0.88 a.p.f.u., Wang et al., 2004)
elements of the octahedral sheet, Fe, VIAl, Mg and do exist. Sokolovaite, a Cs analogue of poly-
Li. A few siderophyllites contain Mn lithionite, was proposed by Pautov et al. (IMA
(0.30 0.35 a.p.f.u., Abdalla et al., 1994; 2004-012; Burke and Ferraris, 2005).
Mohamed et al., 1999), with Cs and Rb contents Tainiolite (28 analyses) and tainiolitic micas
of up to 0.20 and 0.15 a.p.f.u., respectively. (31 analyses): in contrast to common true K micas,

290
CLASSIFICATION OF MICAS

characterized either by high Mg or high Li, (2) Fe-rich tainiolitic micas; characterized by
tainiolite has high Mg (0.5 2.3 a.p.f.u.) and high Mg6Li = 0.3 0.7; Fetot >0.9; Si = 2.6 3.1; in
Li (0.4 1.0 a.p.f.u.) (Appendix 4). Such composi- Red Cross/Tanco pegmatites (Morgan and London,
tions have a unique position within the mica 1987; Hawthorne et al., 1999); transitional to Mg-
group. By containing some Al and Fe, tainolite rich annite, but unusually enriched in Li;
deviates slightly from ideal KLiMg2[Si4O10]F2. (3) Al-rich tainiolitic micas; characterized by
Also, it has moderate concentrations of Rb and Cs. Mg6Li = 0.3 0.7; VIAl >0.6; Si = 2.6 3.1; in
Tainiolite can, of course, be plotted in terms of spodumene pegmatites (Kuznetsova and
mgli/feal, but because of possible coincidence with Zagorskiy, 1984; Semenov and Shmakin, 1988:
unrelated mica compositions, it should be treated ‘magnesian zinnwaldite’, Pesquera et al., 1999);
as a separate subsystem (Fig. 5). Tainiolites are transitional to Li-rich siderophyllite, but
theoretically characterized by Mg6Li >0.5 unusually enriched in Mg.
a.p.f.u. In addition to tainiolite sensu stricto, The positive correlation of Mg and Li applies
other micas with large Mg and large Li contents only to tainiolite sensu stricto. In Fe-rich and Al-
occur that are intermediate between tainiolite and rich tainiolitic micas, MgO and Li2O correlate
other common true K micas. Such micas may be negatively, as in all other micas. We stress that, in
termed tainiolitic micas. These micas are typically the mgli/feal plot, the area of tainiolite sensu
enriched in Cs. Accordingly, we may distinguish stricto shows no overlap with the area of
three groups of tainiolites (Appendix 4): siderophyllite (Fig. 4).
(1) Tainiolite sensu stricto; characterized by Muscovite (1574 analyses): most muscovites
Mg6Li >0.7 a.p.f.u.; Mg >1.9 a.p.f.u.; Si = (55%) have compositions close to the ideal
3.1 4.0 a.p.f.u.; in carbonatites (Le Bas et al., formula and exhibit very limited chemical
1992; Cooper et al., 1995); transitional to variation. The next most common compositions
phlogopite, but unusually enriched in Li; are Fe-rich muscovite and Mg-rich muscovite

FIG. 5. mgli/feal plot for the end-member tainiolite sensu stricto and other pertinent end-members connected by tie
lines. Also shown are the 50/50 divides, which outline the field of micas belonging to tainiolite sensu stricto. See
Figs 1 and 4 for abbreviations.

291
TISCHENDORF ET AL.

(16% each). Li-Fe-rich muscovite (6%), Li-rich Mg, Fe2+, Li and VIAl, or micas with tetrahedral
muscovite (5%), and Mg-Fe-rich muscovite (2%) cations that are different from Si and IVAl.
are comparatively rare (Appendices 5a and b).
Generally, the concentration of other elements in Interlayer
muscovite is small. Related dioctahedral mica Instead of K, the following elements may be
end-members (e.g. roscoelite, chromphyllite, the dominant cation in the mica interlayer: Na,
ganterite), which form solid-solution series with Cs, Rb, NH4, Ca and Ba.
muscovite, explain large concentrations of V, Cr K–Na substitution. The substitution of Na in the
and Ba in the latter (Morand, 1990; Breit, 1995; interlayer of common trioctahedral K micas
Treolar, 1987; Hetherington et al., 2003). (Fig. 7a) generally ranges up to 0.4 a.p.f.u., and
Concentrations of F, up to ~2 a.p.f.u., may only rarely beyond 0.45. Full replacement of K by
occur in Li-rich muscovite. Concentrations of Na in phlogopite and eastonite leads to aspidolite
Rb do not exceed 0.2 a.p.f.u. (Zagorskiy and
Makrygin, 1976; Lagache and Quéméneur, 1997).
Celadonite micas (61 analyses): only limited
information is available about the presence of trace
or minor elements (Appendix 4). End-member
compositions of celadonites are given by Li et al.
(1997) and are confirmed by Rieder et al. (1998).
The general formula is: K(Mg,Fe2+)(Fe3+,Al)
&[Si4O10](OH)2. The mode of graphical presenta-
tion proposed by Li et al. (1997) is equivalent to
mgli/feal. However, because of their Fe3+ concen-
trations, celadonites must be presented either
jointly with muscovite (Tischendorf et al., 2004)
or in a separate plot (Fig. 6).

Uncommon true K micas, other alkali and brittle micas,


and their relation to common true K micas
Uncommon true and brittle micas are similar to
common true K micas because they exhibit the
same kinds of cation substitutions in octahedral
and tetrahedral coordination. These substitutions
follow from (1) the requirement of charge balance
and (2) ion-size constraints of cation coordina-
tions. In practice, the same ‘unusual’ elements,
known to enter uncommon true and brittle micas
(Ba, Ca, Na, Rb, Cs, Mn, Zn, Cr, V), also enter
common true K micas and are normally analysed
for. Exceptions are the highly unusual NH4, B and
Be. Occupancy of the octahedral sheet is the basis
for the classification of common true K micas,
and it can equally well serve the same purpose for
the uncommon true and brittle micas. These latter
mica also can be plotted in terms of mgli and feal
coordinates; however, most of them tend to
cluster along the periphery of the diagram.
Common true K micas, in particular phlogopite,
annite and muscovite, act as end-members of
solid-solution series with uncommon true or
brittle micas. Examples of such series may be FIG. 6. Classification of the celadonite family in the mgli/
micas with the interlayer occupied by atoms other feal diagram.according to the principles of Li et al.
than K, micas with octahedral cations other than (1997).

292
CLASSIFICATION OF MICAS

(19 analyses) and preiswerkite (26 analyses), dominant interlayer cation has yet been observed
respectively. The Na mica ephesite (9 analyses) in nature. The substitution of Rb in the interlayer
has no K counterpart. Likewise, the substitution of common true K micas rarely exceeds
of Na in common dioctahedral K micas is 0.20 a.p.f.u. (Fig. 8). Exceptions are Rb-rich
<0.4 a.p.f.u. (Fig. 7b). The mica with a complete annite (0.45 a.p.f.u. Rb) and a still unnamed Rb
substitution of K by Na is paragonite analogue of ‘zinnwaldite’ (0.82 a.p.f.u. Rb; Černý
(72 analyses). There also exists a Sr-enriched et al., 2003).
variety of paragonite containing up to 0.23 a.p.f.u. K Cs substitution. Common trioctahedral
Sr (Bryanchaninova et al., 2004). The large micas may substitute up to ~0.20 a.p.f.u. Cs
difference in ionic radius between Na+ and K+ (Fig. 9). Černý et al. (2003) reported enrichment
makes likely the existence of a miscibility gap in of Cs in some phlogopite, annite and sidero-
all such binaries, manifest by a significantly phyllite micas. Also, there is a Cs-rich mica
increased number of compositions in which K or described as Cs polylithionite by Černý et al.
Na dominate relative to intermediate composi- (2003, one analysis) and Wang et al. (2004, 13
tions. Guidotti et al. (1994) examined the extent analyses). Sokolovaite is the Cs analogue of
of K Na substitution and associated other polylithionite (Pautov, IMA 2004-012; Burke and
chemical changes. Ferraris, 2005). Complete substitution of K by Cs
K Rb substitution. Although Voncken et al. in dioctahedral micas leads to nanpingite (3
(1987) synthesized the Rb analogue of muscovite, analyses, Yang et al., 1988; Ni and Hughes, 1996;
and Beswick (1973) experimentally demonstrated Peretyazhko et al., 2004). Data indicate a
complete miscibility between K and Rb in miscibility gap in the interval 0.20 0.60 a.p.f.u.
phlogopite, no end-member with Rb as the Cs, rather than complete substitution between K

FIG. 7. (a) Proportion of Na in XIIR for the series phlogopite (phl)–aspidolite (asp). Data for preiswerkite (prei) and
ephesite (eph) are given for comparison. Sodium (>0.1 a.p.f.u.) in phlogopite is shown as averages (n = number of
analyses) at 0.1 a.p.f.u. intervals. Numbers of analyses are given in parantheses; standard deviations are shown in
pale grey. Data sources: Schaller et al. (1967), Keusen and Peters (1980), Schreyer et al. (1980), Oberti et al. (1993),
Godard and Smith (1999), Visser et al. (1999), Costa et al. (2001), Ruiz Cruz (2004), Banno et al. (2005), Bucher et
al. (2005), Konzett et al. (2005). (b) Proportion of Na in XIIR for the series muscovite (mus)–paragonite (par).
Sodium (>0.1 a.p.f.u.) in muscovite is given as averages (n = number of analyses) at 0.1 a.p.f.u. intervals. Numbers
of analyses are given in parentheses; standard deviations are shown in pale grey. Data sources: Ackermand and
Morteani (1973), Höck (1974), Baltatzis and Wood (1977), Hoffer (1978), Katagas and Baltatzis (1980), Grambling
(1984), Harlow (1994, 1995), Bucher et al. (2005), Escuder-Viruete and Pérez-Estaún (2006). Sr-bearing paragonites
are from Bryanchaninova et al. (2004).

293
TISCHENDORF ET AL.

and Cs in both trioctahedral and dioctahedral


micas, which is attributed to the large difference
in ionic radius (Shannon and Prewitt, 1969;
Shannon, 1976).
K NH4 substitution. Among trioctahedral
micas, apparently only phlogopite rich in Fe
contains significant concentrations of NH 4
(~0.30 0.40 a.p.f.u.; D.E. Harlov, pers. comm.,
2005), in accordance with the hydrothermal
synthesis of end-member ammonium phlogopite
(Eugster and Munoz, 1966). Complete solid
solution between muscovite and tobelite has been
confirmed experimentally at T >400ºC (Pöter et al.,
2007). However, the analysed natural dioctahedral
micas show a gap in composition around 0.50 (e.g.
Nieto, 2002). In the NH4 XIIR–NH4 diagram
(Fig. 10), natural compositions display a large
scatter, possibly resulting from uncertainties in the
FIG. 8. Proportion of Rb in XIIR for annite (ann), analysis of N and the inability to analyse H by
siderophyllite (sid), polylithionite (pol), tainiolite (tai) electron microprobe.
and muscovite (mus). Rubidium (>0.1 a.p.f.u.) in K Ca substitution. The Ca concentration of
muscovite and polylithionite is given as averages (n = trioctahedral common true K micas does not
number of analyses) at 0.1 a.p.f.u. intervals. Numbers of exceed ~0.30 a.p.f.u. Larger Ca concentrations,
analyses are given in parentheses. Most data for Rb-rich corresponding to 0.9 1.0 a.p.f.u., are character-
micas come from Skosyreva and Vlasova (1983) and istic for clintonite (48 analyses), a brittle mica
Černý et al. (2003). violating the Löwenstein rule. Clintonite does not
appear to be the end-member of any solid-solution
series. High Ca, coupled with high Li and Be,
leads to the formation of the unusual brittle mica
bityite (13 analyses, Fig. 11a). Margarite (68

FIG. 9. Proportion of Cs (>0.1 a.p.f.u.) in XIIR for


phlogopite (phl), annite (ann), siderophyllite (sid),
polylithionite (pol), muscovite (mus), sokolovaite (sok) FIG. 10. Proportion of NH4 in XIIR for phlogopite (phl),
and nanpingite (nan). Data for Cs rich micas were taken muscovite (mus) and tobelite (tob). Data are taken from
from Yang et al. (1988), Hawthorne et al. (1999), Černý Higashi (1978, 1982, 2000) [Japan], Wilson et al. (1992)
et al. (2003), Peretyazhko et al. (2004) and Wang et al. [Utah, USA] and D.E.Harlov (2005, pers. comm.)
(2004). [Maine, USA; Erzgebirge, Germany].

294
CLASSIFICATION OF MICAS

analyses) is a dioctahedral brittle mica with Ca al., 2003; Hetherington et al., 2003; Ma and
concentrations in the range 0.5 1.0 a.p.f.u. Rossman, 2006) or chernykhite (2 analyses), if
VI
However, the Ca concentration in muscovite V simultaneously substitutes for VIAl.
reported to date is small, indicating the absence Phlogopite, kinoshitalite, annite and ferro-
of a solid-solution series between muscovite and kinoshitalite form complete solid solutions
margarite (Fig. 11b). (Figs 12a, 13). All four of these end-members
K Ba substitution. Unlike the substitutions participate in the series (see also Frimmel et al.,
above, the K Ba replacement in trioctahedral 1995, their Fig. 2). The K Ba substitution in the
micas of the phlogopite–annite series is almost interlayer is coupled with the tetrahedral substitu-
complete (cf. Greenwood, 1998). If the Ba-for-K tion XIIBa + IVAl > XII(K,Na) + IVSi (Brigatti and
substitution exceeds 0.5 a.p.f.u., the mica is Poppi, 1993). The concentration of Ba in
kinoshitalite (57 analyses) or oxykinoshitalite muscovite is usually <0.4 a.p.f.u., and ganterite
(2 analyses), an exotic, Ti-enriched mica known is characterized by Ba ~0.5 a.p.f.u. (Fig. 12b). A
only from an olivine nephelinite (Kogarko et al., composition corresponding to the ideal end-
2005). Ferrokinoshitalite (4 analyses) is a brittle member BaAl2&[Al2Si2O10](OH)2 has not yet
mica with an octahedral sheet resembling that of been reported from nature. The Ba-V-rich mica
annite (Guggenheim and Frimmel, 1999), whereas chernykhite described by Ankinovich et al. (1973)
anandite (5 analyses, Pattiaratchi et al., 1967) has contains only ~0.3 a.p.f.u. Ba and thus does not
an additional condition, namely that IVAl be reach beyond the required 50%.
replaced by IVFe3+ and that S be incorporated
instead of one (OH). In dioctahedral micas, a Octahedral sheet
partial replacement of K by Ba results in the Octahedral substitutions are responsible for the
formation of ganterite (13 analyses, Graeser et formation of uncommon true micas by: (1) the

FIG. 11. (a) Sum XIICa+IVAl as a function of XII(K,Na)+IV(Si,Be) for phlogopite (phl), annite (ann), siderophyllite
(sid), polylithionite (pol), clintonite (cli) and bityite (bit) (including Be-rich margarite). Calcium (>0.1 a.p.f.u.) in
common true K micas is shown as averages in 0.1 a.p.f.u. intervals. Numbers of analyses are given in parentheses,
and Ca contents (in a.p.f.u.) are indicated. Data for uncommon micas come mostly from Bucher-Nurminen (1976),
Guggenheim et al. (1983), Lahti and Saikkonen (1985), Ackermand et al. (1986), MacKinney et al. (1988), Alietti et
al. (1997) and Grew et al. (1999). (b) The sum XIICa+IVAl as a function of XII(K,Na)+IVSi for muscovite (mus)
(Ca>0.05 a.p.f.u.) and margarite (mar). Numbers of analyses are given in parentheses, and Ca contents (in a.p.f.u.)
are indicated. Data for margarite come mainly from Ackermand and Morteani (1973), Höck (1974), Gibson (1979),
Guidotti et al. (1979), Frey et al. (1982), Guggenheim et al. (1983), Lahti (1988), Morand (1990) and Godard and
Smith (1999).

295
TISCHENDORF ET AL.

FIG. 12. (a) Plot of XIIBa+IVAl vs. XII(K,Na)+IVSi for phlogopite (phl) and annite (ann) (Ba >0.1 a.p.f.u.) as well as
for kinoshitalite (kino), ferrokinoshitalite (Fekino) and anandite (ana). Numbers of analyses are given in parantheses,
and the Ba content (in a.p.f.u.) is indicated. Data sources for uncommon micas: Pattiaratchi et al. (1967); Lovering
and Widdowson (1968); Mansker et al. (1979); Filut et al. (1985); Solie and Su (1987); Bol et al. (1989); Dasgupta
et al. (1989); Tracy (1991); Edgar (1992); Bigi et al. (1993); Brigatti and Poppi (1993); Frimmel et al. (1995);
Henderson and Foland (1996); Jiang et al. (1996); Shaw and Penczak (1996); Guggenheim and Frimmel (1999);
Gnos and Armbruster (2000); Tracy and Beard (2003); Doležalová et al. (2005, 2006). (b). The plot of XIIBa+IVAl
vs. XII(K,Na)+IVSi for muscovite (mus) (Ba >0.05 a.p.f.u.) as well as for ganterite (gan) and chernykhite (cher).
Numbers of analyses are given in parantheses, and the Ba content (in a.p.f.u.) is indicated. Data for uncommon micas
were taken from Ankinovich et al. (1973), Graeser et al. (2003), Hetherington et al. (2003) and Ma and Rossman
(2006).

occurrence of common elements in unusually (Yoshii et al., 1973) and for annite up to 0.57
large concentrations (Mn2+, Fe3+, Ti); (2) the Mn a.p.f.u. (Chen and Wu, 1987). Norrishite (8
incorporation of unusual elements in significant analyses) is a rare Li-bearing mica with trivalent
concentrations (Zn, V, Cr); and (3) the incorpora- Mn. All these micas have high Mn, but they never
tion of an element in a valence state uncommon in reach the ideal Mn mica end-member (Eggleton
micas (Mn3+). and Ashley, 1989; Gnos et al., 2003). Montdorite
Incorporation of high Mn. Even though the Mn is an uncommon Mn-bearing, tetrasilicic transi-
concentrations of dioctahedral micas are tional mica that has yet been found at only one
<0.2 a.p.f.u., several trioctahedral Mn-bearing locality and for which only one single analysis is
micas exist, including shirozulite, the Mn available (Robert and Maury, 1979).
analogue of annite, produced by the substitution Hendricksite (3 analyses) may contain up to
of Mn2+ for Fe2+. No compositions close to the 1.1 a.p.f.u. Mn 2+ (Frondel and Ito, 1966;
end-member have been found. The composition Guggenheim et al., 1983) (Fig. 14).
reported in the original description (Ishida et al., Incorporation of high Zn. Hendricksite is the
2004) has only 1.53 a.p.f.u. Mn2+. Masutomilite, only uncommon trioctahedral mica in which the
the Mn-analogue of what used to be termed Zn concentration may reach 1.45 a.p.f.u. No
‘zinnwaldite’, owes its existence to the same Fe2+ doubt exists about the coordination of Zn
> Mn2+ substitution. However, the ideal Mn = because there is insufficient Mg (1 2.5 a.p.f.u.)
1.0 a.p.f.u. of the masutomilite lies beyond the and Fe2+ is low (<1 a.p.f.u.) (Frondel and Ito,
range of natural compositions (Harada et al., 1966; Frondel and Einaudi, 1968; Guggenheim et
1976). The most Mn-rich polylithionite al., 1983). Other phlogopites and annites may
(0.59 a.p.f.u.) was reported by Boggs (1992). have Zn concentrations up to 0.6 a.p.f.u. (Craig et
The most Mn-rich phlogopite has 1.1 a.p.f.u al., 1985; Tracy, 1991). Zinc concentrations in

296
CLASSIFICATION OF MICAS

siderophyllite, polylithionite and the dioctahedral


micas are comparatively small, mostly
<0.03 a.p.f.u. (Fig. 15).
Incorporation of high V. Enhancement in V3+ is
rare in trioctahedral micas (Pan and Fleet, 1991;
Deer et al., 2003, their Table 42, analysis 44).
Larger concentrations occur in dioctahedral
micas, for which the V content varies continu-
ously from V-rich muscovite to either roscoelite
(20 analyses) or the brittle mica chernykhite
(2 analyses). In roscoelite and chernykhite, V
replaces VIAl up to 1.7 a.p.f.u. (Ankinovich et al.,
1973; Hofmann, 1990; Meunier, 1994).
Reznitskiy et al. (1997) reported significant V in
chromphyllite (Fig. 16).
Incorporation of high Cr. Chromium behaves
much as V does. The Cr3+ contents of trioctahe-
dral micas are <0.2 a.p.f.u. (Fig. 17). However,
F IG . 13. XII Ba (>0.3 a.p.f.u.) as a function of Cr is concentrated in dioctahedral micas, for
Mg/(Mg+Fetot) [=Mg#] for phlogopite(phl)/kinoshitalite which there is a continuous series from muscovite
(kino-phl) [Mg#>0.5] and annite(ann)/kinoshitalite through Cr-rich muscovite (Treloar, 1987) to
(kino-ann) as well as ferrokinoshitalite(Fekino) chromphyllite (21 analyses). Chromphyllite
[Mg#<0.5]. The distribution of points for phlogopite-
may also display enrichment in Ba (up to
type and annite-type kinoshitalites may indicate the
0.2 a.p.f.u.; Reznitskiy et al., 1997).
existence of a solid-solution series across the whole
Incorporation of high Fe3+. The nature of entry
system.
of Fe3+ in the octahedral sheet has not been
sufficiently studied, but the deficiency of IVAl is

FIG. 14. Mn vs. the remaining octahedral cations in


phlogopite (phl), annite (ann), siderophyllite (sid),
polylithionite (pol) (Mn >0.3 a.p.f.u.) and muscovite
(mus) (Mn >0.15 a.p.f.u.) as well as for montdorite FIG. 15. Zn vs. the remaining octahedral cations for
(mon), norrishite (nor), shirozulite (shi) and hendricksite phlogopite (phl), annite (ann) (Zn >0.3 a.p.f.u.), sidero-
(hen). Numbers of analyses appear in parentheses. Data phyllite (sid), and muscovite (mus) (Zn >0.05 a.p.f.u.) as
sources for uncommon micas: Frondel and Ito (1966), well as for hendricksite (hen). Numbers of analyses
Robert and Maury (1979), Guggenheim et al. (1983), appear in parentheses. Most data were taken from
Eggleton and Ashley (1989), Gnos et al. (2003) and Frondel and Ito (1966), Guggenheim et al. (1983), Craig
Ishida et al. (2004). et al. (1985) and Tracy (1991).

297
TISCHENDORF ET AL.

probably made up by IVFe3+ (Brigatti et al., 1996;


Tombolini et al., 2002). Indeed, a theoretically
possible tetrahedral composition [Si 2.5Al1.5]
might give rise to a trioctahedral occupancy of
[R2+ 3+ 3+ 2+
2.5Fe0.5] (or [Fe1.5R ] for
VI
R = 2.5). In rare
cases up to 1.5 a.p.f.u. Fe3+ may enter the
octahedral coordination. At greater Fe3+ concen-
trations (>0.4 a.p.f.u.), a good correlation corre-
sponds to the substitution: VIFe3+ + IVAl > VIR2+
+ IVSi (see also Dymek, 1983) (Fig. 18).
Incorporation of high Ti. As in the case of Fe3+,
large concentrations of Ti 4+ in octahedral
coordination are subject to structural limitations.
For example, given a tetrahedral composition
[Al1.5Si2.5], the trioctahedral sheet with VIR = 3
can accommodate a maximum of 0.25 a.p.f.u.
Ti4+. For VIR = 2.5, the corresponding maximum
rises to 0.75 a.p.f.u. Ti4+. For micas with Ti4+
FIG. 16. Contents of V vs. the remaining octahedral concentrations >0.4 0.8 a.p.f.u. (Mansker et al.,
cations for phlogopite (phl) (V >0.3 a.p.f.u.), and 1979; Henderson and Foland, 1996; Zhang et al.,
muscovite (mus) (V >0.2 a.p.f.u.) as well as for 1993), the assumption is that some of the Ti fills
roscoelite (ros), chromphyllite (crph) and chernykhite the tetrahedral site to a sum of 4.0. Good
(cher). Numbers of analyses are given in parentheses. elemental correlations support the substitution
Data sources for uncommon micas: Ankinovich et al. scheme VI Ti 4+ + 2 IV Al > VI R 2+ + 2 IV Si
(1973), Treolar (1987), Hofmann (1990), Meunier (Tschermak-type substitution, see also Mesto et
(1994), Breit (1995) and Reznitskiy et al. (1997). al., 2006) that functions at high Ti4+ concentra-
tions (0.40 0.75 a.p.f.u.) (Fig. 19). A comparison
of the Ti 4+ contents among micas of the
phlogopite–annite series shows that the greatest
concentrations (up to 0.75 a.p.f.u.) are limited to
phlogopite with a Mg# = 0.8 0.9, whereas

FIG. 17. Contents of Cr (>0.1 a.p.f.u.) vs. the remaining


octahedral cations for phlogopite (phl) and muscovite
(mus) as well as for chromphyllite (crph). Numbers of FIG. 18. Plot of VIFe3++IVAl vs. VIR2++2IVSi for
analyses are given in parentheses. Data for chromphyl- phlogopite (phl) and annite (ann) micas whose Fe3+
lite were taken predominantly from Treolar (1987) and content was determined analytically. Shown are a.p.f.u.
Reznitskiy et al. (1997). intervals of Fe3+ of the respective species.

298
CLASSIFICATION OF MICAS

(Weiss et al., 1985; Pekov et al., 2003).


Armbruster et al. (2007) demonstrated extended
solid solution between tainiolite and shirokshinite.

Tetrahedral sheet
In the tetrahedral sheet, Si ranges from 4 to 2
a.p.f.u., and IVAl from 0 to 2 a.p.f.u., accordingly.
The ratio Si/IVAl = 1/3, known in clintonite, is in
violation of the Löwenstein rule and seems to be
an exception. Lack of IVAl requires incorporation
of some IVFe3+ or IVTi4+ to avoid a cation excess
in the octahedral sheet. A clarification of the role
of Ti in the tetrahedral sheet is desirable. In
addition to Fe3+ and Ti, B and Be also play a rare
role, although under-reported in analytical
routines.
Incorporation of Fe3+. Tetra-ferri-annite
(2 analyses; Wones, 1963) and tetra-ferriphlo-
FIG. 19. Plot of VITi+2IVAl against VIR2++2IVSi for gopite (19 analyses; Brigatti et al., 1996) are
phlogopite containing between 0.40 and 0.75 a.p.f.u. Ti. analogues of annite and phlogopite, with IVFe3+
replacing IVAl. Tetra-ferriphlogopite seems to
have a pronounced miscibility with phlogopite
smaller concentrations accompany progressively (Fig. 21, also Brod et al., 2001; Tombolini et al.,
more ferruginous compositions. In annite with 2002). Anandite (5 analyses) is an enigmatic
Mg# <0.4, the Ti concentration does not exceed S-bearing brittle mica, also related to annite.
0.4 a.p.f.u. (Fig. 20). Incorporation of B. Trioctahedral micas invari-
Incorporation of Na. The existence of the ably contain <0.15 a.p.f.u. B, most commonly
trioctahedral mica shirokshinite (4 analyses), a <0.05 a.p.f.u. (Černý et al., 1995; Badanina et al.,
Na analogue of tainiolite, indicates that other 2004). The bulk of the dioctahedral micas also
micas, particularly those from Na-rich assem- contain <0.15 a.p.f.u. B. Generally, no correlation
blages, may have Na in octahedral coordination exists between B and IVAl (Fig. 22). However,

FIG. 20. Contents of Ti (>0.25 a.p.f.u.) as a function of FIG. 21. Relation of IVFe3+ to IVAl in phlogopite (phl)
Mg/(Mg+Fetot) [=Mg#] in Ti-rich phlogopite (Ti phl) and tetra-ferriphlogopite (tetra-ferriphl). Data are taken
and Ti-Fe-rich phlogopite (Ti-Fe phl) [Mg# >0.5] as from Brod et al. (2001; Table 4 and 7) and Tombolini et
well as in Ti-Mg-rich annite (Ti-Mg ann) [Mg# <0.5]. al. (2002; Table 1).

299
TISCHENDORF ET AL.

such a replacement relationship appears if boron Stoppa et al., 1997) in mafic to ultramafic rocks.
is >0.5 a.p.f.u., leading in some cases to Fluorannite is an F-rich annite present in only
boromuscovite (10 analyses; Foord et al., 1991; some evolved A-type granites (Shen et al., 2000,
Novák et al., 1999; Thomas et al., 2003). but also Charoy and Raimbault, 1994). Large Cl
Incorporation of Be. The brittle mica bityite concentrations appear restricted to some of the
(13 analyses) is a geochemical paradox, allowing annites, hendricksitic phlogopites to annites, and
(as in tainiolite) a simultaneous presence of ferrokinoshitalites. Highest Cl concentration is
substantial concentrations of incompatible reported in ferrokinoshitalite from skarns (Tracy,
elements (Be, Li) and a compatible element (Ca) 1991), with an OH/F/Cl ratio of 0.47/0.27/1.26
(Lin and Guggenheim, 1983; Lahti and (a.p.f.u.). In rare cases, O or S is incorporated in
Saikkonen, 1985). In compositions with IVAl trioctahedral micas such as the Ti-rich brittle mica
ranging from 2 to 1 a.p.f.u. (and Be from 0 to oxykinoshitalite (2 analyses), in which Fe is
1 a.p.f.u.), a continuous replacement of IVAl by completely replaced by Ti (Kogarko et al., 2005),
Be, according to the coupled substitution Ca2+ + norrishite (2 analyses; Eggleton and Ashley,
Be2+ > (K,Na)+ + IVAl3+, appears to operate 1989), and anandite (5 analyses; Pattiaratchi et
(Fig. 23). al., 1967).

Anions
Discussion and conclusions
The anion positions are occupied mainly by
(OH) and F and, more rarely, by Cl, S or O. Most Charge balance
Mg-Fe micas (phlogopite, annite, Mg-rich side- By definition, trioctahedral micas should contain
rophyllite), and Al micas (muscovite, celadonite), three cations, and dioctahedral micas two cations,
are OH-rich; Li micas (polylithionite, tainiolite) in octahedral coordination. If the sum of cation
are typically F-rich. Li-rich annite, Li-rich side- charges is constant (= 22, including K), the
rophyllite and Li-rich muscovite are transitional. occupancy of the tetrahedral sheet is fixed. For K
Fluorine supplied by mantle degassing may give micas and other micas with a univalent cation in
rise to F-rich phlogopite (up to 1.65 a.p.f.u.; e.g. the interlayer it follows that:
five octahedral charges (e.g. polylithionite: 2Li+
+ Al3+, tainiolite: 2Mg2+ + Li+, celadonite: Fe3+ +
Mg2+) require [Si4];

FIG. 22. Quantity of IVB in relation to IVAl for


siderophyllite (sid), polylithionite (pol), muscovite
(mus) and boromuscovite (bmus). Numbers of analyses
are given in parentheses. Data for the common true K FIG. 23. Plot of XIICa + IVBe as a function of XII(K,Na) +
micas were taken predominantly from Černý et al. IV
Al for bityite and Be(Li)-rich margarite (mar). Be
(1995) and Badanina et al. (2004); data for boromusco- contents (in a.p.f.u.) are indicated. Numbers of analyses
vite are from Foord et al. (1991), Novák et al. (1999) are given in parentheses. Data were taken from Lahti
and Thomas et al. (2003). and Saikkonen (1985).

300
CLASSIFICATION OF MICAS

six charges as in phlogopite (3Mg2+) or analyses. The Mg-Fe mica group [Si = 2.5 2.9],
muscovite (2Al3+) require [Si3Al]; the Al mica group [Si = 2.9 3.3] as well as the
six-and-a-half charges as in Fe-rich phlogopite Li-Al mica group, including tainiolite, montdorite
(1.5Mg2+ + Fe2+ + 0.5Al3+) or annite (2.5Fe2+ + and celadonite (= tetra-silicic micas) [Si =
0.5Fe3+) require [Si2.5Al1.5]; 3.3 4.0], form separate clusters along the line
seven charges (siderophyllite: 2Fe2+ + Al3+, VI
R = 9 IVSi.
eastonite: 2Mg 2+ + Al3+ ) would require a
tetrahedral sheet of [Al2Si2]. Substitution of elements, solid-solution series, and
Surprisingly, natural common true K micas with miscibility gaps
tetrahedral composition [Al2Si2] are not known.
Their minimum concentration of IVSi is 2.5. A significant property of the micas is that, almost
In contrast, brittle micas (with a divalent cation without exception, they form solid solutions. In
such as Ca and Ba in the interlayer) with this study, we have not examined whether a
six octahedral cation charges (e.g. kinoshitalite particular mica is a member of a complete solid-
[3Mg2+] or margarite [2Al3+]) would require solution series with well defined end-members, or
[Al2Si2] in the tetrahedra; whether it is a result of only a partial element-
seven octahedral cation charges (e.g. clintonite exchange. We have dealt with real analytical
[2Mg2+ + Al3+]) would require an absolute determinations of elements and tried to establish
minimum of tetrahedral Si [Al3Si]. their mutual relationships. In such a case, all
In practice, clintonite has Si1.1 1.3 statements about substitutions of elements in
(48 analyses). Therefore, an increasing proportion minerals should be normalized to the scale of
of divalent cations (Ca2+, Ba2+) in the interlayer examination. Accordingly, microprobe analyses
of true micas, as well as an increase of trivalent can avoid problems (multiple generations of a
(Fe3+, also VIAl3+) and quadrivalent cations (Ti4+) mica, the presence of heterogeneous phases, etc.)
in the octahedral sheet (normally occupied in the and will yield results different from wet-chemical
phlogopite–annite series by divalent cations such analyses. The future application of new and more
as Mg2+, Fe2+), brings about a minimization of Si sophisticated analytical techniques will certainly
in tetrahedral coordination. On the contrary, offer a more detailed view of the phase chemistry.
incorporation of monovalent Li in the octahedral Because of the multicomponent nature of the
sheet (except the uncommon ephesite and bityite) mica chemical system, and the wide possibilities
may increase tetrahedral Si up to 4.0. of mutual replacement of elements in micas,
Figure 24 gives an overview of charge-balance complex relationships govern the occupancy of
as a function of Si. The plot shows mean values individual coordinations and the conditions for a
for analyses of all mica species. True micas obey necessary charge-balance. Guidotti and Sassi
the following relation for cation charge sums: VIR (1998) used their detailed study of metamorphic
= 9 IVSi. The equation for brittle micas is VIR = Na/K white micas as an example of the
8 IVSi. Micas deviating from these relationships miscellaneous isomorphic substitutions. Element
(kinoshitalite, margarite, anandite) have a smaller substitutions in common true K micas are not
proportion of divalent cations in the interlayer restricted to schemes operating within a particular
(0.69 a.p.f.u. Ba, 0.74 a.p.f.u. Ca, 0.88 a.p.f.u. solid-solution series, but deviate into composi-
Ba, respectively). According to its formula, tional space between such series. We may
ganterite (Ba ~0.50 a.p.f.u.) is intermediate distinguish five magmatic evolutionary pathways
between true and brittle micas. Bityite plots in a (Fig. 25):
special position because of its concentration of (I) Phlogopite sensu stricto–Ti-rich phlogopite–
IV
Be2+. Oxykinoshitalite and norrishite are distin- Ti-Fe-rich phlogopite–Fe-rich phlogopite–Mg-Ti-
guished by a different fundamental condition of rich annite–annite sensu stricto–Li-rich annite
24 cation charges; besides, the latter has the (corresponding with a branch of the complete
unique concentration of trivalent manganese. trioctahedral system phlogopite/biotite/sidero-
Ephesite (like eastonite) is a mica that plots at phyllite-lepidomelane according to Foster,
the outer border of the mgli/feal diagram (Figs 2 1960a, representing the Al-deficient path devel-
and 3), indicating a trioctahedral, but abnormal oped during the evolution of mantle-derived
status. Note that the theoretical end-member magmatic rocks);
compositions of siderophyllite and eastonite in (II) Al-rich phlogopite–Al-Fe-rich phlogopite–
Fig. 24 lie well outside the bulk of the mica Al-Mg-rich annite–Al-rich annite–Al-Li-rich

301
TISCHENDORF ET AL.

FIG. 24. Sum of charges of VIR related to IVSi for averages of selected natural mica species. Shown are brittle micas:
anandite, bityite, clintonite, kinoshitalite, margarite; trioctahedral true micas: annite, eastonite, ephesite,
hendricksite, montdorite, phlogopite, polylithionite, preiswerkite, shirokshinite, siderophyllite, tainiolite sensu
stricto; dioctahedral true micas: boromuscovite, celadonite(cel), chromphyllite, ganterite, margarite, muscovite,
nanpingite, paragonite, roscoelite, tobelite; and some theoretical mica end-members: annite, celadonite, clintonite,
eastonite, kinoshitalite, margarite, muscovite, phlogopite, polylithionite, siderophyllite, tainiolite, norrishite, and
oxykinoshitalite (oxy-kino); (a) cluster of Mg-Fe mica group [Si = 2.6 to 2.9], (b) cluster of Al mica group [Si = 2.9
to 3.3], (c) cluster of Li-Al mica group including tainiolite, montdorite, and celadonite (= tetra-silicic micas) [Si =
3.3 to 4.0]; white grey = range of transitional micas between true and brittle micas. For common true K micas holds:
Sum of charges of VIR = 9 IVSi (in a.p.f.u.); for brittle micas: Sum of charges of VIR = 8 IV
Si (in a.p.f.u.).
Abbreviations as in preceding figures.

annite (branch of the complete trioctahedral lithium mica series according to Monier and
system phlogopite/biotite/siderophyllite–lepido- Robert, 1986, zinnwaldite–muscovite subsolidus
melane according to Foster, 1960a; Al-enriched ‘autometasomatic’ trend of Henderson et al.,
path developed during the evolution of mantle- 1989; path developed during late-magmatic
derived magmatic rocks); evolution of granites); and
(III) Al-Mg-rich annite–Mg-rich siderophyllite- (V) Polylithionite–Li-rich muscovite–musco-
siderophyllite sensu stricto–Li-rich siderophyl- vite sensu stricto (aluminium–lithium micas
lite–Fe-rich polylithionite–polylithionite sensu according to Foster, 1960b; path developed
stricto (ferrous lithium-mica series according to during evolution of pegmatites).
Foster, 1960b, lithium–iron micas according to In addition, muscovite, Mg-rich muscovite, Fe-
Rieder et al., 1970; path developed during the rich muscovite and Mg-Fe-rich muscovite are
formation of crust-derived magmatic rocks, components of metamorphic rocks wherein the
including their pegmatitic and aplitic derivates); mica composition varies as a function of the
(IV) Fe-rich polylithionite–Li-Fe-rich musco- conditions of formation. Tainiolite sensu stricto,
vite–Fe-rich muscovite (ferrous aluminium– Fe-rich and Al-rich tainiolitic micas, however, are

302
CLASSIFICATION OF MICAS

mostly hybrid products, if evolved solutions react series phlogopite–Ti-Fe-rich phlogopite–Ti-Mg-


with mafic rocks. rich annite–annite–Li-rich annite (I), Al-rich
The best-documented solid-solution series phlogopite–Al-Fe-rich phlogopite–Al-Mg-rich
between true and brittle micas is that between annite–Li-Al-rich annite (II), Al-Mg-rich annite–
phlogopite and kinoshitalite (Fig. 12a). Larger Ba siderophyllite–Li-rich siderophyllite–Fe-rich
concentrations apparently occur in the whole polylithionite–polylithionite (III), Fe-rich poly-
phlogopite–annite series; however, whether a lithionite–Li-Fe-rich muscovite–Fe-rich musco-
complete miscibility occurs between annite and vite–Mg-Fe-rich muscovite (IV), and
ferrokinoshitalite remains an open question polylithionite–Li-rich muscovite–muscovite–
(Fig. 13). Complete element substitution is also Mg-rich muscovite (V) form the framework of
present in the series muscovite–roscoelite the common true K micas (Fig. 25). These series
(Fig. 16), muscovite–chromphyllite (Fig. 17) and constitute the main substitution patterns present in
phlogopite–tetra-ferriphlogopite (Fig. 21). A natural micas. Most of the main composition
substitution relation probably exists for musco- maxima coincide with the mica species (such as
vite–tobelite (Fig. 10), and may also exist between muscovite, phlogopite and polylithionite). An
common true K micas and Na micas, namely exception is the relative frequency maximum
phlogopite–aspidolite (Fig. 7a) and muscovite– close to mgli = 1.25 and feal = 1.25, which
paragonite (Fig. 7b), although the latter appears encompasses micas formerly termed ‘biotite’
more limited. In contrast, miscibility gaps (Fig. 1). Most of this maximum occurs within
probably exist between common true K micas the Mg-rich part of the annite field, but it also
and Ca-bearing brittle micas (Fig. 11a,b), and straddles the fields of phlogopite and sidero-
between muscovite and boromuscovite (Fig. 22). phyllite. Most of the former ‘biotites’ are
Experiments have shown a complete miscibility intermediate annite–phlogopite solid solutions.
between K and Rb in phlogopite, but a possible Another, less problematic exception is the relative
miscibility with natural common true K micas maximum close to mgli = 1 and feal = 0, which
remains to be studied (Fig. 8). On the contrary, the is cut by the siderophyllite/polylithionite discri-
Cs-rich part in the K Cs system is occupied mination divide and lies precisely where the
(Fig. 9), indicating a complete element exchange. micas formerly termed ‘zinnwaldite’ would have
Although only a few analyses are available in the plotted. Consequently, most ‘zinnwaldites’ corre-
system muscovite–bityite, the data indicate a spond to intermediate polylithionite–siderophyl-
nearly complete replacement of IVAl by IVBe lite solid solutions.
(Fig. 23). Manganese and Zn are enriched in some Incompletely investigated micas can be desig-
micas (masutomilite, montdorite, norrishite, shir- nated with series names such as biotite, phengite,
ozulite, hendricksite) that will form only under or zinnwaldite (Rieder et al., 1998) but, after
special physicochemical conditions and must be detailed investigation, such series names ought to
considered separately (Figs 14, 15). The concen- be abandoned in favour of more precise terms
trations of Ti as well as Fe3+ are limited because of such as Fe-rich phlogopite, Li-Fe-rich muscovite
their large valence (Figs 18 20). To date, no or Li-rich siderophyllite. These names apply from
known mica (apart from oxykinoshitalite) has an end-member out to the 50/50 divide, which is a
predominant Ti in the octahedral position. Finally, universally accepted border that may run, counter-
OH and F are apparently miscible in almost any intuitively, through frequency maxima in compo-
mica. sition plots.
The Fetot/(Fetot+Li) ratio [=Fe#] can be used,
Principles of classif|cation together with VIAl, to describe compositions at or
near the siderophyllite–polylithionite series.
Micas constitute a group of minerals character- Alternatively, it can be used alone to sort all
ized by a predominant substitution of elements. trioctahedral micas, because Fe# = 1.0 holds for
Their classification rests on the existence of end- Fe-bearing phlogopite and end-member annite.
members and their interconnection by solid- Several end-members of the common true K
solution series. micas are starting points for solid-solution series
Common true K micas can be classified using with end-members of uncommon true K micas,
VI
R, VIAl, Mg6Li, accompanied by fractions other alkali element true micas, and brittle micas.
Mg/(Mg+Fetot) [=Mg#], Fetot/(Fetot+Li) [=Fe#], Figure 25 presents the whole mica system.
and Al/(Al+Fetot+Mg) [=Al#], all in a.p.f.u. The Tainiolites form a special sub-system (Fig. 5).

303
TISCHENDORF ET AL.

Concerning the classification of celadonites Relationships of classif|ed micas to the mgli/feal system
(Fig. 6), we follow Li et al. (1997).
Natural compositions of common true K micas The application of the mgli/feal variables offers
represent complex multi-element substitutions an overall view of the whole mica family and
involving Fe2+, Mg, VIAl, Li, Ti, Fe3+ and allows the user to inspect all main compositions.
Mn2+. However, solid-solution series between Mica end-members plot in the mgli/feal diagram
common true K micas and uncommon true at vertices with angles between 90º and 125º
K micas, other alkali-element true micas, and (KMg 3 [AlSi 3 O 10 ](OH) 2 , phlogopite; KFe 2+3
brittle micas are characterized by simpler, [AlSi3O10](OH)2, annite; KLi2Al[Si4O10]F2, poly-
element-for-element, binary substitutions (e.g. lithionite; KAl2&[AlSi3O10](OH)2, muscovite;
K > Na or K > Ba or VIAl > Cr). Figs 2 and 3). Vertices with angles between 155º

FIG. 25. The system of trioctahedral and dioctahedral true and brittle micas (without celadonites) plotted in terms of
mgli and feal variables. Common true K mica species are assigned their areas within the diagram. Evolutionary
pathways of igneous micas are indicated (I to V), documented by compositional averages of mica varieties.
Uncommon true K micas, other alkali element micas, brittle micas, and some further ideal mica members are listed
in the boxes outside of the diagram. The position of the Zn-rich mica hendricksite corresponds to its average
composition in nature. In the mica formulae, the order of elements in the individual sheets conforms to the
recommendations of the Mica sub-committee of the CNMNC (Rieder et al., 1998).

304
CLASSIFICATION OF MICAS

and 165º represent micas with the ideal composi- (3) The mgli/feal variables are based on the
tions KMg2.5Al0.5[Al1.5Si2.5O10](OH)2 (Al-rich main, octahedrally coordinated cations in the
phlogopite), KLiFe 2+ 2 [Si 4 O 10 ](OH) 2 (Li-rich mica structure.
annite) and KLi1.25Al1.75[Al1.5Si2.5O10]F2 (Al-rich (4) The plotting of all theoretical formulae is
trilithionite). Other essential ideal components, straightforward.
such as KLi1.5Al1.5[AlSi3O10]F2 (trilithionite), (5) The grids for accompanying variables such
KMg2Fe2+[AlSi3O10](OH)2 (Fe-rich phlogopite), as VIR, IVSi, as well as VIAl, Mg, Fetot (including
KFe2+ 2 Mg[AlSi3O10](OH)2 (Mg-rich annite) plot Ti + Mn), and Li can be shown in the diagram
along the outer boundary of the polygon. End- (Tischendorf et al., 2004, their Figs 2 and 3).
member siderophyllite K F e 22 + A l (6) The mgli and feal variables correspond well
[Al2Si2O10](OH)2 or KLi0.25Fe2+ 1.75 Mg 0.25Al0.75 with the substitution vectors according to
[Al1.5Si2.5O10](OH)2 plots at a pivotal point of Tschermak (Burt, 1991): mgli represents a
the mica system. The position of tainiolite condensed form of 3MgIVAl[2LiVIAlSi] 1 and
(KLiMg2[Si4O 10]F2) is unique and isolated feal is approximately 3(Fe 2 + Mn 2+ Ti 0.5 ) 2+
(Fig. 5). Likewise, the celadonites, which defini- [2VIAl] 1, neglecting Fe3+.
tively contain Fe3+, must be treated separately from (7) The plot offers the possibility to display
the mainstream micas (Fig. 6). The course of VIR fractionation tendencies in magmatic rocks as
and VIAl in the diagram, as well as points for micas evolution series including all mica species and
lying half-way along the joins of end-members, varieties.
delineate the fields of mica species. (8) The graphical mica presentation applying
The boundaries of mica species in the mgli/feal mgli/feal is highly compatible with the chemical
diagram are theoretical and may not coincide mica classification according to VIAl, VIR, Mg#,
completely with those based on the relevant Fe# and Al#.
elemental ratios used for classification. Such
discrepancies may be caused by two important Acknowledgements
factors:
(1) Ideal mica members are related to VIR = 3.0 K. Breiter (Prague), R. Thomas, and D.E. Harlov
or 2.0, which is the basis underlying the (both Potsdam) contributed unpublished mica
construction of the diagram; however, occupan- analyses. F. Pietschmann (Zittau) helped with
cies of natural micas may differ from these the mathematical procedures. The authors wish to
values; acknowledge the thorough work of A. Hendrich
(2) For plotting, the theoretical compositions and M. Dziggel (Potsdam) who carefully
are reduced to main constituents of the octahedral constructed the figures. The paper benefited
sheet (Fetot, VIAl, Ti, Mn, Mg, Li), but in reality, from constructive reviews by three anonymous
they may contain additional elements such as Zn, referees and editorial comments by C. Geiger
Cr and V. (Kiel) and M. Welch (London). B. Clarke
Overlaps may affect the boundary between (Halifax) read the final version to check for
annite and siderophyllite in particular. Therefore, language correctness. We also acknowledge
Fig. 2 shows two sets of isolines for VIAl = 0.5, valuable discussions with E.A.J. Burke
one for VIR = 3.0 and the other for VIR = 2.75. We (Amsterdam) and E.H. Nickel (Wembley,
recommend use of the VIAl = 0.5 isoline for VIR = Australia).
2.75 for discrimination between these two species
(Figs 3 and 4). References
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TISCHENDORF ET AL.

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Appendices
The crystallo-chemical formulae were calculated on the basis of 22 cation charges. The content of water was
calculated assuming the (OH+F+Cl) site is completely filled; av = average, s = 1-Sigma standard deviation,
n = number of determinations, Mg# = Mg/(Mg+Fetot) (a.p.f.u.), Fe# = Fetot/(Fetot+Li) (a.p.f.u.), Al# =
VI
Al/(VIAl+Fetot+Mg) (a.p.f.u.), mgli = Mg minus Li (a.p.f.u.), feal = VIFetot+Mn+Ti minus VIAl (a.p.f.u.).

311
APPENDIX 1a. Composition (wt.%) of phlogopite and its varieties.

Al-rich phlogopite Phlogopite sensu stricto Ti-rich phlogopite Fe-rich phlogopite Ti-Fe-rich phlogopite Al-Fe-rich phlogopite
av s n av s n av s n av s n av s n av s n

SiO2 39.0 3.3 18 40.1 2.7 512 38.4 2.8 74 37.6 2.0 903 36.9 1.9 221 36.6 1.9 86
TiO2 0.45 0.41 18 1.20 1.61 485 8.09 2.06 74 2.90 1.36 896 6.68 1.79 221 1.64 0.87 85
SnO2 0.001 1 0.004 0.007 8 0.002 0.004 38 0.001 0.001 2 0.001 1
Al2O3 19.3 1.7 18 13.3 3.8 509 11.4 2.5 74 14.6 2.7 903 14.5 2.7 221 19.1 1.4 86
Ga2O3 0.008 1 0.003 0.002 10 0.005 0.004 76 0.005 0.002 9 0.002 0.001 2
Sc2O3 0.002 1 0.002 0.001 9 0.004 0.003 58 0.010 1 0.010 0.005 8
V2O3 0.037 1 0.020 2.900 11 0.060 0.607 118 0.050 0.040 9 0.045 0.042 18
Fe2O3 0.18 0.91 4 0.68 3.94 120 2.18 1.33 3 1.10 3.28 423 0.30 3.19 49 0.45 2.14 23
Cr2O3 0.400 0.800 4 0.720 0.590 267 0.350 0.560 42 0.120 0.318 386 0.130 0.260 67 0.075 0.120 27
FeO 2.09 1.07 18 3.50 2.56 470 4.40 2.30 74 11.9 4.8 896 11.5 3.8 220 14.5 3.3 86
MnO 0.45 2.82 13 0.15 1.99 353 0.06 0.04 47 0.19 0.50 797 0.13 0.13 173 0.19 0.28 71
CoO 0.000 1 0.001 0.000 8 0.008 0.005 61 0.010 0.005 2 0.007 0.004 9
NiO 0.008 1 0.105 0.107 125 0.120 0.060 32 0.004 0.073 167 0.045 0.074 25 0.017 0.032 15
ZnO 0.050 1 0.055 0.014 12 0.060 1.896 133 0.027 0.040 15 0.064 0.043 25
MgO 22.0 1.6 18 24.3 2.3 512 19.7 2.4 74 16.4 4.1 903 14.5 2.4 221 13.0 2.3 86

312
Li2O 0.011 0.008 3 0.006 0.079 125 0.019 0.016 49 0.035 0.074 683 0.050 0.026 190 0.070 0.199 50
CaO 0.10 0.3 10 0.09 0.19 294 0.08 0.21 49 0.25 0.49 628 0.13 0.25 142 0.12 0.23 57
SrO 0.001 0.001 2 0.013 0.011 19 0 0.03 3 0.005 0.062 96 0.010 0.015 9 0.001 0.064 14
BaO 2.50 4.62 8 0.95 2.97 339 1.10 3.28 61 0.62 2.03 533 1.25 2.78 138 0.55 1.32 35
TISCHENDORF ET AL.

PbO 0.002 1 0.001 0.001 9 0 0 2 0.001 0.001 40 0.002 0.004 8


Na2O 0.16 0.67 17 0.45 0.47 477 0.27 0.35 72 0.32 0.42 829 0.53 0.29 212 0.28 0.36 77
K2O 8.93 1.52 18 9.85 1.15 512 9.47 1.46 74 9.22 0.89 903 8.97 1.04 221 8.72 0.95 86
Rb2O 0.020 1 0.02 0.092 96 0.025 0.015 4 0.070 0.149 228 0.050 0.026 35 0.080 1.47 11
Cs2O 0.007 1 0.002 0.035 15 0.010 0.590 79 0.008 0.010 8 0.010 1.97 9
H2O 4.07 3.45 3.32 3.57 3.55 3.71
F 0.34 0.33 6 1.55 2.02 275 1.72 1.51 19 0.93 1.25 576 0.95 1.21 123 0.50 1.04 36
Cl 0.02 1 0.04 0.68 38 0.03 0.03 4 0.11 0.25 226 0.14 0.22 31 0.37 0.48 22
Sum 100.1 100.6 100.7 100.1 100.4 100.1
O = 0.15 0.66 0.73 0.42 0.43 0.29
F+Cl
Total 100.0 99.9 100.0 99.7 100.0 99.8
APPENDIX 1b. Average formulae of phlogopite and its varieties.

Al-rich phlogopite Phlogopite Ti-rich phlogopite Fe-rich phlogopite Ti-Fe-rich phlogopite Al-Fe-rich phlogopite
0.3 0.5 VIAl sensu stricto 0.3 0.75 Ti 0.3 1.4 Fetot 0.3 0.7 Ti 0.3 0.5 VIAl
0.3 1.2 Fetot 0.3 1.2 Fetot

Si 2.760 2.868 2.778 2.789 2.735 2.717


IV
Al 1.240 1.121 0.990 1.211 1.262 1.283
IV
Fe3+ 0.011 0.119 0.003
IV
Ti 0.113
SIVR 4.000 4.000 4.000 4.000 4.000 4.000
VI
Ti 0.024 0.065 0.440 0.162 0.372 0.091
Sn 0.0000 0.0001 0.0001 0.0000 0.0000
VI
Al 0.369 0.000 0.000 0.066 0.000 0.389
Ga 0.0004 0.0001 0.0002 0.0002 0.0001
Sc 0.0001 0.0001 0.0003 0.0006 0.0006
V 0.0021 0.0011 0.0036 0.0030 0.0027
VI
Fe3+ 0.010 0.027 0.000 0.061 0.014 0.025
Cr 0.022 0.041 0.020 0.007 0.008 0.004
Fe2+ 0.124 0.209 0.266 0.738 0.713 0.900
Mn 0.027 0.009 0.004 0.012 0.008 0.012

313
Co 0.0000 0.0001 0.0005 0.0006 0.0004
Ni 0.0005 0.0060 0.0070 0.0002 0.0027 0.0010
Zn 0.0026 0.0029 0.0033 0.0015 0.0035
Mg 2.320 2.590 2.124 1.813 1.601 1.438
Li 0.003 0.002 0.006 0.010 0.015 0.021
CLASSIFICATION OF MICAS

SVIR 2.905 2.953 2.867 2.877 2.740 2.888


Ca 0.008 0.007 0.006 0.020 0.010 0.009
Ba 0.0693 0.0266 0.0312 0.0180 0.0363 0.0160
Na 0.022 0.062 0.038 0.046 0.076 0.040
K 0.806 0.899 0.874 0.872 0.848 0.826
Rb 0.0009 0.0009 0.0012 0.0033 0.0024 0.0038
Cs 0.0002 0.0001 0.0003 0.0003 0.0003
SXIIR 0.906 0.996 0.950 0.960 0.973 0.895
OH 1.922 1.644 1.602 1.768 1.759 1.837
F 0.076 0.351 0.394 0.218 0.223 0.117
Cl 0.002 0.005 0.004 0.014 0.018 0.046
S 2.000 2.000 2.000 2.000 2.000 2.000
Mg# 0.945 0.916 0.889 0.694 0.688 0.609
mgli 2.32 2.59 2.12 1.80 1.59 1.42
feal 0.18 0.31 0.62 0.91 1.11 0.64
APPRENDIX 2a. Composition (wt.%) of annite and its varieties.

Ti-Mg-rich annite Mg-rich annite Al-Mg-rich annite Al-rich annite Annite sensu stricto Li-rich annite Li-Al-rich annite
av s n av s n av s n av s n av s n av s n av s n

SiO2 35.4 1.6 75 35.4 1.7 690 35.2 1.3 453 34.9 1.8 46 34.7 2.1 89 36.5 2.1 10 37.5 1.2 9
TiO2 5.50 1.40 75 3.27 0.85 689 2.65 0.80 450 1.97 0.84 45 3.06 1.13 87 1.85 0.92 10 1.08 0.89 9
SnO2 0.008 0.002 5 0.009 0.011 137 0.008 0.009 110 0.039 0.022 19 0.021 0.012 13 0.051 1 0.057 0.006 2
Al2O3 14.4 2.5 75 15.3 2.2 690 19.1 1.1 453 17.7 1.8 46 12.8 2.8 89 12.7 2.5 10 16.1 2.2 9
Ga2O3 0.008 1 0.01 0.01 142 0.007 0.004 68 0.021 0.014 3 0.015 0.003 4
Sc2O3 0.004 1 0.008 0.01 102 0.005 0.004 108 0.005 0.003 3 0.007 0.004 2
V2 O3 0.021 0.040 10 0.034 0.020 254 0.030 0.037 162 0.006 0.012 6 0.005 0.002 6
Fe2O3 0.90 2.74 20 3.00 3.54 497 1.88 2.42 302 4.30 3.14 33 4.50 3.52 66 3.85 5.43 5 1.30 4.12 3
Cr2O3 0.027 0.046 20 0.018 0.033 338 0.018 0.021 216 0.006 0.003 7 0.004 0.001 6
FeO 21.5 4.4 75 20.7 4.2 685 20.0 2.8 452 25.2 4.3 46 29.1 6.0 89 27.7 8.2 10 26.5 5.7 9
MnO 0.18 0.15 74 0.41 0.49 680 0.32 0.30 448 0.61 0.27 46 0.61 0.68 89 1.33 2.25 10 1.02 0.48 7
CoO 0.005 0.002 6 0.006 0.002 169 0.004 0.002 118 0.001 0.001 6 0.003 0.001 4
NiO 0.008 0.116 10 0.008 0.017 227 0.006 0.007 171 0.001 0.000 6 0.001 0.000 5

314
ZnO 0.066 0.036 13 0.065 0.814 260 0.065 0.049 227 0.135 0.098 9 0.120 0.149 11
MgO 7.86 1.84 75 7.78 2.18 690 6.91 1.90 453 0.91 0.76 46 1.25 0.69 89 0.35 1.77 10 0.22 0.88 9
Li2O 0.17 0.0605 60 0.17 0.15 639 0.20 0.19 358 0.48 0.19 45 0.40 0.20 84 1.01 0.84 10 1.35 0.57 9
CaO 0.21 0.50 49 0.37 0.44 538 0.17 0.31 320 0.26 0.32 30 0.32 0.62 70 0.27 0.30 7 0.94 0.64 5
TISCHENDORF ET AL.

SrO 0.001 0.001 8 0.002 0.043 206 0.001 0.006 115 0.001 0.001 5 0.002 0.000 2
BaO 0.35 2.51 46 0.15 2.36 392 0.01 0.06 250 0.02 0.02 10 0.09 4.49 12
PbO 0.002 0.001 7 0.002 0.01 122 0.002 0.001 89 0.004 0.002 3 0.002 0.00 3
Na2O 0.19 0.25 70 0.19 0.22 673 0.22 0.18 415 0.22 0.18 46 0.22 0.31 84 0.29 0.28 10 0.35 1.22 8
K2 O 9.05 1.05 75 8.79 1.11 690 8.89 0.78 453 8.52 0.80 46 8.56 1.01 89 8.85 0.49 10 8.90 1.25 9
Rb2O 0.105 0.035 11 0.095 0.100 394 0.160 0.600 223 0.250 0.082 28 0.200 0.089 41 0.850 1.358 3 0.360 0.170 2
Cs2O 0.011 0.004 7 0.02 0.26 208 0.035 0.627 171 0.021 0.021 18 0.015 0.013 30 0.1 1 0.068 0.052 2
H2 O 3.47 3.44 3.55 2.91 3.03 2.00 1.84
F 0.81 0.51 60 0.77 0.70 469 0.74 0.63 230 1.77 1.00 44 1.14 1.19 72 3.50 1.49 9 4.03 1.13 8
Cl 0.07 0.493 24 0.25 0.94 137 0.11 0.14 64 0.19 0.09 8 0.45 0.76 16 0.20 1 0.24 1
Total 100.3 100.3 100.3 100.4 100.6 101.4 101.9
O = F+Cl 0.35 0.38 0.34 0.79 0.58 1.52 1.75
Total 100.0 99.9 99.9 99.7 100.0 99.9 100.1
APPENDIX 2b. Average formulae of annite and its varieties.

Ti-Mg-rich annite Mg-rich annite Al-Mg-rich annite Al-rich annite Annite Li-rich annite Li-Al-rich annite
0.3 0.65 Ti 0.3 1.3 Mg 0.3 0.5 VIAl 0.3 0.5 VIAl sensu stricto 0.3 1.0 Li 0.3 0.8 Li
0.3 1.2 Mg 0.3 1.2 Mg 0.3 0.5 VIAl

Si 2.737 2.739 2.685 2.761 2.817 2.953 2.950


IV
Al 1.263 1.261 1.315 1.239 1.183 1.047 1.050
SIVR 4.000 4.000 4.000 4.000 4.000 4.000 4.000
Ti 0.323 0.190 0.152 0.117 0.187 0.113 0.064
Sn 0.0003 0.0003 0.0002 0.0012 0.0007 0.0016 0.0018
VI
Al 0.049 0.134 0.400 0.411 0.042 0.164 0.443
Ga 0.0004 0.0004 0.0003 0.0011 0.0008
Sc 0.0003 0.0006 0.0003 0.0003 0.0005
V 0.0013 0.0021 0.0018 0.0004 0.0003
Fe3+ 0.052 0.175 0.108 0.256 0.275 0.234 0.077
Cr 0.0020 0.0010 0.0010 0.0003 0.0003
Fe2+ 1.390 1.339 1.275 1.667 1.975 1.874 1.743
Mn 0.012 0.027 0.021 0.041 0.042 0.091 0.068
Co 0.0003 0.0003 0.0002 0.0001 0.0002

315
Ni 0.0005 0.0005 0.0004 0.0000 0.0000
Zn 0.0038 0.0037 0.0037 0.0079 0.0072
Mg 0.905 0.897 0.785 0.107 0.151 0.042 0.026
Li 0.053 0.053 0.061 0.153 0.131 0.329 0.427
SVIR 2.793 2.824 2.810 2.763 2.813 2.849 2.850
CLASSIFICATION OF MICAS

Ca 0.017 0.031 0.014 0.022 0.028 0.023 0.079


Ba 0.0106 0.0046 0.0002 0.0006 0.0029
Na 0.028 0.029 0.033 0.034 0.035 0.045 0.053
K 0.892 0.868 0.865 0.868 0.887 0.913 0.893
Rb 0.0052 0.0047 0.0078 0.0127 0.0104 0.0442 0.0182
Cs 0.0004 0.0005 0.0011 0.0007 0.0005 0.0033 0.0023
SXIIR 0.953 0.938 0.921 0.938 0.964 1.028 1.046
OH 1.791 1.778 1.808 1.533 1.645 1.078 0.965
F 0.200 0.189 0.178 0.442 0.293 0.895 1.003
Cl 0.009 0.033 0.014 0.025 0.062 0.027 0.032
S 2.000 2.000 2.000 2.000 2.000 2.000 2.000
Mg# 0.386 0.372 0.362 0.053 0.063 0.020 0.014
mgli 0.85 0.84 0.72 0.05 0.02 0.29 0.40
feal 1.73 1.60 1.16 1.67 2.44 2.15 1.51
APPENDIX 3a. Composition (wt.%) of siderophyllite and polylithionite and their varieties.

Mg-rich siderophyllite Siderophyllite sensu stricto Li-rich siderophyllite Fe-rich polylithionite Polylithionite sensu stricto
av s n av s n av s n av s n av s n

SiO2 35.0 1.9 184 35.9 2.2 131 40.0 2.6 429 46.2 2.5 325 51.0 3.4 318
TiO2 2.18 0.89 182 1.21 0.81 126 0.67 0.56 415 0.21 0.29 286 0.09 0.42 189
SnO2 0.013 0.011 43 0.049 0.039 56 0.047 0.034 117 0.035 0.040 55 0.025 0.027 27
Al2O3 21.4 1.5 184 20.2 2.1 131 21.6 1.9 429 21.2 2.3 325 23.8 4.4 318
Ga2O3 0.009 0.003 29 0.014 0.007 20 0.016 0.010 80 0.0125 0.005 45 0.014 0.008 22
Sc2O3 0.004 0.002 47 0.006 0.006 20 0.006 0.004 68 0.006 0.004 29 0.027 0.004 11
V2O3 0.023 0.015 57 0.005 0.008 26 0.002 0.004 81 0.001 0.002 31 0.001 0.002 8
Fe2O3 1.50 1.58 77 2.25 2.65 66 1.95 2.00 209 1.12 1.76 162 0.35 0.61 159
Cr2O3 0.002 0.014 83 0.004 0.013 27 0.005 0.025 98 0.001 0.016 44 0.0003 0.004 9
FeO 19.5 4.6 184 23.7 4.1 131 17.4 4.4 429 9.78 2.61 322 0.88 1.29 273
MnO 0.41 0.51 179 0.64 0.47 130 0.61 0.65 419 0.90 1.46 312 0.72 1.16 301
CoO 0.003 0.001 25 0.002 0.001 21 0.001 0.001 77 0.001 0.001 27 0.0001 0.000 8
NiO 0.005 0.004 55 0.001 0.002 23 0.001 0.001 82 0.002 0.004 39 0.003 0.006 16
ZnO 0.007 0.055 79 0.085 0.068 36 0.090 0.110 107 0.090 0.071 58 0.037 0.049 27
MgO 6.00 3.34 184 1.10 0.70 131 0.41 1.05 427 0.17 0.86 315 0.12 0.56 264

316
Li2O 0.23 0.38 172 0.8 0.21 128 1.79 0.60 429 3.60 0.85 325 4.91 1.00 318
CaO 0.12 0.30 147 0.22 0.36 93 0.25 0.39 263 0.18 0.33 214 0.23 0.69 177
SrO 0.001 0.001 53 0.001 0.001 18 0.003 0.012 82 0.002 0.004 49 0.005 0.007 30
BaO 0.059 0.143 108 0.014 0.022 40 0.015 0.027 139 0.009 0.021 57 0.016 0.026 48
TISCHENDORF ET AL.

PbO 0.002 0.001 28 0.002 0.002 18 0.001 0.004 81 0.002 0.004 28 0.001 0.001 9
Na2O 0.24 0.21 168 0.25 0.18 124 0.31 0.28 423 0.32 0.39 312 0.44 0.46 308
K2O 8.90 0.93 184 8.95 0.74 131 9.31 0.69 429 9.82 0.84 325 10.2 0.7 316
Rb2O 0.240 0.340 84 0.350 0.170 88 0.630 0.288 307 1.030 0.590 218 1.310 0.811 262
Cs2O 0.015 0.787 79 0.040 0.035 48 0.090 0.347 193 0.120 0.367 197 0.250 0.589 212
H2O 3.18 2.64 1.79 1.17 1.35
F 1.63 1.09 106 2.51 1.40 121 4.66 1.62 412 6.45 1.75 304 6.60 1.69 313
Cl 0.008 0.060 37 0.14 0.10 49 0.09 0.45 152 0.018 0.025 31 0.017 0.014 22
Total 100.7 101.1 101.7 102.4 102.4
O = F+Cl 0.69 1.09 1.98 2.72 2.78
Total 100.0 100.0 99.8 99.7 99.6
APPENDIX 3b. Average formulae of siderophyllite and polylithionite and their varieties.

Mg-rich siderophyllite Siderophyllite Li-rich siderophyllite Fe-rich polylithionite Polylithionite


0.3 2.2 Mg sensu stricto 0.3 1.3 Li 0.3 1.1 Fetot sensu stricto

Si 2.654 2.782 2.982 3.276 3.426


IV
Al 1.346 1.218 1.018 0.724 0.574
SIVR 4.000 4.000 4.000 4.000 4.000
Ti 0.124 0.071 0.038 0.011 0.004
Sn 0.0004 0.0015 0.0014 0.0010 0.0007
VI
Al 0.566 0.628 0.880 1.048 1.310
Ga 0.0004 0.0007 0.0008 0.0006 0.0006
Sc 0.0002 0.0004 0.0004 0.0004 0.0016
V 0.0014 0.0003 0.0001 0.0001 0.0001
Fe3+ 0.086 0.131 0.109 0.060 0.018
Cr 0.0012 0.0002 0.0003 0.0001 0.0000
Fe2+ 1.236 1.536 1.084 0.580 0.049
Mn 0.026 0.042 0.039 0.054 0.041
Co 0.0002 0.0001 0.0000 0.0000 0.0000
Ni 0.0003 0.0001 0.0001 0.0001 0.0002

317
Zn 0.0004 0.0049 0.0050 0.0047 0.0018
Mg 0.678 0.127 0.046 0.018 0.012
Li 0.070 0.249 0.537 1.026 1.323
SVIR 2.791 2.792 2.741 2.804 2.761
CLASSIFICATION OF MICAS

Ca 0.010 0.018 0.020 0.014 0.017


Ba 0.0017 0.0004 0.0004 0.0002 0.0004
Na 0.035 0.038 0.046 0.044 0.057
K 0.861 0.885 0.886 0.888 0.874
Rb 0.0117 0.0174 0.0302 0.0470 0.0566
Cs 0.0005 0.0013 0.0029 0.0036 0.0072
SXIIR 0.920 0.960 0.986 0.997 1.012
OH 1.608 1.367 0.869 0.552 0.603
F 0.391 0.615 1.120 1.446 1.395
Cl 0.001 0.018 0.011 0.002 0.002
S 2.000 2.000 2.000 2.000 2.000
Fe# 0.950 0.870 0.690 0.384 0.048
mgli 0.61 0.12 0.49 1.01 1.31
feal 0.91 1.15 0.39 0.34 1.20
APPENDIX 4. Composition (wt.%) and formulae of tainiolite sensu stricto, tainiolitic micas and celadonite.

Tainiolite Fe-rich Al-rich Celadonite Tainiolite Fe-rich Al-rich Celadonite


sensu stricto tainiolitic micas tainiolitic micas sensu stricto tainiolitic micas tainiolitic micas
av s n av s n av s n av s n Mg6Li = Mg6Li = 0.38 Mg6Li = 0.50 Al# = 0.134
1.58

SiO2 56.2 3.5 28 37.7 3.0 17 41.6 1.3 14 54.2 2.3 61 Si 3.863 2.854 2.995 3.848
IV
TiO2 0.20 0.50 22 1.49 1.20 17 1.23 0.71 13 0.17 0.14 30 Al 0.137 1.146 1.005 0.152
Al2O3 1.90 2.70 26 16.0 4.3 17 20.7 1.6 14 5.05 3.17 59 SIVR 4.000 4.000 4.000 4.000
Fe2O3 0.25 1.24 3 1.50 3.90 7 1.00 1.20 9 16.4 4.9 58 Ti 0.010 0.085 0.067 0.009
VI
FeO 0.97 0.16 28 17.5 5.9 17 10.4 2.3 14 4.12 3.43 48 Al 0.014 0.282 0.752 0.270
MnO 0.29 0.48 22 0.33 0.15 17 0.26 0.18 14 0.13 0.09 17 Fe3+ 0.013 0.085 0.054 0.876
MgO 19.6 1.90 28 9.66 3.72 17 6.46 1.88 14 5.98 1.49 61 Fe2+ 0.056 1.108 0.626 0.245
Li2O 2.85 0.69 28 1.14 0.55 17 2.51 1.00 14 Mn 0.017 0.021 0.016 0.008
CaO 0.26 0.73 9 0.09 0.12 15 0.22 0.44 11 0.43 0.77 54 Mg 2.007 1.090 0.693 0.633
Na2O 0.41 0.58 23 0.17 0.21 14 0.19 0.18 14 0.24 0.63 39 Li 0.788 0.347 0.727

318
K2O 10.6 0.7 28 8.54 1.80 17 8.49 1.16 14 8.93 1.52 61 SVIR 2.905 3.018 2.935 2.041
Rb2O 0.90 1 0.75 2.36 14 1.12 1.19 9 Ca 0.019 0.007 0.017 0.033
Cs2O 0.13 1 0.65 2.20 12 0.99 1.21 14 Na 0.055 0.025 0.027 0.033
H2O 0.71 2.81 1.86 3.96 K 0.929 0.825 0.780 0.809
TISCHENDORF ET AL.

F 7.70 1.87 26 2.15 0.95 14 4.86 1.63 14 0.55 0.95 8 Rb 0.040 0.037 0.052
Cl 0.02 1 0.5 2.7 2 0.03 0.02 7 Cs 0.004 0.021 0.030
SXIIR 1.047 0.915 0.906 0.875
OH 0.324 1.424 0.893 1.873
F 1.674 0.512 1.107 0.123
Cl 0.002 0.064 0.004
Total 103.0 101.0 101.9 100.2 S 2.000 2.000 2.000 2.000
O = F+Cl 3.25 1.02 2.05 0.24 mgli 1.22 0.74 0.03 0.63
Total 99.7 100.0 99.8 100.0 feal 0.08 1.02 0.01 0.87
APPENDIX 5a. Composition (wt.%) of muscovite and its varieties.

Li-rich muscovite Muscovite Fe-rich muscovite Li-Fe-rich muscovite Mg-rich muscovite Mg-Fe-rich muscovite
sensu stricto
av s n av s n av s n av s n av s n av s n

SiO2 47.2 2.9 71 46.0 2.0 862 45.7 2.1 251 45.9 1.8 97 51.0 3.7 252 50.5 3.9 31
TiO2 0.09 0.38 53 0.36 0.44 791 0.33 0.34 231 0.22 0.29 88 0.27 0.80 214 0.19 0.31 27
SnO2 0.038 0.031 10 0.019 0.032 113 0.022 0.033 37 0.032 0.022 12 0.026 0.080 3
Al2O3 31.8 3.6 71 34.6 2.4 862 30.8 2.8 251 27.7 3.8 97 26.8 4.2 252 23.7 4.0 31
Ga2O3 0.031 0.016 5 0.018 0.014 57 0.024 0.011 24 0.046 0.021 9 0.013 0.002 3
Sc2O3 0.002 1 0.005 0.0047 125 0.002 0.001 12 0.002 0.001 4 0.001 0.001 3
V2O3 0.002 0.001 2 0.030 2.408 144 0.009 2.796 23 0.005 0.002 9 0.080 5.971 13
Fe2O3 0.40 0.91 40 0.15 0.87 207 1.50 1.48 134 1.35 2.48 48 0.70 1.17 41 2.05 1.78 12
Cr2O3 0.000 3 0.030 2.417 210 0.020 0.283 33 0.004 0.003 4 0.090 3.817 86 0.090 3.053 7
FeO 1.30 1.06 63 1.33 0.84 812 4.00 2.27 244 6.24 3.01 95 1.70 0.93 208 4.20 1.86 27
MnO 0.33 0.50 67 0.05 0.15 668 0.16 0.37 219 0.37 0.60 89 0.04 0.14 139 0.13 0.30 22
CoO 0.002 0.001 66 0.001 0.001 6 0.001 0.001 3
NiO 0.001 0.003 3 0.002 0.002 94 0.001 0.001 25 0.002 0.001 6 0.001 0.741 6 0.020 1
ZnO 0.064 0.055 7 0.010 0.125 220 0.020 0.056 27 0.090 0.155 6 0.040 0.203 20

319
MgO 0.26 0.74 71 1.20 0.46 844 1.07 0.76 249 0.37 0.71 96 3.85 1.60 252 3.40 0.94 31
Li2O 1.72 0.86 71 0.18 0.18 440 0.22 0.20 192 1.38 0.50 97 0.03 0.08 24 0.04 0.35 4
CaO 0.15 0.40 53 0.05 0.17 593 0.07 0.20 189 0.08 0.35 55 0.06 0.13 152 0.15 0.34 22
SrO 0.004 0.011 13 0.005 0.040 145 0.050 0.108 39 0.002 0.002 7 0.002 0.002 3
BaO 0.006 0.011 21 0.200 2.530 412 0.090 2.657 77 0.017 0.016 26 0.400 3.156 63 0.130 0.210 8
CLASSIFICATION OF MICAS

PbO 0.003 0.003 34 0.001 0.001 17 0.003 0.008 11 0.001 0.001 3


Na2O 0.49 0.30 71 0.74 0.47 846 0.40 0.33 247 0.44 0.57 93 0.38 0.29 212 0.18 0.19 29
K2O 10.0 0.8 71 9.98 1.20 862 10.5 1.2 251 10.1 0.9 97 10.0 1.2 252 10.4 1.0 31
Rb2O 1.040 0.930 47 0.190 0.334 282 0.220 0.303 127 0.570 0.377 54 0.020 0.033 3 0.030 0.210 3
Cs2O 0.120 0.238 47 0.025 0.418 187 0.020 0.199 64 0.040 0.279 39 0.003 0.003 3 0.005 0.008 3
H2O 3.32 4.28 3.96 2.93 4.37 4.25
F 2.35 1.68 61 0.45 0.57 409 0.90 1.08 174 2.94 1.43 87 0.25 0.41 45 0.31 1.24 8
Cl 0.12 0.59 10 0.05 0.41 111 0.03 0.54 50 0.10 0.77 31 0.03 0.07 15 0.04 1
Total 100.8 100.0 100.1 100.9 100.2 99.8
O = F+Cl 1.02 0.20 0.39 1.26 0.11 0.14
Total 99.8 99.8 99.7 99.7 100.0 99.7
APPENDIX 5b. Average formulae of muscovite and its varieties.

Li-rich Muscovite Fe-rich Li-Fe-rich Mg-rich Mg-Fe-rich


muscovite sensu stricto muscovite muscovite muscovite muscovite
0.2 1.0 Li 0.2 1.0 Fetot 0.2 0.9 Li 0.2 1.0 Mg 0.2 0.7 Mg
0.2 0.9 Fetot 0.2 0.5 Fetot

Si 3.168 3.074 3.123 3.180 3.398 3.441


IV
Al 0.832 0.926 0.877 0.820 0.602 0.559
SIVR 4.000 4.000 4.000 4.000 4.000 4.000
Ti 0.004 0.018 0.017 0.011 0.014 0.010
Sn 0.0010 0.0005 0.0006 0.0009 0.0007
VI
Al 1.683 1.800 1.604 1.441 1.503 1.345
Ga 0.0013 0.0008 0.0011 0.0002 0.0006
Sc 0.0001 0.0003 0.0001 0.0001 0.0000
V 0.0001 0.0016 0.0005 0.0003 0.0043
Fe3+ 0.020 0.008 0.077 0.070 0.035 0.105
Cr 0.0016 0.0011 0.0002 0.0047 0.0048
Fe2+ 0.073 0.074 0.229 0.361 0.095 0.239
Mn 0.019 0.003 0.009 0.022 0.002 0.008
Co 0.0001 0.0000 0.0000

320
Ni 0.0001 0.0001 0.0001 0.0001 0.0001 0.0011
Zn 0.0032 0.0005 0.0010 0.0046 0.0020
Mg 0.026 0.120 0.109 0.038 0.382 0.345
TISCHENDORF ET AL.

Li 0.464 0.048 0.060 0.384 0.008 0.011


SVIR 2.295 2.077 2.110 2.333 2.051 2.069
Ca 0.011 0.004 0.005 0.006 0.004 0.011
Ba 0.0002 0.0052 0.0024 0.0005 0.0105 0.0035
Na 0.064 0.096 0.053 0.059 0.049 0.024
K 0.856 0.851 0.915 0.892 0.850 0.904
Rb 0.0449 0.0081 0.0097 0.0253 0.0009 0.0013
Cs 0.0034 0.0007 0.0006 0.0012 0.0001 0.0001
SXIIR 0.979 0.965 0.986 0.984 0.914 0.944
OH 1.487 1.899 1.803 1.347 1.944 1.928
F 0.499 0.095 0.194 0.642 0.053 0.067
Cl 0.014 0.006 0.003 0.011 0.003 0.005
S 2.000 2.000 2.000 2.000 2.000 2.000
Al# 0.934 0.899 0.794 0.754 0.746 0.661
mgli 0.44 0.07 0.05 0.35 0.37 0.33
feal 1.57 1.70 1.27 0.98 1.36 0.98

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