M I N E R A L O G I C A L MAGAZINE, MARCH 1 9 7 6 , VOL. 40, PP.

4 5 3 - 6 6

The geochemistry of biotites from granites of

northern Portugal with special reference to
their tin content
A. M. R. N E I V A 1
Department of Mineralogy and Geology, University of Coimbra, Portugal
SUMMARY.Biotites from a number of granites have been analysed for major oxides and a wide range
of trace elements. Their compositions are found to be typical of biotites from granite and to show
element fractionation in presumed differentiation series. Estimates are made of the fugacity of oxygen
and water during the crystallization of the granites. Pmo is fotmd to increase slightly through the
differentiation series, andfo, for a temperature of 7oo ~ is estimated to be between Io -is and Io -12.
Tin mineralization is connected with the igneous rocks and the relationship of tin in the micas to
the rock compositions is described and the factors controlling the distribution of tin are discussed.
The biotites have only up to 2I % of the tin of the granites. In general Sn increases in the biotites
with decreasing temperature of equilibration and with increase in the degree of albitization of the
granites. High Sn in biotites seems to be an indicator of potential mineralization.
B IO TI TE S f r o m the v a r i o u s granites o f Alijd-Sanfins, n o r t h e r n P o r t u g a l , have been
a n a l y s e d as p a r t o f a study o f the geochemistry o f the rocks. Some o f the granites are
associated with tin a n d tungsten m i n e r a l i z a t i o n a n d the present p a p e r deals with the
a c c u m u l a t i o n o f tin in the biotite. I n a d d i t i o n , the relationship between the tin c o n t e n t
o f the biotites a n d the m o d a l a n d chemical c o m p o s i t i o n o f the granites is discussed as
well as the m o r e general chemistry a n d c o n d i t i o n s o f f o r m a t i o n o f the micas. Thirteen
different types o f granite, labelled G I to G X I I I have been recognized (Neiva, 1970.
T h e y have been i n t r u d e d into phyllites a n d metagreywackes, which show p o l y p h a s e
d e f o r m a t i o n . T h e m a i n structural o r i e n t a t i o n is H e r c y n i a n . The rocks are all m u s c o v i t e - b i o t i t e - a l b i t e - g r a n i t e s b u t they all also b e a r quartz, m i c r o p e r t h i t i c microcline,
apatite, zircon, ilmenite, a n d futile. S o m e have t o u r m a l i n e a n d in granite G X I I I ,
delessite, sphene, pyrite, a n d zoisite were found.
G I is the oldest granite a n d is relatively fine-grained a n d gneissose. G I I to G V I I
are c o n c o r d a n t intrusions except for G V, which occurs as fine-grained gneissose
inclusions in G I V a n d which m a y represent granitized phyllite. G r a n i t e s G I I to G
V I I are believed to be r e l a t e d to one a n o t h e r as a differentiation series. T h e y do n o t
have strong aureoles b u t effected m u s c o v i t i z a t i o n a n d t o u r m a l i n i z a t i o n . G I X cuts
G I V a n d G V I I I a l o n g faults. G X to G X H I are d i s c o r d a n t a n d are all porphyritic.
G X cuts G V I I I , penetrates a n d s u r r o u n d s G I V a n d G IX, a n d i n t r u d e d between the
phyllite a n d G V I I ; it is sometimes i n t r u d e d a l o n g N E . - S W . faults. G X I is gneissose
a n d p i n k a n d G X I I a n d G X I I I are p i n k a n d red granites respectively a n d all three
occur as veins a n d small stocks. These last three granites f o r m a n o t h e r p r e s u m e d
Present address: University of Brasilia, 7o-ooo Brasilia, D.F., Brazil.
9 Copyright the Mineralogical Society.

A. M. R. N E I V A

454

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BIOTITES FROM PORTUGAL

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456

A . M . R . NEIVA

differentiation series. They cut G X and were intruded in places along NE.-SW.
faults between G X and the phyllite (Table I).
Biotites from all granites were analysed except for G VH (which has only o - 1 %
chlorite after biotite), G X I I I (because the biotite could not be separated from the
chlorite), and G V. The biotites occur as subhedral grains pleochroic from ~, and/3
brown to c~ pale yellow. They have apatite and zircon inclusions with pleochroic
haloes and are sometimes partly altered to chlorite. X-ray powder photography
showed them to be either I M or 3T polymorphs and a Weissenberg photograph of the
biotite from G X gave a 3T structure. The biotites were separated with a Frantz
magnetic separator and purified by centrifuging in heavy liquids. A purity of about
99"8 % was estimated by optical and X-ray examination--zircon and apatite being the
principal contaminants. Chlorite was removed satisfactorily.
SiO2, TiO~, A120,, total iron, MnO, MgO, and CaO were determined by XRF following
the method of Norrish and Hutton (I969) using the C.S.I.R.O. standard FS 25. These oxides
were also determined in two samples by standard wet chemical methods in order to check
the results. Na~O and K~O were determined by flame photometry and FeO and water by
classical methods. Trace elements Be, Ga, Cr, V, Sn, Li, Ni, Zr, Co, Sr, Pb, Ba, Rb, and Cs
were determined by emission spectroscopy. A muscovite base was used and Pd was the
internal standard. A large quartz-glass Hilger spectrograph was used and the intensities
were measured on a Jarrell-Ash photodensitometer. A precision of
to 25 % is estimated.
The limits of sensitivity are in (ppm): Be 5, Ga 2, Cr 4, V 4, Sn 5, Li I, Ni z, Co 5, Zr 5,
Sr 3, Pb 5, Ba 5. An Associated Electrical Industries Ltd., MS 7 spark source mass spectrograph was used to determine C1, F, Ge, W, Mo, Nb, Zn, In, Cu, Sc, Bi, Er, Yt, Dy, Tb, Gd,
Sm, Nd, Pr, Ce, La, Au, T1. The technique of Nicholls et al. (I967) was employed with
rhenium as internal standard. The precision was estimated to be ~ 7 % with a detection
limit of o-oI ppm.

Chemistry of the biotites. The major and trace element concentrations and structural
formulae of the analysed biotites are given in Table II.
The major element chemistry of the micas shows them to be typical granite biotites.
Plotted in the Al~O3 : total iron : MgO diagram the biotites fall in the field of coexistence with muscovite (Nockolds, I947) and in the magmatic field defined by Gokhale
(1968). In the (Fe20~-+-TiO2) : M g O : ( F e O + M n O ) triangle they correspond with
plutonic biotites of igneous origin (Heinrich, I946; Gokhale, I968) and fall in the
areas of granite biotites defined by Engel and Engel (196o). The minerals are all Fe 2+
biotites and occupy the granite field in the triangle Mg : ( A I + F e ~ + + T i ) : (Fe2++Mn)
defined by Foster (196o) . Several of them fall outside the field of coexistence with
muscovite defined by Albuquerque (I973) in the diagram Ti: Al'i: Fe 3+ (fig. Ia). They
show a decrease in Ti and increase in Fe a+ in the biotites of the presumed differentiation series. As Ti is normally thought to decrease with temperature of formation, this
variation is in keeping with the notion of differentiation. The position of G X I I mica
on Albuquerque's figure suggests that the mineral has been oxidized.
The F, C1, OH, proportions of the micas shows a progressive increase in F and
decrease in O H through the two series and biotites from G I and G V I I I plot apart

BIOTITES

FROM

PORTUGAL

457

from the series (fig. zb). Variations in the micas in element proportions and certain
ratios are shown in figs. 2 and 3. In general the variations for the series G II to G VI
are typical for series of granites and broadly as would be expected from general principles. Similar sequences have been found, for example, by Nockolds and Mitchell
0948) for the elements A1, Fe z+, Mn, Li, Cu, Ti, Mg, V, Ni, and Co; Sen, Nockolds
and Allen Q959) for Mg, Fe2++FO +, Li, V, Ni, and Co; Rub 0972) for Sn, Nb, Li,
Ti

PkSB

90

10

80

20

1~

.-...
"'~

".,

60

.//. 40
/" "...

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Vl
@

I
o

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3o/

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,;

,,'_ ......

IV *VIII
21;"

t
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80

70

60

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>'I

:/"

;~r~J.;,

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50

40
la

30

20

vul.

1o

Fe3+

OH

lb

FIo. za: Ti-AlVL-Fe3+ diagram after (Albuquerque, I973). Dotted lines: fields of biotites coexisting
with pyroxene. Dash-dot lines: fields of biotites coexisting with amphibole. Dashed lines: fields of
biotites unaccompanied by other ferromagnesian minerals or coexisting with muscovite or aluminosilicates. 9 Alij6-Sanfins biotite, b: F-C1-OH diagram of biotites from granites of northern Portugal.

and-F; Kozlov (i969) for F; Lyakhovich (I97o) and Mogarovskiy et al. (z968) for Nb;
and by Ishikawa, Shibata, and Negishi 0963) for V, Ni, and Co. Also, as expected,
the series of minerals show an increase in F/Li ratio though Tauson 0967) found this
ratio to be constant in biotite from the different granitoid rocks of the main phases of
the Verkhne Undisk mesabyssal batholith. Biotites from G I, G VIII, G IX, and G X
differ from one another and from the two series. G I biotite for example contains
more A1, C1, Zn, Bi, and less Fe 3+, Fe~++Fe 3+, Mn, Mg, and Cr than any other and
the ratios Fe~+/Mg, Cs/K are greater and Mn/Fe ~+, Ga/AI, Cr/Fe 3+ are lower than in
any of the other biotites. G VIII biotite contains less Mn, Li, W, Nb, and Cs, and
more Ti, Mg, Ni, In, Co, and Ce than those of G II to G VI. Similarly the ratios total
FeO/MgO, Fe2+/Mg, Mn/Fe ~+, Li/Mg are lower and Ni/Fe ~+, Ni/Mg, and Co/Mg

458

A. M. R. N E I V A

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BIOTITES FROM PORTUGAL

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A. M. R. N E I V A

460

ppm >1507
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Xl

Xll

FIG. 2. Variation diagrams of the major and trace elements of the biotites from the granites of
northern Portugal.

BIOTITES

4.5-

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130~

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,

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XI Xl=l

FIG. 3. Variation diagrams of the major/trace elements ratios of the biotites from the granites of
northern Portugal.

rth

462

A.M.R.

NEIVA

are greater than in the biotites of G II to G VI. These findings show that the G VIII
biotite does not belong to either series. G IX biotite contains less A1, Fe 2+ and more
Mg, K, V, Ni, Co, Gd, Ba and also lower total FeO/MgO, Fe2+/Mg and greater
Ni/Fe 2+ and Ni/Mg ratios than the biotite of any other granite. This granite is slightly
more basic than the others and according to Albuquerque (I973) it is normal for the
biotites of more basic rocks to contain more V, Ni, Co, Ba and greater Ni/Fe 2 Ni/Mg
ratios than those of more acid. The biotite of G X is unique in containing more Dy,
Tb, Gd, Sin, Nd, La, and Au and less Sc and greater ~ Ce/~ Y ratios than any other
Fe3+~/

F e 3+

40
OXll

eXI
1

Ni-

Nio

~I
IVo

Fe 2+

90

9!

\
70

III
-.-e_

.VIII

\
50

Mg

FIG. 4. FeZ+-Fe2+-Mg diagram of biotites from granites of northern Portugal. Lines: composition of
biotites in the system KFe3+A1Si3Otz(H_1)-KFe2+A1Si3010(OH)2-KMgaA1SizO10(OH)~ at constant
fo2 (after Wones and Eugster, 1965). 9 Alij6-Sanfins biotites.

biotite and there is a break in composition between G X biotite and the G XI and
G XII biotites for some elements and ratios. There are also differences between the
two presumed differentiation series. In particular, Mg, Ca, Mn, Sn, V, Co, and Zr
vary in opposite ways in the two sets of micas.
Conditions of biotite formation. Wones and Eugster 0965) have studied the stability
of biotite and given an 'educated guess' as to the biotite compositions likely under
particular buffered conditions of fo~. The present biotite compositions have been
plotted on this diagram and most fall close to either the Fe2SiO4-SiO2-F%O4 or the
Ni-NiO curve (fig. 4)- If it is assumed that the biotites finally equilibrated at a temperature of about 7oo ~ it is then possible to estimate roughly their fo~ value. At this
temperature and for the composition of these particular biotites the micas should be in
equilibrium with potash-feldspar and iron oxides. Variations in total pressure will not
greatly affect this equilibrium for the curves are not especially sensitive to pressure
changes. From the molar composition of the biotites and the estimated fo~ the fri~o
can be calculated (these calculations are inevitably approximate and assume that the

BIOTITES FROM PORTUGAL

463

activity of coexisting phases is unity). The l o g f o ~ values and PH~o values (from
fn~o) obtained by these calculations are:
Biotite
Logfo~
Pl~2o
(bars)

G I

G II

G IV

G VI

G VIII

--I9'7

--17"6 --16'3

--I6-2

--16.2

--15"8 --14'2

G X1
G XII
--15"3 --14"2 --12"3

178

2o0o

20oo

935

5ooo

G III

819

G IX

4ooo

G X

Taken at face value the results show that fo~ increases slightly during the crystallization of both series of differentiates. This contrasts with results given by Albuquerque
(I973), who found t h a t f o ~decreased during the crystallization of rocks varying from
tonalite to granite. However, it seems reasonable to expect increase in PH~o to be
equated with more oxidized minerals and if the later granites are residual from the
earlier they might be expected to have a higher concentration of volatiles. The biotites
from G I, G XI, and G XlI give wild results for the calculation of P~i~o. For G I the
result is very low and the determined composition may not be sufficiently accurate.
For G XI and G XlI the P ~ o value is very high and this may be attributed to postsolidification oxidation of the micas. The reddening of the feldspars may be an indication of this oxidation. The later granites show the highest Pi-i=o and since Ptot~l
> PH~o, it seems that at least the later granites crystallized at a depth of more than
15 km. The total amount of mica increases through the series G II to G VI as the
estimated PH~o increases. The calculated PH~o is lower in G VIII than in G VI and
this is satisfactorily reflected in the reduced total quantity of mica in G VIII.
The role o f tin in biotites has been widely discussed. Hesp (I971) noted a strong
resemblance between the behaviour of Sn and Fe 2+, Fe 3+, and Ti *+ and considered
that it would be diadochic with Ca 2+. Dmitriev et al. (1962) suggested that Fe 3+ was
more closely related than Fe 2+ and Barsukov (I957), Barsukov and Durasova (I966),
Hesp (1970, and Oliveira (1972) noted a positive correlation between Li and Sn. This
was explained by Barsukov (1957) as the result of isomorphous replacement of
(Fe2++Mg 2+) by (Li++Fe3+). Hesp (1971) and Levashev et al. (I971) found a
negative correlation between Sn and Ti and attributed this to the greater degree of
covalency of the Sn-O bond relative to the Ti-O and hence to the greate r electronegativity of Sn. There are also negative correlations between total iron and Sn
and between Fe2+/Fe ~+ and Sn (Rattingan, 1964, reported in Hesp, 1971). In the
present micas Sn is positively correlated with Si and Li and negatively with A1iv, Ti,
and Fe ~+, total iron, and Fe2+/Fe 3 Li is therefore negatively correlated with Ti
(fig. 5a). Thus support is found for the previous work and it seems likely that Sn
substitutes in octahedral sites.
Hesp (1971) proposed an empirical function based on these relationships t h a t he
called the tin-holding capacity (THC) of biotites. The expression given was T H C
[(Fe3++Li+)/(Fe2++Mg2+)]--[(Ti~++Mn~+)/io] and this was found to be correlated
with the Sn content of the mica. Calculation of the function for the present biotites,
however, shows no direct correlation with Sn though there is, as Hesp also showed, a
negative correlation between THC and the modal amount of biotite and chlorite in
the granites. It has also been found that another formula proposed by Hesp is obeyed

A. M. R. N E I V A

464

5nBiot = 3 07 X * 2t 0
r =0.830

140
L
.39

Ti : - 0 , 2 7
Xl

140
,iV

Vie

r = - 0.842

VIH
9

100

IX
9

10(

011

qll

.s .3~

VI~

Li *0.41

'",x

V1

xl

o ~0

~oo

u~

_c
S n eiot=307.54 [(Na-Ca)/K]-65,39
r = 0.721

20

"IV

.23

0.25
Li

045
ions

0.65

20

10

140
BnBiot = -5.03 Microcline * 252.54

~~i
140 9
Vl

9
IV

lO0

r :-0.565

ix

nl vm

II

20

30

40

X:IOTHC * SnGr- 2(moda{'/o Biotite .Chlorite)

0.4

,o

r=0.819

I Vill

IX

i I

2o12

IV
G0

It,Ill

=
/

Vl
9 ~11 .

20
32
modal'/.

3g

d
Z=Sn 6

Mic rocline

rr == 0.917
0.917

11
28

o '~

o.'5
(No- Ca) IK

"Io Sn in Biotite = 536 (lOT HC * modal'/, Biotite)-1327

iV e eVj

~ ~,o~

~f

10 THC modaP/~

50

*modal'l.Plag-(modal'f.

Biotite

B0 e

20!

" t ' S n a i ~ = 4'44 ( B i ~

-5.33
VIII

8-

II ol

Biot*Chl*

9 M u s c ) i n granite

Chi) -

IXe

Bner =-5.67(Blot , C h 0 , 4 4 . 4 6
r =-0.578

, VII
50S n e t = 0.22 S neio,~ 9 7.51
r = 0.865

~~

~45

~,~25

u~

Xl

Vl

.i

illI

IV

x.'"
x.x:;,

60

100

Sn in Biotite (p.p.rn.)

g4
~10-

XII

20

d.

.~-30-

J
I

140
g

i
modal ~

~
Biotite

;
* Chlorite

'h

, -,
2
modal

.
3

. .
4

"/o Biotite*Ch(orite

FIG. 5a: Correlation between Ti and Li ions of biotite from granites of northern Portugal. b: Tin in
biotite as function of [IoTHC+SnGr--Z(modal % biotite+chlorite)]. THC -- tin-holding capacity.
Snor = tin content of granite (ppm). c: Correlation between Sn in biotite and the degree of albitization
of the granites, d: Correlation between Sn in biotite and modal percentage of microcline in the
granite, e: Correlation between Sn in biotite and [Snor + m o d a l % plagioclase--(modal % biotite +
chlorite+muscovite)] in granite, f: Correlation between Sn in biotite as a percentage of total Sn
and I o T H C + m o d a l % biotite), g: Correlation between Sn in granite and Sn in biotite, h: Correlation
between Sn in granite and modal percentage of biotite +chlorite in the granite, i: Correlation between
Sn in biotite as a percentage of total tin and modal percentage of biotite+chlorite in the granite.

by the present rocks, i.e. Sn (biotite) is proportional to [IoTHC-t-Sn(granite)-a(modal % biotite+chlorite)] (fig. 5b).
The tin content of the biotites is related to several chemical amd modal variations
in the present granites and many of these relationships reflect the degree of albitization
of the granites (fig. 5c). As albite increases at the expense of microcline so the tin

BIOTITES FROM PORTUGAL

465

content of the biotite rises. This effect is shown by both differentiation series. The tin
content of the granites themselves also rises as the amount of microcline falls (fig. 5 d)
so that the mineralization appears to be related to the albitization as Karaeva (I968)
has suggested. It is therefore not surprising to find that the tin content of the granites
is positively correlated with Na +, Li and Cs + and negatively correlated with Ti,
Fe 3+, K +, Cr, Ni, Zr, and Sr of the granites. The tin content of the biotites can be
correlated with numerous empirical formulae. For example the Sn(biotite) is proportional to Sn(granite)-~ modal % plagioclase--(modal % biotite+chlorite+muscovite) (fig. 5e); the percentage of tin in biotite is also proportional to I o T H C + m o d a l
% biotite (fig. 5f) and I o T H C + m o d a l % (biotite+chlorite). The combination o f
positive correlation between tin in granite and biotite (fig. 5g) and negative correlation
between tin in granite and the modal percentage biotite (fig. 5h) means that the higher
quantities of tin are concentrated in smaller amounts of the mica. However, the
amount of tin in the tin-rich granites is such that the tin-rich micas contain a smaller
percentage of the total tin than does the mica of the tin-poor granites (fig. 5i). Hence
high Sn content of biotites reflects possible mineralization. Barsukov 0957) indicated
that the tin was held isomorphously in the biotite lattice, but Hesp ( I 9 7 0 found that
some biotites held less than 45 % of the total rock tin and in high-tin granites this fell
to I t to zo %. The present biotites hold less than at most 2~ % of the available tin.
Conclusions. The biotites can be distinguished from one another by both major and
trace elements and they show sequential change through the presumed differentiation
series. Their chemistry also indicates differing fo, values. At 7oo ~ fo~ can have
values ranging from i t -is to io -1~ and tends to increase slightly through the differentiation series. P~t,o calculated from the fo, and mica composition also increases
through both series, reflecting increase in the modal quantity of mica. It is inferred that
at least two of the granites formed at a depth greater than 15 kilometres, though the
calculations have to be used with caution for there is the possibility of subsequent
change in the Fe2+/Fe 3+ ratios of the micas. The tin content of the biotites is probably
not dependent o f f o ' or total pressure but on temperature. It increases with decrease
of temperature and varies inversely with Ti in the Y group in the differentiation older
to younger rocks, suggesting that the mechanism of concentration is fractional
crystallization. Tin probably substitutes isomorphously for some o.f the octahedral
cations and is not influenced by the presence of fluorine.
Various empirical formulae relate the tin content of the micas to the granite chemical and modal composition. The biotites contain less than 2I % of the tin content of
the granites and the amount is directly related to the granite composition. A high tin
content of the granite corresponds with a high tin content of biotite, a low modal
percentage of biotite and a low percentage of the total tin held in the biotite. The
development of the high tin content of the granites is directly related to the degree of
albitization and hence high tin (and lithium) contents of biotites seem to reflect
possible mineralization.

Acknowledgements. Part of this research work was carried out in the Department of Mineralogy
and Petrology, University of Cambridge, England, supervised by Dr. S. R. Nockolds, whose
encouragement is gratefully acknowledged. The trace element determinations with the

466

A.M.R.

NEIVA

spark-source mass spectrograph were carried out in the Department of Geology, University
of Manchester, England, and thanks are due to Dr. G. D. Nicholls for the use of the facilities
of his laboratory. The author also thanks Professor J. M. Cotelo Neiva for his encouragement.
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-

[Manuscript received 7 July I974, revised 9 M a y I975]