True and brittle micas - Commission on New Minerals

Transcription

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
1
2
3
4
AND
M. RIEDER4
Bautzner Strasse 16, D-02763 Zittau, Germany
Institute of Earth Sciences, University of Potsdam, P.O. Box 601553, D-14415 Potsdam, Germany
GeoForschungsZentrum Potsdam, Telegrafenberg, D-14473 Potsdam, Germany
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
Guidotti{, our colleague, friend and co-author of a
recent paper on micas (Tischendorf et al., 2004),
we present in this paper a survey and analysis of
composition and solid solution in the mica group,
comprising trioctahedral and dioctahedral,
common and uncommon true K micas, other
alkali-element-bearing micas, and brittle micas.
The principles behind the subdivision, and the
graphical presentation adopted, follow the recommendations of the Mica Sub-committee of the
International Mineralogical Association’s
Commission on New Minerals, Nomenclature
MICAS are widespread in igneous, metamorphic
and sedimentary rocks. Their crystal structure
accommodates a plethora of elements, leading to
a large and diverse mineral group. The compositional diversity of micas has led to numerous
attempts at classification and graphical presentation (Foster, 1960a,b; Tröger, 1962; Rieder et al.,
1970, 1998; Koval et al., 1972; Gottesmann and
Tischendorf, 1978; Černý and Burt, 1984; Monier
and Robert, 1986; Jolliff et al., 1987; Burt, 1991;
Tischendorf et al., 1997, 2004; Sun Shihua and
Yu Jie, 1999, 2000).
* E-mail: [email protected]
DOI: 10.1180/minmag.2007.071.3.285
# 2007 The Mineralogical Society
{
Died 19 May 2005
TISCHENDORF ET AL.
and Classification (IMA-CNMNC) (Rieder et al.,
1998) and the IMA principles of mineral
classification. This paper treats the micas only in
terms of their compositions, an approach that
permits a quick and easy classification of any
mica.
(2) uncommon brittle micas (0.4%): contain V,
Be, Fe3+, Ti or S and O as major elements, in
addition to Ca or Ba [in anandite, bityite,
chernykhite, oxykinoshitalite].
Common true K micas
Principles of classif|cation
Methods
Our classification scheme uses four major,
octahedrally-coordinated cations (Mg, Fetot,
VI
Al, Li) together with the existence of solid
solutions. It considers only IMA-approved endmember names and strictly applies the 50/50 rule
(e.g. Nickel, 1992).
The main parameters in this classification are
VI
R, VIAl and the product Mg6Li (all in a.p.f.u.).
The value of VIR = 2.5 differentiates trioctahedral
from dioctahedral micas. The limiting value
between micas of the phlogopite–annite and
siderophyllite–polylithionite series (VIAl = 0.5)
results from the application of the 50/50 rule. The
same is valid for the parameter Mg6Li, which
separates tainiolite micas (Mg6Li >0.3) from all
other trioctahedral micas (Mg6Li <0.3).
This study is based on mica analyses obtained by
different analytical methods (wet chemical, X-ray
fluorescence, electron- and ion-microprobe
analysis). Data sources not listed in the
References are given in previous publications
(e.g. Tischendorf et al., 1997, 1999, 2001a,b,
2004) or are noted in Deer et al. (2003).
The crystallo-chemical formulae were calculated on the basis of 22 cation charges, except for
oxy-micas with 24 cation charges. The concentration of Li2O, if essential but not known, was
estimated using the empirical equations published
by Tischendorf et al. (2004, their Appendix).
Results
Compositionally, micas are subdivided into true
micas, with monovalent cations in the interlayer,
and brittle micas containing divalent cations in the
interlayer. Our evaluation of mica analyses yielded
the following quantitative subdivisions (in percentages of the total population of ~6750 analyses).
True micas (96.8% of all analyses) comprise:
(1) common true K micas (93.1%): [annite,
celadonite, muscovite, phlogopite, polylithionite,
siderophyllite, tainiolite];
(2) uncommon true K micas (1.6%): contain a
minor element (Mn2+, Fe3+ or F) in an aboveaverage concentration [fluorannite, masutomilite,
montdorite, shirozulite, tetra-ferriannite, tetraferriphlogopite], an uncommon element (Zn, V,
Cr, Mn3+ or B) as major element [in boromuscovite, chromphyllite, hendricksite, roscoelite,
norrishite] or a common element in an uncommon
coordination (e.g. Na+ in shirokshinite);
(3) uncommon true non-K micas (2.1%):
contain the monovalent cations Na, Rb, Cs or
NH4 as major element substituting for K [in
aspidolite, ephesite, nanpingite, paragonite, preiswerkite, sokolovaite, tobelite].
Brittle micas (3.2% of all analyses) comprise:
(1) common brittle micas (2.8%): contain Ca or
Ba as major cations proxying for K [in clintonite,
ferrokinoshitalite, ganterite, kinoshitalite,
margarite];
(1) Phlogopite–annite series
trioctahedral (VIR >2.5); VIAl <0.5; Mg6Li <0.3
end-members: phlogopite KMg3[AlSi3O10](OH)2,
annite KFe2+
3 [AlSi3O10](OH)2
classification according to the ratio Mg/
(Mg+Fetot) [= Mg#]
phlogopite: Mg# >0.5
annite: Mg# <0.5
(2) Siderophyllite polylithionite series
trioctahedral (VIR >2.5); VIAl >0.5; Mg6Li <0.3
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
[Al2Si2O10](OH)2, polylithionite
KLi2Al[Si4O10]F2;
classification according to the ratio Fe tot /
(Fetot+Li) [= Fe#]
siderophyllite: Fe# >0.5
polylithionite: Fe# <0.5
(3) Tainiolite group
trioctahedral (VIR >2.5); Mg6Li for tainiolite
sensu stricto >0.7, for tainiolitic micas 0.3 0.7
end-member: tainiolite KLiMg2[Si4O10]F2
(4) Muscovite celadonite series
dioctahedral (VIR <2.5); Mg6Li <0.3
end-members: muscovite KAl 2 &[AlSi 3 O 10 ]
(OH)2, celadonite: KMgFe3+&[Si4O10](OH)2;
classification according to VIAl/(VIAl+Fetot+Mg)
[= Al#]
muscovite: Al# >0.5
celadonite: Al# <0.5
286
CLASSIFICATION OF MICAS
Celadonites are further subdivided according to Li
et al. (1997) as confirmed by Rieder et al. (1998).
Distribution of natural compositions in the mgli feal
plot
Mica compositions may be described in twodimensional triangular or three-dimensional plots
(cf. Tischendorf et al., 2004, for a compilation).
We have proposed a simple two-dimensional
presentation according to the occupancy of the
octahedral sheet, using the parameters Mg minus
Li (= mgli) and VIFetot+Mn+Ti minus VIAl (=
feal) a.p.f.u. (Tischendorf et al., 1997, 2004).
Figure 1 shows common true K micas,
excluding only tainiolite and celadonite. The
maximum in the frequency distribution of natural
muscovite compositions is close to the endmember composition. Two frequency peaks
occur in the phlogopite–annite series, and one
occurs in the siderophyllite–polylithionite join.
Very few compositions plot in the relatively large
areas in the Mg-Al sector (lower right) and in
smaller areas in the Fe-Li sector (upper left) of the
plot. Figure 2 shows the numbers of cations per
formula unit for compositions in the phlogopite–
annite, siderophyllite–polylithionite and
muscovite–celadonite series. Figure 3 shows
species resulting from the application of the
50/50 rule. Joins combining related end-members
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 endmembers, 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 muscovite 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
In the following, we point out important
compositional features of common true K micas
in Fig. 4, some of which shed new light on the
relationships between common true K micas,
uncommon true micas and brittle micas. Because
of the wide compositional variation of common
true K mica species, we characterize varieties
according to their compositions (Appendices 1 5).
Phlogopite (1814 analyses): Many compositions (43%) have insufficient IVAl, suggesting that
Fe3+ and/or Ti4+ may be present in the tetrahedral
sheet. Of these compositions, 28% are so close to
the end-member formula that they may be referred
to as phlogopite sensu stricto; 50% are Fe-rich
288
phlogopites, 12% Ti-Fe-rich phlogopites, 5% AlFe-rich phlogopites, 4% Ti-rich phlogopites (up to
0.75 a.p.f.u. Ti), and 1% Al-rich phlogopites (up
to 0.5 a.p.f.u. VIAl; for example Ferry, 1981)
(Appendices 1a and b). Few phlogopites have
larger Mn contents, but some (4%) contain
considerable fluorine (>1 a.p.f.u.; Stoppa et al.,
1997, Motoyoshi and Hensen, 2001); the latter
should be termed F-rich phlogopite. Phlogopite
enriched in Zn or V (up to 0.6 a.p.f.u.) is
uncommon. The maximum contents (in a.p.f.u.)
are 0.20 for Cr, 0.12 for Cs, 0.04 for Ni and 0.07
for Rb. Barium behaves differently, because a
solid-solution series exists from phlogopite–
kinoshitalite (cf. Figs 11a and 12).
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
the samples analysed appear to have no VIAl.
Only 7% refer to annite sensu stricto. Most
annites (50%) are classified as Mg-rich annite,
33% as Al-Mg-rich annite, 5% as Ti-Mg-rich
annite (up to 0.65 a.p.f.u. Ti), and 3% as Al-rich
annite. About 2% of the annite micas contain
>0.3 a.p.f.u. Li and, therefore, represent Li- or LiAl-rich annite (Appendices 2a and 2b). Li-rich
annite is usually also enriched in F (up to
1.4 a.p.f.u.; e.g. Kile and Foord, 1998). A few
annites are Cl-rich (in the range 0.3 0.9 a.p.f.u.;
Oen and Lustenhouwer, 1992). Also uncommon
are annites containing large concentrations of Zn
(0.3 0.6 a. p . f.u.; Tr a c y , 1 9 91 ) o r M n
289
(0.3 0.6 a.p.f.u.). Large concentrations of Ba
(0.3 0.5 a.p.f.u.) may be an indication of a
solid-solution series between annite and ferrokinoshitalite (cf. Figs 11a and 12).
Siderophyllite (748 analyses): most micas
(58%) classified in this group are Li-rich siderophyllites (with F up to 1.8 a.p.f.u.), followed by
Mg-rich siderophyllite (25%), and siderophyllite
sensu stricto (17%) (Appendices 3a and 3b).
However, compositions corresponding to ideal
KFe2+
2 Al[Al2Si2O10](OH)2 do not occur in nature
(Fig. 24). Because Si4+ does not occur below
2.5 a.p.f.u. (except for micas with Ba2+ and/or
Ca 2+ and/or Fe 3+ >0.5 a.p.f.u. and/or Ti4+
>0.25 a.p.f.u.), the octahedral sheet must accom-
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+)
cations to balance charges. Therefore, a more
realistic composition would be KFe2+
1.75Al0.75
Li0.25Mg0.25[Si2.5Al1.5O10](OH)2 (for VIR = 3.0)
or KFe 2+
1.75 Al 0.75 & 0.25 Li 0.125 Mg 0.125 [Si 2.875
Al1.125O10](OH)2 (for VIR = 2.75), respectively
(Appendix 3b, and Tischendorf et al., 2004).
Compositionally, siderophyllite is an atypical endmember mica, because it plots in the centre of all
K-mica compositions. It contains all the principal
elements of the octahedral sheet, Fe, VIAl, Mg and
Li. A few siderophyllites contain Mn
(0.30 0.35 a.p.f.u., Abdalla et al., 1994;
Mohamed et al., 1999), with Cs and Rb contents
of up to 0.20 and 0.15 a.p.f.u., respectively.
290
Polylithionite (648 analyses): half of all
polylithionites are polylithionite sensu stricto,
the rest being Fe-rich polylithionite. About 80%
of the compositions contain 1.0 2.0 a.p.f.u. F
(Appendices 3a and 3b). The Rb concentration
seldom exceeds 0.3 a.p.f.u., but one Rb-rich
polylithionite (unnamed) contains 0.82 a.p.f.u.
Rb (Černý et al., 2003). Concentrations of Cs in
polylithionite are usually large, and Cs-rich
varieties (up to 0.88 a.p.f.u., Wang et al., 2004)
do exist. Sokolovaite, a Cs analogue of polylithionite, was proposed by Pautov et al. (IMA
2004-012; Burke and Ferraris, 2005).
Tainiolite (28 analyses) and tainiolitic micas
(31 analyses): in contrast to common true K micas,
characterized either by high Mg or high Li,
tainiolite has high Mg (0.5 2.3 a.p.f.u.) and high
Li (0.4 1.0 a.p.f.u.) (Appendix 4). Such compositions have a unique position within the mica
group. By containing some Al and Fe, tainolite
deviates slightly from ideal KLiMg2[Si4O10]F2.
Also, it has moderate concentrations of Rb and Cs.
Tainiolite can, of course, be plotted in terms of
mgli/feal, but because of possible coincidence with
unrelated mica compositions, it should be treated
as a separate subsystem (Fig. 5). Tainiolites are
theoretically characterized by Mg6Li >0.5
a.p.f.u. In addition to tainiolite sensu stricto,
other micas with large Mg and large Li contents
occur that are intermediate between tainiolite and
other common true K micas. Such micas may be
termed tainiolitic micas. These micas are typically
enriched in Cs. Accordingly, we may distinguish
three groups of tainiolites (Appendix 4):
(1) Tainiolite sensu stricto; characterized by
Mg6Li >0.7 a.p.f.u.; Mg >1.9 a.p.f.u.; Si =
3.1 4.0 a.p.f.u.; in carbonatites (Le Bas et al.,
1992; Cooper et al., 1995); transitional to
phlogopite, but unusually enriched in Li;
(2) Fe-rich tainiolitic micas; characterized by
Mg6Li = 0.3 0.7; Fetot >0.9; Si = 2.6 3.1; in
Red Cross/Tanco pegmatites (Morgan and London,
1987; Hawthorne et al., 1999); transitional to Mgrich annite, but unusually enriched in Li;
(3) Al-rich tainiolitic micas; characterized by
Mg6Li = 0.3 0.7; VIAl >0.6; Si = 2.6 3.1; in
spodumene pegmatites (Kuznetsova and
Zagorskiy, 1984; Semenov and Shmakin, 1988:
‘magnesian zinnwaldite’, Pesquera et al., 1999);
transitional to Li-rich siderophyllite, but
unusually enriched in Mg.
The positive correlation of Mg and Li applies
only to tainiolite sensu stricto. In Fe-rich and Alrich tainiolitic micas, MgO and Li2O correlate
negatively, as in all other micas. We stress that, in
the mgli/feal plot, the area of tainiolite sensu
stricto shows no overlap with the area of
siderophyllite (Fig. 4).
Muscovite (1574 analyses): most muscovites
(55%) have compositions close to the ideal
formula and exhibit very limited chemical
variation. The next most common compositions
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.
Mg, Fe2+, Li and VIAl, or micas with tetrahedral
cations that are different from Si and IVAl.
(16% each). Li-Fe-rich muscovite (6%), Li-rich
muscovite (5%), and Mg-Fe-rich muscovite (2%)
are comparatively rare (Appendices 5a and b).
Generally, the concentration of other elements in
muscovite is small. Related dioctahedral mica
end-members (e.g. roscoelite, chromphyllite,
ganterite), which form solid-solution series with
muscovite, explain large concentrations of V, Cr
and Ba in the latter (Morand, 1990; Breit, 1995;
Treolar, 1987; Hetherington et al., 2003).
Concentrations of F, up to ~2 a.p.f.u., may
occur in Li-rich muscovite. Concentrations of
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 presentation proposed by Li et al. (1997) is equivalent to
mgli/feal. However, because of their Fe3+ concentrations, celadonites must be presented either
jointly with muscovite (Tischendorf et al., 2004)
or in a separate plot (Fig. 6).
Interlayer
Instead of K, the following elements may be
the dominant cation in the mica interlayer: Na,
Cs, Rb, NH4, Ca and Ba.
K–Na substitution. The substitution of Na in the
interlayer of common trioctahedral K micas
(Fig. 7a) generally ranges up to 0.4 a.p.f.u., and
only rarely beyond 0.45. Full replacement of K by
Na in phlogopite and eastonite leads to aspidolite
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 coordinations. 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
micas with the interlayer occupied by atoms other
than K, micas with octahedral cations other than
FIG. 6. Classification of the celadonite family in the mgli/
feal diagram.according to the principles of Li et al.
(1997).
292
(19 analyses) and preiswerkite (26 analyses),
respectively. The Na mica ephesite (9 analyses)
has no K counterpart. Likewise, the substitution
of Na in common dioctahedral K micas is
<0.4 a.p.f.u. (Fig. 7b). The mica with a complete
substitution of K by Na is paragonite
(72 analyses). There also exists a Sr-enriched
variety of paragonite containing up to 0.23 a.p.f.u.
Sr (Bryanchaninova et al., 2004). The large
difference in ionic radius between Na+ and K+
makes likely the existence of a miscibility gap in
all such binaries, manifest by a significantly
increased number of compositions in which K or
Na dominate relative to intermediate compositions. Guidotti et al. (1994) examined the extent
of K Na substitution and associated other
chemical changes.
K Rb substitution. Although Voncken et al.
(1987) synthesized the Rb analogue of muscovite,
and Beswick (1973) experimentally demonstrated
complete miscibility between K and Rb in
phlogopite, no end-member with Rb as the
dominant interlayer cation has yet been observed
in nature. The substitution of Rb in the interlayer
of common true K micas rarely exceeds
0.20 a.p.f.u. (Fig. 8). Exceptions are Rb-rich
annite (0.45 a.p.f.u. Rb) and a still unnamed Rb
analogue of ‘zinnwaldite’ (0.82 a.p.f.u. Rb; Černý
et al., 2003).
K Cs substitution. Common trioctahedral
micas may substitute up to ~0.20 a.p.f.u. Cs
(Fig. 9). Černý et al. (2003) reported enrichment
of Cs in some phlogopite, annite and siderophyllite micas. Also, there is a Cs-rich mica
described as Cs polylithionite by Černý et al.
(2003, one analysis) and Wang et al. (2004, 13
analyses). Sokolovaite is the Cs analogue of
polylithionite (Pautov, IMA 2004-012; Burke and
Ferraris, 2005). Complete substitution of K by Cs
in dioctahedral micas leads to nanpingite (3
analyses, Yang et al., 1988; Ni and Hughes, 1996;
Peretyazhko et al., 2004). Data indicate a
miscibility gap in the interval 0.20 0.60 a.p.f.u.
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
analysis of N and the inability to analyse H by
electron microprobe.
K Ca substitution. The Ca concentration of
trioctahedral common true K micas does not
exceed ~0.30 a.p.f.u. Larger Ca concentrations,
corresponding to 0.9 1.0 a.p.f.u., are characteristic for clintonite (48 analyses), a brittle mica
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. 8. Proportion of Rb in XIIR for annite (ann),
siderophyllite (sid), polylithionite (pol), tainiolite (tai)
and muscovite (mus). Rubidium (>0.1 a.p.f.u.) in
muscovite and polylithionite is given as averages (n =
number of analyses) at 0.1 a.p.f.u. intervals. Numbers of
analyses are given in parentheses. Most data for Rb-rich
micas come from Skosyreva and Vlasova (1983) and
Černý et al. (2003).
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)
and nanpingite (nan). Data for Cs rich micas were taken
from Yang et al. (1988), Hawthorne et al. (1999), Černý
et al. (2003), Peretyazhko et al. (2004) and Wang et al.
(2004).
FIG. 10. Proportion of NH4 in XIIR for phlogopite (phl),
muscovite (mus) and tobelite (tob). Data are taken from
Higashi (1978, 1982, 2000) [Japan], Wilson et al. (1992)
[Utah, USA] and D.E.Harlov (2005, pers. comm.)
[Maine, USA; Erzgebirge, Germany].
294
analyses) is a dioctahedral brittle mica with Ca
concentrations in the range 0.5 1.0 a.p.f.u..
However, the Ca concentration in muscovite
reported to date is small, indicating the absence
of a solid-solution series between muscovite and
margarite (Fig. 11b).
K Ba substitution. Unlike the substitutions
above, the K Ba replacement in trioctahedral
micas of the phlogopite–annite series is almost
complete (cf. Greenwood, 1998). If the Ba-for-K
substitution exceeds 0.5 a.p.f.u., the mica is
kinoshitalite (57 analyses) or oxykinoshitalite
(2 analyses), an exotic, Ti-enriched mica known
only from an olivine nephelinite (Kogarko et al.,
2005). Ferrokinoshitalite (4 analyses) is a brittle
mica with an octahedral sheet resembling that of
annite (Guggenheim and Frimmel, 1999), whereas
anandite (5 analyses, Pattiaratchi et al., 1967) has
an additional condition, namely that IVAl be
replaced by IVFe3+ and that S be incorporated
instead of one (OH). In dioctahedral micas, a
partial replacement of K by Ba results in the
formation of ganterite (13 analyses, Graeser et
al., 2003; Hetherington et al., 2003; Ma and
Rossman, 2006) or chernykhite (2 analyses), if
VI
V simultaneously substitutes for VIAl.
Phlogopite, kinoshitalite, annite and ferrokinoshitalite form complete solid solutions
(Figs 12a, 13). All four of these end-members
participate in the series (see also Frimmel et al.,
1995, their Fig. 2). The K Ba substitution in the
interlayer is coupled with the tetrahedral substitution XIIBa + IVAl > XII(K,Na) + IVSi (Brigatti and
Poppi, 1993). The concentration of Ba in
muscovite is usually <0.4 a.p.f.u., and ganterite
is characterized by Ba ~0.5 a.p.f.u. (Fig. 12b). A
composition corresponding to the ideal endmember BaAl2&[Al2Si2O10](OH)2 has not yet
been reported from nature. The Ba-V-rich mica
chernykhite described by Ankinovich et al. (1973)
contains only ~0.3 a.p.f.u. Ba and thus does not
reach beyond the required 50%.
Octahedral sheet
Octahedral substitutions are responsible for the
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
large concentrations (Mn2+, Fe3+, Ti); (2) the
incorporation of unusual elements in significant
concentrations (Zn, V, Cr); and (3) the incorporation of an element in a valence state uncommon in
micas (Mn3+).
Incorporation of high Mn. Even though the Mn
concentrations of dioctahedral micas are
<0.2 a.p.f.u., several trioctahedral Mn-bearing
micas exist, including shirozulite, the Mn
analogue of annite, produced by the substitution
of Mn2+ for Fe2+. No compositions close to the
end-member have been found. The composition
reported in the original description (Ishida et al.,
2004) has only 1.53 a.p.f.u. Mn2+. Masutomilite,
the Mn-analogue of what used to be termed
‘zinnwaldite’, owes its existence to the same Fe2+
> Mn2+ substitution. However, the ideal Mn =
1.0 a.p.f.u. of the masutomilite lies beyond the
range of natural compositions (Harada et al.,
1976). The most Mn-rich polylithionite
(0.59 a.p.f.u.) was reported by Boggs (1992).
The most Mn-rich phlogopite has 1.1 a.p.f.u
296
(Yoshii et al., 1973) and for annite up to 0.57
Mn a.p.f.u. (Chen and Wu, 1987). Norrishite (8
analyses) is a rare Li-bearing mica with trivalent
Mn. All these micas have high Mn, but they never
reach the ideal Mn mica end-member (Eggleton
and Ashley, 1989; Gnos et al., 2003). Montdorite
is an uncommon Mn-bearing, tetrasilicic transitional mica that has yet been found at only one
locality and for which only one single analysis is
available (Robert and Maury, 1979).
Hendricksite (3 analyses) may contain up to
1.1 a.p.f.u. Mn 2+ (Frondel and Ito, 1966;
Guggenheim et al., 1983) (Fig. 14).
Incorporation of high Zn. Hendricksite is the
only uncommon trioctahedral mica in which the
Zn concentration may reach 1.45 a.p.f.u. No
doubt exists about the coordination of Zn
because there is insufficient Mg (1 2.5 a.p.f.u.)
and Fe2+ is low (<1 a.p.f.u.) (Frondel and Ito,
1966; Frondel and Einaudi, 1968; Guggenheim et
al., 1983). Other phlogopites and annites may
have Zn concentrations up to 0.6 a.p.f.u. (Craig et
al., 1985; Tracy, 1991). Zinc concentrations in
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 continuously 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 trioctahedral micas are <0.2 a.p.f.u. (Fig. 17). However,
Cr is concentrated in dioctahedral micas, for
which there is a continuous series from muscovite
through Cr-rich muscovite (Treloar, 1987) to
chromphyllite (21 analyses). Chromphyllite
may also display enrichment in Ba (up to
0.2 a.p.f.u.; Reznitskiy et al., 1997).
Incorporation of high Fe3+. The nature of entry
of Fe3+ in the octahedral sheet has not been
sufficiently studied, but the deficiency of IVAl is
F IG . 13. XII Ba (>0.3 a.p.f.u.) as a function of
Mg/(Mg+Fetot) [=Mg#] for phlogopite(phl)/kinoshitalite
(kino-phl) [Mg#>0.5] and annite(ann)/kinoshitalite
(kino-ann) as well as ferrokinoshitalite(Fekino)
[Mg#<0.5]. The distribution of points for phlogopitetype and annite-type kinoshitalites may indicate the
existence of a solid-solution series across the whole
system.
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
(mon), norrishite (nor), shirozulite (shi) and hendricksite
(hen). Numbers of analyses appear in parentheses. Data
sources for uncommon micas: Frondel and Ito (1966),
Robert and Maury (1979), Guggenheim et al. (1983),
Eggleton and Ashley (1989), Gnos et al. (2003) and
Ishida et al. (2004).
FIG. 15. Zn vs. the remaining octahedral cations for
phlogopite (phl), annite (ann) (Zn >0.3 a.p.f.u.), siderophyllite (sid), and muscovite (mus) (Zn >0.05 a.p.f.u.) as
well as for hendricksite (hen). Numbers of analyses
appear in parentheses. Most data were taken from
Frondel and Ito (1966), Guggenheim et al. (1983), Craig
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
3+
3+ 2+
VI
[R2+
R = 2.5). In rare
2.5Fe0.5] (or [Fe1.5R ] for
cases up to 1.5 a.p.f.u. Fe3+ may enter the
octahedral coordination. At greater Fe3+ concentrations (>0.4 a.p.f.u.), a good correlation corresponds 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+
concentrations >0.4 0.8 a.p.f.u. (Mansker et al.,
1979; Henderson and Foland, 1996; Zhang et al.,
1993), the assumption is that some of the Ti fills
the tetrahedral site to a sum of 4.0. Good
elemental correlations support the substitution
scheme VI Ti 4+ + 2 IV Al > VI R 2+ + 2 IV Si
(Tschermak-type substitution, see also Mesto et
al., 2006) that functions at high Ti4+ concentrations (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. 16. Contents of V vs. the remaining octahedral
cations for phlogopite (phl) (V >0.3 a.p.f.u.), and
muscovite (mus) (V >0.2 a.p.f.u.) as well as for
roscoelite (ros), chromphyllite (crph) and chernykhite
(cher). Numbers of analyses are given in parentheses.
Data sources for uncommon micas: Ankinovich et al.
(1973), Treolar (1987), Hofmann (1990), Meunier
(1994), Breit (1995) and Reznitskiy et al. (1997).
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
analyses are given in parentheses. Data for chromphyllite were taken predominantly from Treolar (1987) and
Reznitskiy et al. (1997).
FIG. 18. Plot of VIFe3++IVAl vs. VIR2++2IVSi for
phlogopite (phl) and annite (ann) micas whose Fe3+
content was determined analytically. Shown are a.p.f.u.
intervals of Fe3+ of the respective species.
298
(Weiss et al., 1985; Pekov et al., 2003).
Armbruster et al. (2007) demonstrated extended
solid solution between tainiolite and shirokshinite.
smaller concentrations accompany progressively
more ferruginous compositions. In annite with
Mg# <0.4, the Ti concentration does not exceed
0.4 a.p.f.u. (Fig. 20).
Incorporation of Na. The existence of the
trioctahedral mica shirokshinite (4 analyses), a
Na analogue of tainiolite, indicates that other
micas, particularly those from Na-rich assemblages, may have Na in octahedral coordination
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-ferriphlogopite (19 analyses; Brigatti et al., 1996) are
analogues of annite and phlogopite, with IVFe3+
replacing IVAl. Tetra-ferriphlogopite seems to
have a pronounced miscibility with phlogopite
(Fig. 21, also Brod et al., 2001; Tombolini et al.,
2002). Anandite (5 analyses) is an enigmatic
S-bearing brittle mica, also related to annite.
Incorporation of B. Trioctahedral micas invariably contain <0.15 a.p.f.u. B, most commonly
<0.05 a.p.f.u. (Černý et al., 1995; Badanina et al.,
2004). The bulk of the dioctahedral micas also
contain <0.15 a.p.f.u. B. Generally, no correlation
exists between B and IVAl (Fig. 22). However,
FIG. 20. Contents of Ti (>0.25 a.p.f.u.) as a function of
Mg/(Mg+Fetot) [=Mg#] in Ti-rich phlogopite (Ti phl)
and Ti-Fe-rich phlogopite (Ti-Fe phl) [Mg# >0.5] as
well as in Ti-Mg-rich annite (Ti-Mg ann) [Mg# <0.5].
FIG. 21. Relation of IVFe3+ to IVAl in phlogopite (phl)
and tetra-ferriphlogopite (tetra-ferriphl). Data are taken
from Brod et al. (2001; Table 4 and 7) and Tombolini et
al. (2002; Table 1).
FIG. 19. Plot of VITi+2IVAl against VIR2++2IVSi for
phlogopite containing between 0.40 and 0.75 a.p.f.u. Ti.
299
TISCHENDORF ET AL.
Stoppa et al., 1997) in mafic to ultramafic rocks.
Fluorannite is an F-rich annite present in only
some evolved A-type granites (Shen et al., 2000,
but also Charoy and Raimbault, 1994). Large Cl
concentrations appear restricted to some of the
annites, hendricksitic phlogopites to annites, and
ferrokinoshitalites. Highest Cl concentration is
reported in ferrokinoshitalite from skarns (Tracy,
1991), with an OH/F/Cl ratio of 0.47/0.27/1.26
(a.p.f.u.). In rare cases, O or S is incorporated in
trioctahedral micas such as the Ti-rich brittle mica
oxykinoshitalite (2 analyses), in which Fe is
completely replaced by Ti (Kogarko et al., 2005),
norrishite (2 analyses; Eggleton and Ashley,
1989), and anandite (5 analyses; Pattiaratchi et
al., 1967).
such a replacement relationship appears if boron
is >0.5 a.p.f.u., leading in some cases to
boromuscovite (10 analyses; Foord et al., 1991;
Novák et al., 1999; Thomas et al., 2003).
Incorporation of Be. The brittle mica bityite
(13 analyses) is a geochemical paradox, allowing
(as in tainiolite) a simultaneous presence of
substantial concentrations of incompatible
elements (Be, Li) and a compatible element (Ca)
(Lin and Guggenheim, 1983; Lahti and
Saikkonen, 1985). In compositions with IVAl
ranging from 2 to 1 a.p.f.u. (and Be from 0 to
1 a.p.f.u.), a continuous replacement of IVAl by
Be, according to the coupled substitution Ca2+ +
Be2+ > (K,Na)+ + IVAl3+, appears to operate
(Fig. 23).
Anions
The anion positions are occupied mainly by
(OH) and F and, more rarely, by Cl, S or O. Most
Mg-Fe micas (phlogopite, annite, Mg-rich siderophyllite), and Al micas (muscovite, celadonite),
are OH-rich; Li micas (polylithionite, tainiolite)
are typically F-rich. Li-rich annite, Li-rich siderophyllite and Li-rich muscovite are transitional.
Fluorine supplied by mantle degassing may give
rise to F-rich phlogopite (up to 1.65 a.p.f.u.; e.g.
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
micas were taken predominantly from Černý et al.
(1995) and Badanina et al. (2004); data for boromuscovite are from Foord et al. (1991), Novák et al. (1999)
and Thomas et al. (2003).
Discussion and conclusions
Charge balance
By definition, trioctahedral micas should contain
three cations, and dioctahedral micas two cations,
in octahedral coordination. If the sum of cation
charges is constant (= 22, including K), the
occupancy of the tetrahedral sheet is fixed. For K
micas and other micas with a univalent cation in
the interlayer it follows that:
five octahedral charges (e.g. polylithionite: 2Li+
+ Al3+, tainiolite: 2Mg2+ + Li+, celadonite: Fe3+ +
Mg2+) require [Si4];
FIG. 23. Plot of XIICa + IVBe as a function of XII(K,Na) +
IV
Al for bityite and Be(Li)-rich margarite (mar). Be
contents (in a.p.f.u.) are indicated. Numbers of analyses
are given in parentheses. Data were taken from Lahti
and Saikkonen (1985).
300
six charges as in phlogopite (3Mg2+) or
muscovite (2Al3+) require [Si3Al];
six-and-a-half charges as in Fe-rich phlogopite
(1.5Mg2+ + Fe2+ + 0.5Al3+) or annite (2.5Fe2+ +
0.5Fe3+) require [Si2.5Al1.5];
seven charges (siderophyllite: 2Fe2+ + Al3+,
eastonite: 2Mg 2+ + Al3+ ) would require a
tetrahedral sheet of [Al2Si2].
Surprisingly, natural common true K micas with
tetrahedral composition [Al2Si2] are not known.
Their minimum concentration of IVSi is 2.5.
In contrast, brittle micas (with a divalent cation
such as Ca and Ba in the interlayer) with
six octahedral cation charges (e.g. kinoshitalite
[3Mg2+] or margarite [2Al3+]) would require
[Al2Si2] in the tetrahedra;
seven octahedral cation charges (e.g. clintonite
[2Mg2+ + Al3+]) would require an absolute
minimum of tetrahedral Si [Al3Si].
In practice, clintonite has Si1.1 1.3
(48 analyses). Therefore, an increasing proportion
of divalent cations (Ca2+, Ba2+) in the interlayer
of true micas, as well as an increase of trivalent
(Fe3+, also VIAl3+) and quadrivalent cations (Ti4+)
in the octahedral sheet (normally occupied in the
phlogopite–annite series by divalent cations such
as Mg2+, Fe2+), brings about a minimization of Si
in tetrahedral coordination. On the contrary,
incorporation of monovalent Li in the octahedral
sheet (except the uncommon ephesite and bityite)
may increase tetrahedral Si up to 4.0.
Figure 24 gives an overview of charge-balance
as a function of Si. The plot shows mean values
for analyses of all mica species. True micas obey
the following relation for cation charge sums: VIR
= 9 IVSi. The equation for brittle micas is VIR =
8 IVSi. Micas deviating from these relationships
(kinoshitalite, margarite, anandite) have a smaller
proportion of divalent cations in the interlayer
(0.69 a.p.f.u. Ba, 0.74 a.p.f.u. Ca, 0.88 a.p.f.u.
Ba, respectively). According to its formula,
ganterite (Ba ~0.50 a.p.f.u.) is intermediate
between true and brittle micas. Bityite plots in a
special position because of its concentration of
IV
Be2+. Oxykinoshitalite and norrishite are distinguished by a different fundamental condition of
24 cation charges; besides, the latter has the
unique concentration of trivalent manganese.
Ephesite (like eastonite) is a mica that plots at
the outer border of the mgli/feal diagram (Figs 2
and 3), indicating a trioctahedral, but abnormal
status. Note that the theoretical end-member
compositions of siderophyllite and eastonite in
Fig. 24 lie well outside the bulk of the mica
analyses. The Mg-Fe mica group [Si = 2.5 2.9],
the Al mica group [Si = 2.9 3.3] as well as the
Li-Al mica group, including tainiolite, montdorite
and celadonite (= tetra-silicic micas) [Si =
3.3 4.0], form separate clusters along the line
VI
R = 9 IVSi.
Substitution of elements, solid-solution series, and
miscibility gaps
301
A significant property of the micas is that, almost
without exception, they form solid solutions. In
this study, we have not examined whether a
particular mica is a member of a complete solidsolution series with well defined end-members, or
whether it is a result of only a partial elementexchange. We have dealt with real analytical
determinations of elements and tried to establish
their mutual relationships. In such a case, all
statements about substitutions of elements in
minerals should be normalized to the scale of
examination. Accordingly, microprobe analyses
can avoid problems (multiple generations of a
mica, the presence of heterogeneous phases, etc.)
and will yield results different from wet-chemical
analyses. The future application of new and more
sophisticated analytical techniques will certainly
offer a more detailed view of the phase chemistry.
Because of the multicomponent nature of the
mica chemical system, and the wide possibilities
of mutual replacement of elements in micas,
complex relationships govern the occupancy of
individual coordinations and the conditions for a
necessary charge-balance. Guidotti and Sassi
(1998) used their detailed study of metamorphic
Na/K white micas as an example of the
miscellaneous isomorphic substitutions. Element
substitutions in common true K micas are not
restricted to schemes operating within a particular
solid-solution series, but deviate into compositional space between such series. We may
distinguish five magmatic evolutionary pathways
(Fig. 25):
(I) Phlogopite sensu stricto–Ti-rich phlogopite–
Ti-Fe-rich phlogopite–Fe-rich phlogopite–Mg-Tirich annite–annite sensu stricto–Li-rich annite
(corresponding with a branch of the complete
trioctahedral system phlogopite/biotite/siderophyllite-lepidomelane according to Foster,
1960a, representing the Al-deficient path developed during the evolution of mantle-derived
magmatic rocks);
(II) Al-rich phlogopite–Al-Fe-rich phlogopite–
Al-Mg-rich annite–Al-rich annite–Al-Li-rich
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:
IV
Si (in a.p.f.u.).
Sum of charges of VIR = 9 IVSi (in a.p.f.u.); for brittle micas: Sum of charges of VIR = 8
Abbreviations as in preceding figures.
annite (branch of the complete trioctahedral
system phlogopite/biotite/siderophyllite–lepidomelane according to Foster, 1960a; Al-enriched
path developed during the evolution of mantlederived magmatic rocks);
(III) Al-Mg-rich annite–Mg-rich siderophyllitesiderophyllite sensu stricto–Li-rich siderophyllite–Fe-rich polylithionite–polylithionite sensu
stricto (ferrous lithium-mica series according to
Foster, 1960b, lithium–iron micas according to
Rieder et al., 1970; path developed during the
formation of crust-derived magmatic rocks,
including their pegmatitic and aplitic derivates);
(IV) Fe-rich polylithionite–Li-Fe-rich muscovite–Fe-rich muscovite (ferrous aluminium–
302
lithium mica series according to Monier and
Robert, 1986, zinnwaldite–muscovite subsolidus
‘autometasomatic’ trend of Henderson et al.,
1989; path developed during late-magmatic
evolution of granites); and
(V) Polylithionite–Li-rich muscovite–muscovite sensu stricto (aluminium–lithium micas
according to Foster, 1960b; path developed
during evolution of pegmatites).
In addition, muscovite, Mg-rich muscovite, Ferich muscovite and Mg-Fe-rich muscovite are
components of metamorphic rocks wherein the
mica composition varies as a function of the
conditions of formation. Tainiolite sensu stricto,
Fe-rich and Al-rich tainiolitic micas, however, are
mostly hybrid products, if evolved solutions react
with mafic rocks.
The best-documented solid-solution series
between true and brittle micas is that between
phlogopite and kinoshitalite (Fig. 12a). Larger Ba
concentrations apparently occur in the whole
phlogopite–annite series; however, whether a
complete miscibility occurs between annite and
ferrokinoshitalite remains an open question
(Fig. 13). Complete element substitution is also
present in the series muscovite–roscoelite
(Fig. 16), muscovite–chromphyllite (Fig. 17) and
phlogopite–tetra-ferriphlogopite (Fig. 21). A
substitution relation probably exists for muscovite–tobelite (Fig. 10), and may also exist between
common true K micas and Na micas, namely
phlogopite–aspidolite (Fig. 7a) and muscovite–
paragonite (Fig. 7b), although the latter appears
more limited. In contrast, miscibility gaps
probably exist between common true K micas
and Ca-bearing brittle micas (Fig. 11a,b), and
between muscovite and boromuscovite (Fig. 22).
Experiments have shown a complete miscibility
between K and Rb in phlogopite, but a possible
miscibility with natural common true K micas
remains to be studied (Fig. 8). On the contrary, the
Cs-rich part in the K Cs system is occupied
(Fig. 9), indicating a complete element exchange.
Although only a few analyses are available in the
system muscovite–bityite, the data indicate a
nearly complete replacement of IVAl by IVBe
(Fig. 23). Manganese and Zn are enriched in some
micas (masutomilite, montdorite, norrishite, shirozulite, hendricksite) that will form only under
special physicochemical conditions and must be
considered separately (Figs 14, 15). The concentrations of Ti as well as Fe3+ are limited because of
their large valence (Figs 18 20). To date, no
known mica (apart from oxykinoshitalite) has
predominant Ti in the octahedral position. Finally,
OH and F are apparently miscible in almost any
mica.
Principles of classif|cation
Micas constitute a group of minerals characterized by a predominant substitution of elements.
Their classification rests on the existence of endmembers and their interconnection by solidsolution series.
Common true K micas can be classified using
VI
R, VIAl, Mg6Li, accompanied by fractions
Mg/(Mg+Fetot) [=Mg#], Fetot/(Fetot+Li) [=Fe#],
and Al/(Al+Fetot+Mg) [=Al#], all in a.p.f.u.. The
303
series phlogopite–Ti-Fe-rich phlogopite–Ti-Mgrich annite–annite–Li-rich annite (I), Al-rich
phlogopite–Al-Fe-rich phlogopite–Al-Mg-rich
annite–Li-Al-rich annite (II), Al-Mg-rich annite–
siderophyllite–Li-rich siderophyllite–Fe-rich
polylithionite–polylithionite (III), Fe-rich polylithionite–Li-Fe-rich muscovite–Fe-rich muscovite–Mg-Fe-rich muscovite (IV), and
polylithionite–Li-rich muscovite–muscovite–
Mg-rich muscovite (V) form the framework of
the common true K micas (Fig. 25). These series
constitute the main substitution patterns present in
natural micas. Most of the main composition
maxima coincide with the mica species (such as
muscovite, phlogopite and polylithionite). An
exception is the relative frequency maximum
close to mgli = 1.25 and feal = 1.25, which
encompasses micas formerly termed ‘biotite’
(Fig. 1). Most of this maximum occurs within
the Mg-rich part of the annite field, but it also
straddles the fields of phlogopite and siderophyllite. Most of the former ‘biotites’ are
intermediate annite–phlogopite solid solutions.
Another, less problematic exception is the relative
maximum close to mgli = 1 and feal = 0, which
is cut by the siderophyllite/polylithionite discrimination divide and lies precisely where the
micas formerly termed ‘zinnwaldite’ would have
plotted. Consequently, most ‘zinnwaldites’ correspond to intermediate polylithionite–siderophyllite solid solutions.
Incompletely investigated micas can be designated with series names such as biotite, phengite,
or zinnwaldite (Rieder et al., 1998) but, after
detailed investigation, such series names ought to
be abandoned in favour of more precise terms
such as Fe-rich phlogopite, Li-Fe-rich muscovite
or Li-rich siderophyllite. These names apply from
an end-member out to the 50/50 divide, which is a
universally accepted border that may run, counterintuitively, through frequency maxima in composition plots.
The Fetot/(Fetot+Li) ratio [=Fe#] can be used,
together with VIAl, to describe compositions at or
near the siderophyllite–polylithionite series.
Alternatively, it can be used alone to sort all
trioctahedral micas, because Fe# = 1.0 holds for
Fe-bearing phlogopite and end-member annite.
Several end-members of the common true K
micas are starting points for solid-solution series
with end-members of uncommon true K micas,
other alkali element true micas, and brittle micas.
Figure 25 presents the whole mica system.
Tainiolites form a special sub-system (Fig. 5).
TISCHENDORF ET AL.
Concerning the classification of celadonites
(Fig. 6), we follow Li et al. (1997).
Natural compositions of common true K micas
represent complex multi-element substitutions
involving Fe2+, Mg, VIAl, Li, Ti, Fe3+ and
Mn2+. However, solid-solution series between
common true K micas and uncommon true
K micas, other alkali-element true micas, and
brittle micas are characterized by simpler,
element-for-element, binary substitutions (e.g.
K > Na or K > Ba or VIAl > Cr).
Relationships of classif|ed micas to the mgli/feal system
The application of the mgli/feal variables offers
an overall view of the whole mica family and
allows the user to inspect all main compositions.
Mica end-members plot in the mgli/feal diagram
at vertices with angles between 90º and 125º
(KMg 3 [AlSi 3 O 10 ](OH) 2 , phlogopite; KFe 2+
3
[AlSi3O10](OH)2, annite; KLi2Al[Si4O10]F2, polylithionite; KAl2&[AlSi3O10](OH)2, muscovite;
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
and 165º represent micas with the ideal compositions KMg2.5Al0.5[Al1.5Si2.5O10](OH)2 (Al-rich
phlogopite), KLiFe 2+
2 [Si 4 O 10 ](OH) 2 (Li-rich
annite) and KLi1.25Al1.75[Al1.5Si2.5O10]F2 (Al-rich
trilithionite). Other essential ideal components,
such as KLi1.5Al1.5[AlSi3O10]F2 (trilithionite),
KMg2Fe2+[AlSi3O10](OH)2 (Fe-rich phlogopite),
KFe2+
2 Mg[AlSi3O10](OH)2 (Mg-rich annite) plot
along the outer boundary of the polygon. Endmember siderophyllite
K F e 22 + A l
[Al2Si2O10](OH)2 or KLi0.25Fe2+
Mg
0.25Al0.75
1.75
[Al1.5Si2.5O10](OH)2
plots at a pivotal point of
the mica system. The position of tainiolite
(KLiMg2[Si4O 10]F2) is unique and isolated
(Fig. 5). Likewise, the celadonites, which definitively contain Fe3+, must be treated separately from
the mainstream micas (Fig. 6). The course of VIR
and VIAl in the diagram, as well as points for micas
lying half-way along the joins of end-members,
delineate the fields of mica species.
The boundaries of mica species in the mgli/feal
diagram are theoretical and may not coincide
completely with those based on the relevant
elemental ratios used for classification. Such
discrepancies may be caused by two important
factors:
(1) Ideal mica members are related to VIR = 3.0
or 2.0, which is the basis underlying the
construction of the diagram; however, occupancies of natural micas may differ from these
values;
(2) For plotting, the theoretical compositions
are reduced to main constituents of the octahedral
sheet (Fetot, VIAl, Ti, Mn, Mg, Li), but in reality,
they may contain additional elements such as Zn,
Cr and V.
Overlaps may affect the boundary between
annite and siderophyllite in particular. Therefore,
Fig. 2 shows two sets of isolines for VIAl = 0.5,
one for VIR = 3.0 and the other for VIR = 2.75. We
recommend use of the VIAl = 0.5 isoline for VIR =
2.75 for discrimination between these two species
(Figs 3 and 4).
The advantages of the application of mgli/feal
variables for classification are:
(1) A graphical presentation of all common true
K micas, trioctahedral and dioctahedral, Libearing and non-Li-bearing, is possible in a
single diagram in two dimensions. Separate
plots should be used only for tainiolites and
celadonites.
(2) The a.p.f.u. values from the crystallochemical formulae are easy to convert into the mgli/feal
variables.
(3) The mgli/feal variables are based on the
main, octahedrally coordinated cations in the
mica structure.
(4) The plotting of all theoretical formulae is
straightforward.
(5) The grids for accompanying variables such
as VIR, IVSi, as well as VIAl, Mg, Fetot (including
Ti + Mn), and Li can be shown in the diagram
(Tischendorf et al., 2004, their Figs 2 and 3).
(6) The mgli and feal variables correspond well
with the substitution vectors according to
Tschermak (Burt, 1991): mgli represents a
condensed form of 3MgIVAl[2LiVIAlSi] 1 and
feal is approximately 3(Fe 2 + Mn 2+ Ti 0.5 ) 2+
[2VIAl] 1, neglecting Fe3+.
(7) The plot offers the possibility to display
fractionation tendencies in magmatic rocks as
evolution series including all mica species and
varieties.
(8) The graphical mica presentation applying
mgli/feal is highly compatible with the chemical
mica classification according to VIAl, VIR, Mg#,
Fe# and Al#.
Acknowledgements
K. Breiter (Prague), R. Thomas, and D.E. Harlov
(both Potsdam) contributed unpublished mica
analyses. F. Pietschmann (Zittau) helped with
the mathematical procedures. The authors wish to
acknowledge the thorough work of A. Hendrich
and M. Dziggel (Potsdam) who carefully
constructed the figures. The paper benefited
from constructive reviews by three anonymous
referees and editorial comments by C. Geiger
(Kiel) and M. Welch (London). B. Clarke
(Halifax) read the final version to check for
language correctness. We also acknowledge
valuable discussions with E.A.J. Burke
(Amsterdam) and E.H. Nickel (Wembley,
Australia).
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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
SiO2
TiO2
SnO2
Al2O3
Ga2O3
Sc2O3
V2O3
Fe2O3
Cr2O3
FeO
MnO
CoO
NiO
ZnO
MgO
Li2O
CaO
SrO
BaO
PbO
Na2O
K2O
Rb2O
Cs2O
H2O
F
Cl
Sum
O =
F+Cl
Total
312
100.0
39.0
0.45
0.001
19.3
0.008
0.002
0.037
0.18
0.400
2.09
0.45
0.000
0.008
0.050
22.0
0.011
0.10
0.001
2.50
0.002
0.16
8.93
0.020
0.007
4.07
0.34
0.02
100.1
0.15
0.33
0.67
1.52
1.6
0.008
0.3
0.001
4.62
0.91
0.800
1.07
2.82
1.7
3.3
0.41
6
1
18
18
1
18
1
1
1
4
4
18
13
1
1
1
18
3
10
2
8
1
17
18
1
1
Al-rich phlogopite
av
s
n
99.9
40.1
1.20
0.004
13.3
0.003
0.002
0.020
0.68
0.720
3.50
0.15
0.001
0.105
0.055
24.3
0.006
0.09
0.013
0.95
0.001
0.45
9.85
0.02
0.002
3.45
1.55
0.04
100.6
0.66
2.02
0.68
2.7
1.61
0.007
3.8
0.002
0.001
2.900
3.94
0.590
2.56
1.99
0.000
0.107
0.014
2.3
0.079
0.19
0.011
2.97
0.001
0.47
1.15
0.092
0.035
275
38
512
485
8
509
10
9
11
120
267
470
353
8
125
12
512
125
294
19
339
9
477
512
96
15
Phlogopite sensu stricto
av
s
n
100.0
3.32
1.72
0.03
100.7
0.73
19.7
0.019
0.08
0
1.10
0
0.27
9.47
0.025
1.51
0.03
2.4
0.016
0.21
0.03
3.28
0
0.35
1.46
0.015
19
4
74
49
49
3
61
2
72
74
4
32
0.120 0.060
74
74
74
3
42
74
47
2.5
2.8
2.06
1.33
0.560
2.30
0.04
2.18
0.350
4.40
0.06
11.4
38.4
8.09
Ti-rich phlogopite
av
s
n
99.7
37.6
2.90
0.002
14.6
0.005
0.004
0.060
1.10
0.120
11.9
0.19
0.008
0.004
0.060
16.4
0.035
0.25
0.005
0.62
0.001
0.32
9.22
0.070
0.010
3.57
0.93
0.11
100.1
0.42
1.25
0.25
2.0
1.36
0.004
2.7
0.004
0.003
0.607
3.28
0.318
4.8
0.50
0.005
0.073
1.896
4.1
0.074
0.49
0.062
2.03
0.001
0.42
0.89
0.149
0.590
576
226
903
896
38
903
76
58
118
423
386
896
797
61
167
133
903
683
628
96
533
40
829
903
228
79
Fe-rich phlogopite
av
s
n
100.0
36.9
6.68
0.001
14.5
0.005
0.010
0.050
0.30
0.130
11.5
0.13
0.010
0.045
0.027
14.5
0.050
0.13
0.010
1.25
0.002
0.53
8.97
0.050
0.008
3.55
0.95
0.14
100.4
0.43
1.21
0.22
0.040
3.19
0.260
3.8
0.13
0.005
0.074
0.040
2.4
0.026
0.25
0.015
2.78
0.004
0.29
1.04
0.026
0.010
1.9
1.79
0.001
2.7
0.002
123
31
221
221
2
221
9
1
9
49
67
220
173
2
25
15
221
190
142
9
138
8
212
221
35
8
Ti-Fe-rich phlogopite
av
s
n
APPENDIX 1a. Composition (wt.%) of phlogopite and its varieties.
99.8
0.28
8.72
0.080
0.010
3.71
0.50
0.37
100.1
0.29
36.6
1.64
0.001
19.1
0.002
0.010
0.045
0.45
0.075
14.5
0.19
0.007
0.017
0.064
13.0
0.070
0.12
0.001
0.55
1.04
0.48
0.36
0.95
1.47
1.97
1.4
0.001
0.005
0.042
2.14
0.120
3.3
0.28
0.004
0.032
0.043
2.3
0.199
0.23
0.064
1.32
1.9
0.87
36
22
77
86
11
9
86
85
1
86
2
8
18
23
27
86
71
9
15
25
86
50
57
14
35
Al-Fe-rich phlogopite
av
s
n
TISCHENDORF ET AL.
Si
IV
Al
IV
Fe3+
IV
Ti
SIVR
VI
Ti
Sn
VI
Al
Ga
Sc
V
VI
Fe3+
Cr
Fe2+
Mn
Co
Ni
Zn
Mg
Li
SVIR
Ca
Ba
Na
K
Rb
Cs
SXIIR
OH
F
Cl
S
Mg#
mgli
feal
2.868
1.121
0.011
4.000
0.065
0.0001
0.000
0.0001
0.0001
0.0011
0.027
0.041
0.209
0.009
0.0001
0.0060
0.0029
2.590
0.002
2.953
0.007
0.0266
0.062
0.899
0.0009
0.0001
0.996
1.644
0.351
0.005
2.000
0.916
2.59
0.31
4.000
0.024
0.0000
0.369
0.0004
0.0001
0.0021
0.010
0.022
0.124
0.027
0.0000
0.0005
0.0026
2.320
0.003
2.905
0.008
0.0693
0.022
0.806
0.0009
0.0002
0.906
1.922
0.076
0.002
2.000
0.945
2.32
0.18
Phlogopite
sensu stricto
2.760
1.240
Al-rich phlogopite
0.3 0.5 VIAl
313
0.950
1.602
0.394
0.004
2.000
0.889
2.12
0.62
2.124
0.006
2.867
0.006
0.0312
0.038
0.874
0.0012
0.0070
0.000
0.020
0.266
0.004
0.000
2.778
0.990
0.119
0.113
4.000
0.440
Ti-rich phlogopite
0.3 0.75 Ti
4.000
0.162
0.0001
0.066
0.0002
0.0003
0.0036
0.061
0.007
0.738
0.012
0.0005
0.0002
0.0033
1.813
0.010
2.877
0.020
0.0180
0.046
0.872
0.0033
0.0003
0.960
1.768
0.218
0.014
2.000
0.694
1.80
0.91
2.789
1.211
Fe-rich phlogopite
0.3 1.4 Fetot
4.000
0.372
0.0000
0.000
0.0002
0.0006
0.0030
0.014
0.008
0.713
0.008
0.0006
0.0027
0.0015
1.601
0.015
2.740
0.010
0.0363
0.076
0.848
0.0024
0.0003
0.973
1.759
0.223
0.018
2.000
0.688
1.59
1.11
2.735
1.262
0.003
Ti-Fe-rich phlogopite
0.3 0.7 Ti
0.3 1.2 Fetot
APPENDIX 1b. Average formulae of phlogopite and its varieties.
4.000
0.091
0.0000
0.389
0.0001
0.0006
0.0027
0.025
0.004
0.900
0.012
0.0004
0.0010
0.0035
1.438
0.021
2.888
0.009
0.0160
0.040
0.826
0.0038
0.0003
0.895
1.837
0.117
0.046
2.000
0.609
1.42
0.64
2.717
1.283
Al-Fe-rich phlogopite
0.3 0.5 VIAl
0.3 1.2 Fetot
314
100.0
99.9
60
24
35.4
3.27
0.009
15.3
0.01
0.008
0.034
3.00
0.018
20.7
0.41
0.006
0.008
0.065
7.78
0.17
0.37
0.002
0.15
0.002
0.19
8.79
0.095
0.02
3.44
0.77
0.25
Total
0.51
0.493
75
75
5
75
1
1
0.040 10
2.74
20
0.046 20
4.4
75
0.15
74
0.002
6
0.116 10
0.036 13
1.84
75
0.0605 60
0.50
49
0.001
8
2.51
46
0.001
7
0.25
70
1.05
75
0.035 11
0.004
7
1.6
1.40
0.002
2.5
100.3
0.38
35.4
5.50
0.008
14.4
0.008
0.004
0.021
0.90
0.027
21.5
0.18
0.005
0.008
0.066
7.86
0.17
0.21
0.001
0.35
0.002
0.19
9.05
0.105
0.011
3.47
0.81
0.07
0.70
0.94
1.7
0.85
0.011
2.2
0.01
0.01
0.020
3.54
0.033
4.2
0.49
0.002
0.017
0.814
2.18
0.15
0.44
0.043
2.36
0.01
0.22
1.11
0.100
0.26
469
137
690
689
137
690
142
102
254
497
338
685
680
169
227
260
690
639
538
206
392
122
673
690
394
208
Mg-rich annite
av
s
n
Total
100.3
O = F+Cl
0.35
SiO2
TiO2
SnO2
Al2O3
Ga2O3
Sc2O3
V2 O3
Fe2O3
Cr2O3
FeO
MnO
CoO
NiO
ZnO
MgO
Li2O
CaO
SrO
BaO
PbO
Na2O
K2 O
Rb2O
Cs2O
H2 O
F
Cl
Ti-Mg-rich annite
av
s
n
99.9
100.3
0.34
35.2
2.65
0.008
19.1
0.007
0.005
0.030
1.88
0.018
20.0
0.32
0.004
0.006
0.065
6.91
0.20
0.17
0.001
0.01
0.002
0.22
8.89
0.160
0.035
3.55
0.74
0.11
0.63
0.14
1.3
0.80
0.009
1.1
0.004
0.004
0.037
2.42
0.021
2.8
0.30
0.002
0.007
0.049
1.90
0.19
0.31
0.006
0.06
0.001
0.18
0.78
0.600
0.627
230
64
453
450
110
453
68
108
162
302
216
452
448
118
171
227
453
358
320
115
250
89
415
453
223
171
Al-Mg-rich annite
av
s
n
99.7
100.4
0.79
34.9
1.97
0.039
17.7
0.021
0.005
0.006
4.30
0.006
25.2
0.61
0.001
0.001
0.135
0.91
0.48
0.26
0.001
0.02
0.004
0.22
8.52
0.250
0.021
2.91
1.77
0.19
1.00
0.09
1.8
0.84
0.022
1.8
0.014
0.003
0.012
3.14
0.003
4.3
0.27
0.001
0.000
0.098
0.76
0.19
0.32
0.001
0.02
0.002
0.18
0.80
0.082
0.021
44
8
46
45
19
46
3
3
6
33
7
46
46
6
6
9
46
45
30
5
10
3
46
46
28
18
Al-rich annite
av
s
n
100.0
100.6
0.58
34.7
3.06
0.021
12.8
0.015
0.007
0.005
4.50
0.004
29.1
0.61
0.003
0.001
0.120
1.25
0.40
0.32
0.002
0.09
0.002
0.22
8.56
0.200
0.015
3.03
1.14
0.45
1.19
0.76
2.1
1.13
0.012
2.8
0.003
0.004
0.002
3.52
0.001
6.0
0.68
0.001
0.000
0.149
0.69
0.20
0.62
0.000
4.49
0.00
0.31
1.01
0.089
0.013
72
16
89
87
13
89
4
2
6
66
6
89
89
4
5
11
89
84
70
2
12
3
84
89
41
30
Annite sensu stricto
av
s
n
APPRENDIX 2a. Composition (wt.%) of annite and its varieties.
99.9
101.4
1.52
0.28
0.49
1.358
0.29
8.85
0.850
0.1
2.00
3.50
0.20
1.49
1.77
0.84
0.30
8.2
2.25
27.7
1.33
0.35
1.01
0.27
5
5.43
3.85
9
1
10
10
3
1
10
10
7
10
10
10
10
1
10
36.5
2.1
1.85 0.92
0.051
12.7
2.5
Li-rich annite
av
s
n
100.1
101.9
1.75
0.35
8.90
0.360
0.068
1.84
4.03
0.24
0.22
1.35
0.94
26.5
1.02
1.30
37.5
1.08
0.057
16.1
1.13
1.22
1.25
0.170
0.052
0.88
0.57
0.64
5.7
0.48
4.12
1.2
0.89
0.006
2.2
8
1
8
9
2
2
9
9
5
9
7
3
9
9
2
9
Li-Al-rich annite
av
s
n
TISCHENDORF ET AL.
Si
Al
SIVR
Ti
Sn
VI
Al
Ga
Sc
V
Fe3+
Cr
Fe2+
Mn
Co
Ni
Zn
Mg
Li
SVIR
Ca
Ba
Na
K
Rb
Cs
SXIIR
OH
F
Cl
S
Mg#
mgli
feal
IV
2.737
1.263
4.000
0.323
0.0003
0.049
0.0004
0.0003
0.0013
0.052
0.0020
1.390
0.012
0.0003
0.0005
0.0038
0.905
0.053
2.793
0.017
0.0106
0.028
0.892
0.0052
0.0004
0.953
1.791
0.200
0.009
2.000
0.386
0.85
1.73
Ti-Mg-rich annite
0.3 0.65 Ti
0.3 1.2 Mg
2.739
1.261
4.000
0.190
0.0003
0.134
0.0004
0.0006
0.0021
0.175
0.0010
1.339
0.027
0.0003
0.0005
0.0037
0.897
0.053
2.824
0.031
0.0046
0.029
0.868
0.0047
0.0005
0.938
1.778
0.189
0.033
2.000
0.372
0.84
1.60
Mg-rich annite
0.3 1.3 Mg
2.685
1.315
4.000
0.152
0.0002
0.400
0.0003
0.0003
0.0018
0.108
0.0010
1.275
0.021
0.0002
0.0004
0.0037
0.785
0.061
2.810
0.014
0.0002
0.033
0.865
0.0078
0.0011
0.921
1.808
0.178
0.014
2.000
0.362
0.72
1.16
Al-Mg-rich annite
0.3 0.5 VIAl
0.3 1.2 Mg
2.761
1.239
4.000
0.117
0.0012
0.411
0.0011
0.0003
0.0004
0.256
0.0003
1.667
0.041
0.0001
0.0000
0.0079
0.107
0.153
2.763
0.022
0.0006
0.034
0.868
0.0127
0.0007
0.938
1.533
0.442
0.025
2.000
0.053
0.05
1.67
Al-rich annite
0.3 0.5 VIAl
2.817
1.183
4.000
0.187
0.0007
0.042
0.0008
0.0005
0.0003
0.275
0.0003
1.975
0.042
0.0002
0.0000
0.0072
0.151
0.131
2.813
0.028
0.0029
0.035
0.887
0.0104
0.0005
0.964
1.645
0.293
0.062
2.000
0.063
0.02
2.44
Annite
sensu stricto
APPENDIX 2b. Average formulae of annite and its varieties.
315
0.053
0.893
0.0182
0.0023
1.046
0.965
1.003
0.032
2.000
0.014
0.40
1.51
0.045
0.913
0.0442
0.0033
1.028
1.078
0.895
0.027
2.000
0.020
0.29
2.15
1.743
0.068
1.874
0.091
0.026
0.427
2.850
0.079
0.077
0.234
0.042
0.329
2.849
0.023
2.950
1.050
4.000
0.064
0.0018
0.443
Li-Al-rich annite
0.3 0.8 Li
0.3 0.5 VIAl
2.953
1.047
4.000
0.113
0.0016
0.164
Li-rich annite
0.3 1.0 Li
SiO2
TiO2
SnO2
Al2O3
Ga2O3
Sc2O3
V2O3
Fe2O3
Cr2O3
FeO
MnO
CoO
NiO
ZnO
MgO
Li2O
CaO
SrO
BaO
PbO
Na2O
K2O
Rb2O
Cs2O
H2O
F
Cl
Total
O = F+Cl
Total
35.0
2.18
0.013
21.4
0.009
0.004
0.023
1.50
0.002
19.5
0.41
0.003
0.005
0.007
6.00
0.23
0.12
0.001
0.059
0.002
0.24
8.90
0.240
0.015
3.18
1.63
0.008
100.7
0.69
100.0
184
182
43
184
29
47
57
77
83
184
179
25
55
79
184
172
147
53
108
28
168
184
84
79
106
37
1.9
0.89
0.011
1.5
0.003
0.002
0.015
1.58
0.014
4.6
0.51
0.001
0.004
0.055
3.34
0.38
0.30
0.001
0.143
0.001
0.21
0.93
0.340
0.787
1.09
0.060
Mg-rich siderophyllite
av
s
n
35.9
1.21
0.049
20.2
0.014
0.006
0.005
2.25
0.004
23.7
0.64
0.002
0.001
0.085
1.10
0.8
0.22
0.001
0.014
0.002
0.25
8.95
0.350
0.040
2.64
2.51
0.14
101.1
1.09
100.0
316
1.40
0.10
2.2
0.81
0.039
2.1
0.007
0.006
0.008
2.65
0.013
4.1
0.47
0.001
0.002
0.068
0.70
0.21
0.36
0.001
0.022
0.002
0.18
0.74
0.170
0.035
121
49
131
126
56
131
20
20
26
66
27
131
130
21
23
36
131
128
93
18
40
18
124
131
88
48
Siderophyllite sensu stricto
av
s
n
40.0
0.67
0.047
21.6
0.016
0.006
0.002
1.95
0.005
17.4
0.61
0.001
0.001
0.090
0.41
1.79
0.25
0.003
0.015
0.001
0.31
9.31
0.630
0.090
1.79
4.66
0.09
101.7
1.98
99.8
1.62
0.45
2.6
0.56
0.034
1.9
0.010
0.004
0.004
2.00
0.025
4.4
0.65
0.001
0.001
0.110
1.05
0.60
0.39
0.012
0.027
0.004
0.28
0.69
0.288
0.347
412
152
429
415
117
429
80
68
81
209
98
429
419
77
82
107
427
429
263
82
139
81
423
429
307
193
Li-rich siderophyllite
av
s
n
46.2
0.21
0.035
21.2
0.0125
0.006
0.001
1.12
0.001
9.78
0.90
0.001
0.002
0.090
0.17
3.60
0.18
0.002
0.009
0.002
0.32
9.82
1.030
0.120
1.17
6.45
0.018
102.4
2.72
99.7
1.75
0.025
2.5
0.29
0.040
2.3
0.005
0.004
0.002
1.76
0.016
2.61
1.46
0.001
0.004
0.071
0.86
0.85
0.33
0.004
0.021
0.004
0.39
0.84
0.590
0.367
304
31
325
286
55
325
45
29
31
162
44
322
312
27
39
58
315
325
214
49
57
28
312
325
218
197
Fe-rich polylithionite
av
s
n
APPENDIX 3a. Composition (wt.%) of siderophyllite and polylithionite and their varieties.
51.0
0.09
0.025
23.8
0.014
0.027
0.001
0.35
0.0003
0.88
0.72
0.0001
0.003
0.037
0.12
4.91
0.23
0.005
0.016
0.001
0.44
10.2
1.310
0.250
1.35
6.60
0.017
102.4
2.78
99.6
1.69
0.014
3.4
0.42
0.027
4.4
0.008
0.004
0.002
0.61
0.004
1.29
1.16
0.000
0.006
0.049
0.56
1.00
0.69
0.007
0.026
0.001
0.46
0.7
0.811
0.589
313
22
318
189
27
318
22
11
8
159
9
273
301
8
16
27
264
318
177
30
48
9
308
316
262
212
Polylithionite sensu stricto
av
s
n
TISCHENDORF ET AL.
Si
Al
SIVR
Ti
Sn
VI
Al
Ga
Sc
V
Fe3+
Cr
Fe2+
Mn
Co
Ni
Zn
Mg
Li
SVIR
Ca
Ba
Na
K
Rb
Cs
SXIIR
OH
F
Cl
S
Fe#
mgli
feal
IV
2.654
1.346
4.000
0.124
0.0004
0.566
0.0004
0.0002
0.0014
0.086
0.0012
1.236
0.026
0.0002
0.0003
0.0004
0.678
0.070
2.791
0.010
0.0017
0.035
0.861
0.0117
0.0005
0.920
1.608
0.391
0.001
2.000
0.950
0.61
0.91
Mg-rich siderophyllite
0.3 2.2 Mg
2.782
1.218
4.000
0.071
0.0015
0.628
0.0007
0.0004
0.0003
0.131
0.0002
1.536
0.042
0.0001
0.0001
0.0049
0.127
0.249
2.792
0.018
0.0004
0.038
0.885
0.0174
0.0013
0.960
1.367
0.615
0.018
2.000
0.870
0.12
1.15
Siderophyllite
sensu stricto
2.982
1.018
4.000
0.038
0.0014
0.880
0.0008
0.0004
0.0001
0.109
0.0003
1.084
0.039
0.0000
0.0001
0.0050
0.046
0.537
2.741
0.020
0.0004
0.046
0.886
0.0302
0.0029
0.986
0.869
1.120
0.011
2.000
0.690
0.49
0.39
Li-rich siderophyllite
0.3 1.3 Li
3.276
0.724
4.000
0.011
0.0010
1.048
0.0006
0.0004
0.0001
0.060
0.0001
0.580
0.054
0.0000
0.0001
0.0047
0.018
1.026
2.804
0.014
0.0002
0.044
0.888
0.0470
0.0036
0.997
0.552
1.446
0.002
2.000
0.384
1.01
0.34
Fe-rich polylithionite
0.3 1.1 Fetot
APPENDIX 3b. Average formulae of siderophyllite and polylithionite and their varieties.
3.426
0.574
4.000
0.004
0.0007
1.310
0.0006
0.0016
0.0001
0.018
0.0000
0.049
0.041
0.0000
0.0002
0.0018
0.012
1.323
2.761
0.017
0.0004
0.057
0.874
0.0566
0.0072
1.012
0.603
1.395
0.002
2.000
0.048
1.31
1.20
Polylithionite
sensu stricto
317
318
26
1
1.87
101.0
1.02
100.0
0.95
2.7
3.0
1.20
4.3
3.90
5.9
0.15
3.72
0.55
0.12
0.21
1.80
2.36
2.20
14
2
17
17
17
7
17
17
17
17
15
14
17
14
12
37.7
1.49
16.0
1.50
17.5
0.33
9.66
1.14
0.09
0.17
8.54
0.75
0.65
2.81
2.15
0.5
28
22
26
3
28
22
28
28
9
23
28
1
1
3.5
0.50
2.70
1.24
0.16
0.48
1.90
0.69
0.73
0.58
0.7
56.2
0.20
1.90
0.25
0.97
0.29
19.6
2.85
0.26
0.41
10.6
0.90
0.13
0.71
7.70
0.02
Total
103.0
O = F+Cl
3.25
Total
99.7
SiO2
TiO2
Al2O3
Fe2O3
FeO
MnO
MgO
Li2O
CaO
Na2O
K2O
Rb2O
Cs2O
H2O
F
Cl
Fe-rich
tainiolitic micas
av
s
n
Tainiolite
sensu stricto
av
s
n
101.9
2.05
99.8
41.6
1.23
20.7
1.00
10.4
0.26
6.46
2.51
0.22
0.19
8.49
1.12
0.99
1.86
4.86
1.63
1.3
0.71
1.6
1.20
2.3
0.18
1.88
1.00
0.44
0.18
1.16
1.19
1.21
14
14
13
14
9
14
14
14
14
11
14
14
9
14
Al-rich
tainiolitic micas
av
s
n
8
7
3.96
0.55 0.95
0.03 0.02
100.2
0.24
100.0
54
39
61
0.43 0.77
0.24 0.63
8.93 1.52
n
61
30
59
58
48
17
61
s
2.3
0.14
3.17
4.9
3.43
0.09
1.49
54.2
0.17
5.05
16.4
4.12
0.13
5.98
av
Celadonite
Si
Al
SIVR
Ti
VI
Al
Fe3+
Fe2+
Mn
Mg
Li
SVIR
Ca
Na
K
Rb
Cs
SXIIR
OH
F
Cl
S
mgli
feal
IV
3.863
0.137
4.000
0.010
0.014
0.013
0.056
0.017
2.007
0.788
2.905
0.019
0.055
0.929
0.040
0.004
1.047
0.324
1.674
0.002
2.000
1.22
0.08
2.854
1.146
4.000
0.085
0.282
0.085
1.108
0.021
1.090
0.347
3.018
0.007
0.025
0.825
0.037
0.021
0.915
1.424
0.512
0.064
2.000
0.74
1.02
2.000
0.03
0.01
2.995
1.005
4.000
0.067
0.752
0.054
0.626
0.016
0.693
0.727
2.935
0.017
0.027
0.780
0.052
0.030
0.906
0.893
1.107
0.875
1.873
0.123
0.004
2.000
0.63
0.87
2.041
0.033
0.033
0.809
3.848
0.152
4.000
0.009
0.270
0.876
0.245
0.008
0.633
Tainiolite
Fe-rich
Al-rich
Celadonite
sensu stricto tainiolitic micas tainiolitic micas
Mg6Li = Mg6Li = 0.38 Mg6Li = 0.50 Al# = 0.134
1.58
APPENDIX 4. Composition (wt.%) and formulae of tainiolite sensu stricto, tainiolitic micas and celadonite.
TISCHENDORF ET AL.
47.2
SiO2
TiO2
0.09
SnO2
0.038
Al2O3
31.8
Ga2O3
0.031
Sc2O3
0.002
V2O3
0.002
Fe2O3
0.40
Cr2O3
0.000
FeO
1.30
MnO
0.33
CoO
NiO
0.001
ZnO
0.064
MgO
0.26
Li2O
1.72
CaO
0.15
SrO
0.004
BaO
0.006
PbO
Na2O
0.49
K2O
10.0
Rb2O
1.040
Cs2O
0.120
H2O
3.32
F
2.35
Cl
0.12
Total
100.8
O = F+Cl
1.02
Total
99.8
av
3
7
71
71
53
13
21
71
71
47
47
61
10
0.003
0.055
0.74
0.86
0.40
0.011
0.011
0.30
0.8
0.930
0.238
1.68
0.59
1.06
0.50
0.001
0.91
71
53
10
71
5
1
2
40
3
63
67
n
2.9
0.38
0.031
3.6
0.016
s
Li-rich muscovite
46.0
0.36
0.019
34.6
0.018
0.005
0.030
0.15
0.030
1.33
0.05
0.002
0.002
0.010
1.20
0.18
0.05
0.005
0.200
0.003
0.74
9.98
0.190
0.025
4.28
0.45
0.05
100.0
0.20
99.8
319
0.57
0.41
2.0
0.44
0.032
2.4
0.014
0.0047
2.408
0.87
2.417
0.84
0.15
0.001
0.002
0.125
0.46
0.18
0.17
0.040
2.530
0.003
0.47
1.20
0.334
0.418
409
111
862
791
113
862
57
125
144
207
210
812
668
66
94
220
844
440
593
145
412
34
846
862
282
187
Muscovite
sensu stricto
av
s
n
45.7
0.33
0.022
30.8
0.024
0.002
0.009
1.50
0.020
4.00
0.16
0.001
0.001
0.020
1.07
0.22
0.07
0.050
0.090
0.001
0.40
10.5
0.220
0.020
3.96
0.90
0.03
100.1
0.39
99.7
av
1.08
0.54
2.1
0.34
0.033
2.8
0.011
0.001
2.796
1.48
0.283
2.27
0.37
0.001
0.001
0.056
0.76
0.20
0.20
0.108
2.657
0.001
0.33
1.2
0.303
0.199
s
174
50
251
231
37
251
24
12
23
134
33
244
219
6
25
27
249
192
189
39
77
17
247
251
127
64
n
Fe-rich muscovite
45.9
0.22
0.032
27.7
0.046
0.002
0.005
1.35
0.004
6.24
0.37
0.001
0.002
0.090
0.37
1.38
0.08
0.002
0.017
0.003
0.44
10.1
0.570
0.040
2.93
2.94
0.10
100.9
1.26
99.7
av
1.43
0.77
1.8
0.29
0.022
3.8
0.021
0.001
0.002
2.48
0.003
3.01
0.60
0.001
0.001
0.155
0.71
0.50
0.35
0.002
0.016
0.008
0.57
0.9
0.377
0.279
s
87
31
97
88
12
97
9
4
9
48
4
95
89
3
6
6
96
97
55
7
26
11
93
97
54
39
n
Li-Fe-rich muscovite
av
0.001
0.040
3.85
0.03
0.06
0.002
0.400
0.001
0.38
10.0
0.020
0.003
4.37
0.25
0.03
100.2
0.11
100.0
0.41
0.07
0.741
0.203
1.60
0.08
0.13
0.002
3.156
0.001
0.29
1.2
0.033
0.003
3.7
0.80
0.080
4.2
0.002
0.001
5.971
1.17
3.817
0.93
0.14
s
45
15
6
20
252
24
152
3
63
3
212
252
3
3
252
214
3
252
3
3
13
41
86
208
139
n
Mg-rich muscovite
51.0
0.27
0.026
26.8
0.013
0.001
0.080
0.70
0.090
1.70
0.04
APPENDIX 5a. Composition (wt.%) of muscovite and its varieties.
1.24
0.19
1.0
0.210
0.008
8
1
29
31
3
3
8
0.130 0.210
0.18
10.4
0.030
0.005
4.25
0.31
0.04
99.8
0.14
99.7
31
4
22
1
12
7
27
22
31
31
27
n
0.94
0.35
0.34
3.40
0.04
0.15
0.020
1.78
3.053
1.86
0.30
4.0
23.7
2.05
0.090
4.20
0.13
3.9
0.31
s
50.5
0.19
av
Mg-Fe-rich muscovite
Si
IV
Al
SIVR
Ti
Sn
VI
Al
Ga
Sc
V
Fe3+
Cr
Fe2+
Mn
Co
Ni
Zn
Mg
Li
SVIR
Ca
Ba
Na
K
Rb
Cs
SXIIR
OH
F
Cl
S
Al#
mgli
feal
320
0.0001
0.0032
0.026
0.464
2.295
0.011
0.0002
0.064
0.856
0.0449
0.0034
0.979
1.487
0.499
0.014
2.000
0.934
0.44
1.57
0.073
0.019
3.168
0.832
4.000
0.004
0.0010
1.683
0.0013
0.0001
0.0001
0.020
Li-rich
muscovite
0.2 1.0 Li
3.074
0.926
4.000
0.018
0.0005
1.800
0.0008
0.0003
0.0016
0.008
0.0016
0.074
0.003
0.0001
0.0001
0.0005
0.120
0.048
2.077
0.004
0.0052
0.096
0.851
0.0081
0.0007
0.965
1.899
0.095
0.006
2.000
0.899
0.07
1.70
Muscovite
sensu stricto
3.123
0.877
4.000
0.017
0.0006
1.604
0.0011
0.0001
0.0005
0.077
0.0011
0.229
0.009
0.0000
0.0001
0.0010
0.109
0.060
2.110
0.005
0.0024
0.053
0.915
0.0097
0.0006
0.986
1.803
0.194
0.003
2.000
0.794
0.05
1.27
Fe-rich
muscovite
0.2 1.0 Fetot
3.180
0.820
4.000
0.011
0.0009
1.441
0.0002
0.0001
0.0003
0.070
0.0002
0.361
0.022
0.0000
0.0001
0.0046
0.038
0.384
2.333
0.006
0.0005
0.059
0.892
0.0253
0.0012
0.984
1.347
0.642
0.011
2.000
0.754
0.35
0.98
Li-Fe-rich
muscovite
0.2 0.9 Li
0.2 0.9 Fetot
0.0001
0.0020
0.382
0.008
2.051
0.004
0.0105
0.049
0.850
0.0009
0.0001
0.914
1.944
0.053
0.003
2.000
0.746
0.37
1.36
3.398
0.602
4.000
0.014
0.0007
1.503
0.0006
0.0000
0.0043
0.035
0.0047
0.095
0.002
Mg-rich
muscovite
0.2 1.0 Mg
APPENDIX 5b. Average formulae of muscovite and its varieties.
0.345
0.011
2.069
0.011
0.0035
0.024
0.904
0.0013
0.0001
0.944
1.928
0.067
0.005
2.000
0.661
0.33
0.98
0.0011
0.105
0.0048
0.239
0.008
1.345
3.441
0.559
4.000
0.010
Mg-Fe-rich
muscovite
0.2 0.7 Mg
0.2 0.5 Fetot
TISCHENDORF ET AL.

True and brittle micas - Commission on New Minerals

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