Lithos 50 Ž2000.

241–253
www.elsevier.nlrlocaterlithos

Fluorine as a tool in the petrogenesis of quartz-bearing magmatic

associations: applications of an improved F–OH biotite–apatite
thermometer grid
)
Ricardo Sallet
´ CP 1639, Natal 59072-970, RN, Brazil
Department of Geology, Federal UniÕersity of Rio Grande do Norte, Campus UniÕersitario
Received 1 October 1998; accepted 23 April 1999

Abstract

Fluorine contents of whole rock and biotites allow to discriminate quartz-bearing magmatic associations through the
nature of protoliths and petrogenetic processes. F and Rb are used to discriminate crustal and mantle derived melts. With the
exception of calcalkaline association in which mantle contribution may be significant, the other quartz-bearing associations
are essentially derived from crustal melting by biotite andror amphibole vapor-absent reactions. Based on experimental data
and on an improved biotite–apatite thermometer grid, closure temperatures from near-liquidus to near-solidus conditions as
well as Ž f H 2 Orf HF . evolution during cooling are determined for the different magmatic associations. It appears that the
liquidus temperature and Ž f H 2 Orf HF . decreases in the order high-silica alkaline, high-K calcalkaline and calcalkaline
associations while the solidus temperature follows an inverse order. The Ž f H 2 Orf HF . values for the peraluminous
associations vary over a wide range and overlap the Ž f H 2 Orf HF . values of the high-K calcalkaline and calcalkaline
associations. q 2000 Elsevier Science B.V. All rights reserved.

Keywords: Fluorine; Biotite; Apatite; Thermometer; Petrogenesis

1. Introduction loss to a fluid phase, particularly in F-rich systems

Fluorine is a trace element not often used in
petrogenetic studies. The main reason why the F
content of igneous rocks and their F-bearing hydrous
minerals are not typically reported in the literature is
related to the geochemical behaviour of this element
and to analytical limitations. The F content of ig-
neous rocks as presently measured may not represent
the original magmatic content, due to possible partial
)
Fax: q55-84-215-3806; E-mail: sallet@geologia.ufrn.br
ŽWebster and Duffield, 1994.. If so, the possibility
of a inhomogenous rate of F loss would limit the use
of F as a tracer. Fluorine is an element not included
in the routine analytical multi-element package, such
as in XRF and ICP. A separated analytical procedure
is thus required, being the ion-selective electrode
method the most usually employed. In addition, both
the ion-selective method for bulk analysis and the
microprobe method have limitations due to their
relatively low precison. Despite these disadvantages,
this work attempts to show how F may be used as a
tool for petrogenetic studies, particularly in combina-

0024-4937r00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 4 - 4 9 3 7 Ž 9 9 . 0 0 0 3 6 - 5
242 R. Sallet r Lithos 50 (2000) 241–253
tion with a newly proposed biotite–apatite ther-
mometer.
2. Fluorine in magmatic associations
F contents in mantle rocks are very low as well as
those of the derived tholeiitic melts ŽAllmann and
Koritnig, 1972; Aoki et al., 1981; Gundmundur et
al., 1986.. The presence of F in mantle rocks is
related to the modal abundance of phlogopite and
apatite in peridotite xenoliths as well as to the rela-
tively higher F contents observed within the associ-
ated host alkaline melts ŽSmith et al., 1981; Vukadi-
novic and Edgar, 1993.. Like other incompatible
elements, the continental crust strongly concentrates
F in hydrous minerals such as apatite, titanite, am-
phiboles, micas and topaz and in fluorite. Thus,
almost all the F present in the continental crust
resides in granitoids and felsic to intermediate meta-
morphic rocks. High to very high F contents also
characterize evolved high-silica alkaline rhyolites and
granites of A-type affinity with topaz andror fluorite
as common accessories ŽChristiansen et al., 1983a;
Whalen et al., 1987; Webster and Duffield, 1994..
It is well known that F contents in igneous rocks
increase with increasing alkalinity ŽTauson, 1974;
Bailey, 1977; Aoki et al., 1981.. F contents may be
related to the nature of the magma sources, mantelic
vs. crustal, and to the nature of the melting pro-
cesses, dry vs. wet. Experimental data suggest that
high-silica alkaline F-lithophile enriched melts Že.g.,
topaz rhyolites and related A-type granites. are de-
rived from biotite andror amphibole vapor-absent
melting of F-rich high-grade metamorphic rocks
ŽCreaser et al., 1991; Skjerlie and Johnston, 1993..
F content variations of consanguineous rocks show
variable and complex trends ŽBailey, 1977; Webster
and Duffield, 1994.. However, two main trends are
observed reflecting the incompatible or compatible
behavior of F. Ži. F contents increase as a result of
differentiation by crystal fractionation of essentially
anhydrous assemblages so bulk partition coefficient
D F - 1. This case is observed in dry alkaline high-
silica rhyolites and related A-type granites where
biotite, the main OH–F-bearing phase, is typically a
late-stage phase ŽClemens et al., 1986; Webster et
al., 1987; Sallet et al., 1997.. More, the low Mg, Fe,
and H 2 O contents of these magmas inhibit crystal-
lization of significant amounts of biotite and permit
the characteristic late-stage crystallization of fluorite
andror topaz. Žii. F contents decrease as a result of
differentiation by crystal fractionation of hydrous
minerals so bulk partition coefficient D F ) 1. This
case is observed within wet calcalkaline magmas
where apatite, amphibole, and biotite are typically
early formed phases. F enters the OH site and be-
haves as a compatible element Že.g., Kanisawa, 1979;
Christiansen and Lee, 1986..
Basic to intermediate igneous rocks are rich in
F-bearing hydrous mafic minerals, namely amphi-
boles and biotites. Their F content should thus reflect
the F contents of the melt from which they crystal-
lize. The significance of the intimate association of
these rocks with granites in batholiths can be ana-
lyzed through F contents. In a composite massif or
batholith, if the granitic rocks are F-enriched relative
to the basic and intermediate rocks, it may be con-
cluded that granites are not linked to them by means
of crystal fractionation. This is commonly observed
ŽTauson, 1967; Bailey, 1977; Czamanske et al., 1981.
and the magma source, andror the nature of melting
processes, must be considered to explain the varia-
tion in F contents.
3. F whole rock and biotite systematics
Magmatic associations can display large variation
in alkalinity and silica content. A study of the
whole-rock F systematics must then be based on a
comparison of rocks of similar silica contents. Rocks
of the calcalkaline, high-K calcalkaline, high-silica
alkaline and peraluminous associations have con-
trasting F contents.
3.1. F Õs. Rb whole rock systematics
Like F, Rb is an incompatible element concen-
trated in the continental crust. A Rb–F diagram is
thus a potential tool for the discrimination of mag-
matic associations and can constrain the mantle vs.
continental crust nature of the magma sources. As
both Rb and F may be mobilized by fluids, data from
the literature, for quartz-bearing magmatic associa-
tions, were compiled and selected in order to include
 R. Sallet r Lithos 50 (2000) 241–253 243

only rocks that do not present noticeable hydrother-
mal alteration. As shown in Fig. 1, in the Rb vs. F
plot, a field of crustal derived rocks comprising the
high-silica alkaline and peraluminous associations is
defined in constrast with a field including mantle and
related calcalkaline rocks. This latter is bounded at
the high F contents by mantle derived potassic mafic
lavas. Mantle rocks are very depleted in F and Rb,
whereas derived calcalkaline magmas are character-
ized by higher but still low Rb and F contents. The
relative enrichment may be related to partial melting
followed by differentiation andror crustal contribu-
tion. The high-K calcalkaline magmas display mod-
erate F and Rb contents, whereas the high-silica
alkaline magmas exhibit high to extremely high F
and Rb contents. The peraluminous associations are
Rb-rich but present a wide range of F contents.
In contrast to the calcalkaline associations, which
do not display clear correlations in the Rb vs. F plot,
the rocks of the high-silica alkaline and peralumi-
nous associations commonly display positive correla-
tions. Some well-defined fractionation trends are
shown in Fig. 1. The less evolved rocks of these
associations plot at the low-F and relatively low-Rb
portion of the fractional trend within the crustal
rocks field. These already Rb andror F enriched
parental magmas may reach very high F and
lithophile levels in the residual magmas after felds-
pathic fractional crystallization ŽChristiansen et al.,
1984; Landenberger and Collins, 1996.. This suggest
that intermediate to felsic parental magmas are at the
origin of F and lithophile enriched high-silica alka-
line and peraluminous magmas. Experimental data
favor biotite and amphibole vapor-absent partial
melting of middle to lower crustal rocks ŽSkjerlie
and Johnston, 1993; Patino˜ Douce and Beard, 1995..
The incompatible behaviour of Rb and the Rb-F
positive correlations observed in high-silica alkaline
associations are not consistent with the residual-
source model for the genesis of high-silica alkaline
lithophile-enriched magmatic associations ŽCollins et
al., 1982; Landenberger and Collins, 1996.. In fact,
after an early partial melting episode, the proposed
F-enriched residual protholith should be depleted in
Rb.
The positive correlation between F and Rb may
therefore be disturbed, at the local scale, by fluid
exsolution producing either F or lithophile loss.

Fig. 1. F vs. Rb diagram. Crustal magmatic associations field is defined with data from: high-K calcalkaline associations ŽIhlen et al., 1982;
Carten et al., 1988; Sallet, 1988b., high-silica alkaline associations ŽChristiansen et al., 1983a,b, 1984; Whalen et al., 1987; Price et al.,
1992; Charoy and Raimbault, 1994; Webster and Duffield, 1994; Landenberger and Collins, 1996., Sn rhyolites ŽHuspeni et al., 1984.,
Ongonites ŽAntipin et al., 1980. and peraluminous associations ŽClark et al., 1993.. Calcalkaline association field is defined with data from
ŽIshihara and Terashima, 1977; Landenberger and Collins, 1996. and is bounded at the high F contents by potassic lavas ŽZhang et al.,
1995.. Mantle field is assumed to be limited by 10 ppm F and Rb. Trends within the crustal field are: Nova Scotia peraluminous granitoids
ŽClark et al., 1993., closed circles; Suzhou A-type granites ŽCharoy and Raimbault, 1994., open squares and Tomas Range and Spor
Mountain topaz rhyolites ŽChristiansen et al., 1984., open circles. Triangles represents high and low Ca granites averages ŽTurekian and
Wedphol, 1961..
244 R. Sallet r Lithos 50 (2000) 241–253

Within the Henderson and Ute Mo-bearing stocks,

Colorado, the center is F and Rb enriched, whereas
the border is depleted ŽCarten et al., 1988.. In the
Taylor Creek Sn-bearing rhyolites, New Mexico, F
are enriched in glass inclusions related to the host
rhyolite ŽWebster and Duffield, 1994.. The Tabuleiro
high-silica granites, Santa Catarina State, Brazil,
show inverted correlations between F and fractiona-
tion indexes like RbrSr and EurEuU suggesting
fluid exsolution fractionation ŽSallet et al., 1997..
Since F partitions substantially into the fluid phase in
F-rich melts ŽWebster, 1990., the more differentiated
and F-rich the melt is, the more F enters the exsolved
fluid and produces the observed negative correla-
tions.

3.2. F-biotite systematics

F contents of biotite also can discriminate be-

tween magmatic associations ŽWestra and Keith,
1981; Munoz, 1984; Ague and Brimhall, 1987; Sal-
let, 1988a.. However, according to Munoz Ž1984., F
contents of biotite varies in part as a function of its
MgrFe ratio: high MgrFe biotites tend to incorpo-
rate more F than low MgrFe biotites. Based on
F–OH exchange experiments, that author improved
the fluorine intercept value — IVŽF. — to correct
for the MgrFe control:
IV Ž F . s 1.52 X Mg q 0.42 XAn q 0.20 X Sid
y log Ž X FrXOH .
and
X Mg s MgrS octaedral cations,
X Sid s Ž 3 y SirAl. r1.75 1 y X Mg ,
Fig. 2. Biotite IVŽF. histograms for magmatic associations. Data
are from: calcalkaline associations ŽDodge et al., 1969; Cza-
manske et al., 1981; Weiss and Troll, 1989; Gribble et al., 1990;
Cotkin and Medaris, 1993.; high-K calcalkaline associations ŽBar-
` and Cotten, 1979; Sallet, 1988a and inedit data; Emslie and
riere
Ž 1. Loveridge, 1992; Trønnes and Brandon, 1992.; high-silica alka-
line associations ŽImeokparia, 1984a,b; Sallet, 1988b; Tsareva et
al., 1992; Nash, 1993.; peraluminous associations ŽNeiva et al.,
1987; Konings et al., 1988; Pichavant et al., 1988; Chen et al.,
1989; Sevigny et al., 1989; Silva and Neiva, 1990; Thorpe et al.,
1990; Neiva and Gomes, 1991; Fitzsimons, 1996..

XAn s 1 y Ž X Mg q X Sid . .
The biotite IVŽF. allows a direct comparison of the
relative degree of F enrichment in biotite with differ-
ent MgrFe ratios. Increased enrichments correspond
to decreased IVŽF.. A biotite IVŽF. systematics show
that calcalkaline biotites have high IVŽF., high-K
calcalkaline biotites middle IVŽF., and high-silica
alkaline display low IVŽF.. Biotites from peralumi-
nous granitoids show a wide range of IVŽF. values
ranging from calcalkaline values to the high-silica
alkaline ones ŽFig. 2.. The observed tendency with
Ž 2.
whole rock F contents is clearly shown by the biotite
IVŽF. systematics. The biotite IVŽF. may be thus
useful to compare the F contents of magmatic associ-
ations regardless of the degree of differentiation of
the compared rocks.
As biotite IVŽF. is a function of the X FrXOH
ratio within the biotite hydroxyl site, the calculated
values of this parameter may results from F–OH
exchange equilibrium in one of the following sys-
tems: magma–biotite; magma–fluid–biotite and
 R. Sallet r Lithos 50 (2000) 241–253
fluid–biotite. The data used in the systematics shown
in Fig. 2 are not directly related to mineralized
bodies. The observed discrimination between biotites
from different magmatic associations is clear enough
to consider that, if fluids are present, their FrOH
ratios are significantly controlled by the nature of the
magma from which they are derived. On the other
hand, a systematic subsolidus reset of biotites by
meteoric fluids would have a tendency to obliterate
the above discrimination. Thus, biotite IVŽF. can be
used as a comparative and qualitative measurement
of F enrichment in igneous systems Že.g., Munoz,
1984; Icenhower and London, 1997..
4. Biotite–apatite thermometer grid
The biotite–apatite thermometer is based on
F–OH exchange at the hydroxyl site of these miner-
als. This geothermometer was first proposed by
Stormer and Carmichael Ž1971., and subsequently
modified by Ludington Ž1978. to include the effects
of octahedral cations on the biotite F contents. Zhu
and Sverjensky Ž1992. recalibrated the thermometer
based on solid solution models. The version used
here is based on biotite–fluid and apatite–fluid F–OH
experimental data and equilibrium relations ŽSallet,
1988b; Sallet and Sabatier, 1996..
4.1. Formulation
4.1.1. Biotite F–OH exchange
F–OH exchange equilibrium between biotite and
either a silicate melt or a aqueous fluid phase Žsys-
tem in the following discussion. is written as:
biotite Ž OH . q HF s biotite Ž F . q H 2 O.
The log of the equilibrium constant is:
log K s log Ž aFraOH . bt q log Ž aH 2 O raHF . syst .
By assuming a standard state of pure H 2 O and HF,
at 1 bar and the temperature of interest, and F–OH
ideal mixing at the hydroxyl site, activities may be
replaced by fugacities at the system activity term and
by mole fractions at the biotite activity term. The log
of the equilibrium constant is thus written as:
log K s log Ž X FrXOH . bt q log Ž f H 2 O rf HF . syst .
245
Munoz and Ludington Ž1974. experiments — 1 and
2 kbar and 500–8278C — on mica F–OH exchange
show that FrOH ratio is a function of: activity of F
or HF present during crystallization; nature of octa-
hedral sheet elements, especially FerFeq Mg ratio
and F–OH exchange temperature. According to their
data, the equilibrium constant for the biotite-system
F–OH exchange as well as the logŽ f H 2 O rf HF . of the
system are related to temperature and mica composi-
tion by the following relations:
log K s 2100rTq 1.52 X Mg q 0.42 XAn q 0.20 X Sid ,
Ž 6.
log Ž f H 2 O rf HF . s 2100rTq IV Ž F . . Ž 7.
4.1.2. Apatite F–OH exchange
F–OH exchange equilibrium between apatite and
the system is written as:
apatite Ž OH . q HF s apatite Ž F . q H 2 O Ž 8.
and the log of the equilibrium constant is:
log K s log Ž X FrXOH . ap q log Ž f H 2 O rf HF . syst . Ž 9.
Korzhinskiy Ž1981. experiments — 1, 2 and 4 kbar
and 500–7008C — on apatite F–OH exchange show
that: pressure has a negligible effect; F–OH ex-
change behaves as ideal solid solution; at a fixed
Ž f H O rf HF . increasing T decreases the FrOH ratio
2
of apatite. The experimental data relate the equilib-
rium constant and log Ž f H 2 O rf HF . syst to temperature
and apatite composition according to:
log K s y0.0085T Ž K . q 13.25 Ž 10 .
and
Ž 3. log Ž f H 2 O rf HF . syst s y0.0085T Ž K . q 13.25
y log Ž X FrXOH . ap . Ž 11 .
Ž 4.
4.1.3. Biotite–apatite F–OH equilibrium
Biotite–apatite F–OH exchange equilibrium is
expressed as:
apatite Ž OH . q biotite Ž F . s apatite Ž F .
q biotite Ž OH . . Ž 12 .
For equilibrium conditions F–OH exchange be-
Ž 5. tween apatite and biotite equilibrates under the same
246 R. Sallet r Lithos 50 (2000) 241–253

fugacity ratio Ž f H 2 O rf HF . syst . Thus, from Eqs. Ž7.
and Ž11., it follows that:
log Ž f H 2 O rf HF . syst s y0.0085T q 13.25
y log Ž X FrXOH . ap
s IV Ž F . q 2100rT .
Rearranging this expression by eliminating the
term log Ž f H 2 O rf HF . we have:
0.0085T 2 y 13.25 y IV Ž F . y log Ž X FrXOH . ap T
q 2100 s 0.
Solving this equation only one set of results shows
coherent temperatures. The other one is close to zero
or even displays negative values. A biotite–apatite
T–IVŽF. thermometer grid may be constructed calcu-
lating Ž X FrXOH .ap isopleths from Eq. Ž13. by vary-
ing IVŽF. ŽFig. 3.. For a fixed value of Ž X FrXOH .ap ,
the temperature increases with decreasing IVŽF. val-
ues. However, it should be noted that Ž X FrXOH .ap
isopleths can be represented by a corresponding set
of Ž X F .ap isopleths for Cl-poor apatites with Ž XCl .ap
s 0 and Ž X F q XOH .ap s 1. Owing to the preferential
partition of Cl into the fluid phase, magmatic apatite
from quartz-bearing associations usually has very
low Cl contents ŽCzamanske et al., 1981; Candela,
1986; Webster and Holloway, 1990., hence the
Ž 13 . Ž XCl .ap can be negleted. For Cl-rich fluid–rock sys-
tems the Ž X F .ap isopleths grid cannot be calculated,
hence a Ž X FrXOH .ap grid must be plotted. Within
the thermometer grid, a logŽ f H 2 O rf HF . syst isopleth
grid is also plotted calculated as per Eq. Ž5. ŽMunoz
Ž 14 . and Ludington, 1974..
4.2. Application
The apatite–biotite thermometer was applied for
various rock types. A direct check was carried out
against two-feldspars thermometry with two samples
from the Pedras Grandes granites, Santa Catarina
State, Brazil. Biotite and apatite were directly ana-
lyzed with a Cameca microprobe at Camparis, Uni-

Fig. 3. Petrogenetic model in the T–IVŽF. thermometer grid. The boxes of quartz-bearing magmatic associations are labelled calk
Žcalcalkaline., hk Žhigh-K calcalkaline., alk Žalkaline silica saturated. and peral Žperaluminous. and plotted within the biotite IVŽF. and
solidus T range. Crust protholiths field is constructed with data from Skjerlie and Johnston Ž1993.. Solidus temperature data are from
Manning Ž1981., Webster et al. Ž1987., Icenhower and London Ž1995., and Scaillet et al. Ž1995.. Liquidus to solidus arrows are represented
for the associations calk, hk and alk. For the petrogenesis of peraluminous associations, see explanation in the text.
 R. Sallet r Lithos 50 (2000) 241–253 247

versity of Paris 6. Mean compositions were calcu- Table 2

lated for each sample ŽTables 1 and 2.. Due to the Electron micropobe analyses of apatites from the Pedras Grandes
ŽI5 and I12. and Ploumanac’h granites ŽP1.. XOH calculated
highly perthitic character of the K-feldspars and the assuming FqClqOH s1 per formulae unit. ns Number of dis-
presence of zoned plagioclases, these minerals were crete analyses averaged
firstly separated with bromoform, then crushed and I5 Ž ns12. I12 Ž ns 5. P1 Ž ns8.
analyzed by XRF at the University of Lausanne
CaO 53.23 53.14 54.87
ŽTable 3.. The biotite–apatite pair yields 695 and
P2 O5 41.37 40.80 40.84
5968C which is comparable to 698 and 6128C yielded F 3.62 3.75 3.80
by the feldspar thermometry at 5 kbar ŽHaselton et Cl 0.01 0.00 0.02
al., 1983. ŽTable 4.. F,Cl5O 1.53 1.58 1.71
An indirect check was carried out on a sample Total 96.70 96.14 99.53
XF 0.95 0.99 0.99
from the collection ŽUniversity of Paris 6. of the XCl 0.01 0.00 0.00
Ploumanac’h granite, France. Biotite and apatite were XOH 0.04 0.01 0.01
analyzed with microprobe at Camparis ŽTables 1 and
2.. The calculated temperature from the biotite–
apatite pair, 6208C, is comparable to those of 550–
temperatures of 772 and 7468C, which agrees with
6008C obtained by Barriere` and Cotten Ž1979. with
that of 7508C based on phenocryst composition
the magnetite–ilmenite thermometer ŽTable 4..
ŽMoore, 1970, 1973.. At the Bishop Tuff, USA, the
Data from the literature were also used to check
mean biotite IVŽF. s 2.04 ŽHildreth, 1977 in Munoz,
the thermometer ŽTable 4.. Biotite–apatite data from
1984. and apatite compositions from early to late
two samples of the quartz latite porphyry at Bing-
stage eruptions ŽHildreth, 1979. lead to temperatures
ham, USA ŽParry et al., 1978., indicate average
of 722 and 7868C, respectively. It conforms with the
Fe–Ti oxide thermometer which indicates a tempera-
Table 1
ture increase from 720 to 7908C from early to late
Electron microprobe analyses of biotites from the Pedras Grandes stages ŽHildreth, 1979.. At the Macusani felsic pera-
ŽI5 and I12. and Ploumanac’h granites ŽP1.. XOH calculated luminous volcanics, the biotite–apatite pair yields
assuming FqClqOH s1 per formulae unit. ns Number of dis- 8788C, whereas biotite-spinel MgrFe 2qq Feq3 par-
crete analyses averaged tition indicates temperature of about 8008C ŽPicha-
I5 Ž ns10. I12 Ž ns11. P1 Ž ns10. vant et al., 1988.. The relatively higher temperature
BaO 0.09 0.08 0.00
TiO 2 2.76 2.6 3.25
MnO 0.79 0.46 0.05 Table 3
FeO 22.99 22.68 27.44 XRF analyses of feldspars from the Pedras Grandes granites.
K 2O 9.49 9.72 9.29 Temperatures are calculated according to the two-feldspar formu-
CaO 0.02 0.02 0.02 lation of Haselton et al. Ž1983. at 5 kbar. kf — Potassic-feldspar
Na 2 O 0.07 0.08 0.05 and pl — plagioclase
Al 2 O 3 15.1 15.4 13.43 I5 I12
SiO 2 36.35 36.83 35.40
kf pl kf pl
MgO 6.72 7.66 6.34
F 1.15 1.32 1.41 K 2O 12.58 2.92 13.65 2.31
Cl 0.04 0.03 0.23 CaO 0.26 2.04 0.28 3.16
F,Cl5O 0.49 0.59 0.64 Na 2 O 2.85 8.56 2.05 8.32
Total 95.08 96.29 96.27 Al 2 O 3 18.72 20.97 18.72 21.93
XF 0.28 0.32 0.35 SiO 2 65.29 65.25 64.81 63.89
XOH 1.72 1.68 1.62 LOI 0.21 0.63 0.51 0.30
XCl 0.00 0.00 0.03 Total 99.91 100.37 100.02 99.91
X Mg 0.31 0.35 0.27 XAb 0.25 0.74 0.18 0.72
X Sid 0.38 0.36 0.32 XAn 0.02 0.09 0.02 0.15
XAn 0.31 0.28 0.41 XOr 0.73 0.17 0.80 0.13
IVŽF. 1.48 1.45 1.31 T Ž8C. 698 596
248 R. Sallet r Lithos 50 (2000) 241–253

Table 4
Biotite–apatite thermometry results compared with results from other thermometers. See text for explanation
Rock type Sample IVŽF. bt Ž X F rXOH .ap T Ž8C. Other methods T Ž8C.
Santa Catarina granites I5 1.48 23.75 695 pl–kf 698
I12 1.45 99.00 596 612
Ploumanac’h granite P1 1.31 99.00 620 mt–ilm 550–600
Bingham latites 623 2.35 1.05 772 phenocryst 750
620 1.61 10.03 746
Bishop Tuff early 2.04 0.64 722 mt–ilm 720
late 2.04 1.69 786 790
Macusani volcanics MH4-3 0.98 4.56 878 bt–spinel 800
Spanish Lamproites Z 1.69 6.72 747
J 1.71 4.71 768 mt–ilm 740–820
PM 2.20 3.57 711
Zimbabwe Great Dyke W2r28 2.96 0.91 684 cr–ol blocking 600–700
Connemara metapelites BY111a 2.21 6.14 671 bt–gt 620
BY111b 2.21 6.69 665

yielded by the biotite–apatite pair is however com-
patible with a vapor-absent, quartz-saturated biotite
melting at pressures from 6 to 8 kbar ŽBohlen et al.,
1983.. Furthermore, such high temperature complies
with the restitic nature of the Macusani biotites, as
claimed by Pichavant et al. Ž1988.. At the Jumilla
lamproite, Spain, the biotite–apatite pair yields
7688C, whereas the Fe–Ti oxide thermometer indi-
cates temperatures of 740–8208C ŽVenturelli et al.,
1988.. At the Great Dyke of Zymbabwe, the
biotite–apatite pair indicates 6848C, whereas
olivine–chromite FerMg partitioning leads to block-
ing temperatures on the order of 600–7008C ŽWil-
son, 1982; Boudreau et al., 1995.. Finally, in a
sample of the Connemara metapelite, the biotite–
apatite pair yields 665–6718C, whereas a tempera-
ture around 6208C has been estimated with the bi-
otite–garnet thermometry ŽYardley et al., 1980;
Yardley, 1985..
Data from Table 4 show that calculated F–OH
exchange temperatures are consistent with expected
temperatures and, overall, agree with those obtained
from others independent thermometers. Closure tem-
peratures are recorded in high-temperature magmatic
conditions, as exemplified by the volcanic to subvol-
canic rocks, and in low-temperatures near solidus to
subsolidus conditions, as exemplified by the granites.
It has to be emphasized that the proposed ther-
mometer should strictly be used in agreement with
the experimental conditions for which it is formu-
lated: P and T range and, particularly, crystal–vapor
equilibrium. However, the consistent results shown
above allow, at least, a comparative and qualitative
estimate of F contents in melts andror fluids in
equilibrium with biotite and apatite during either
vapor-saturated or vapor-undersaturated partial fu-
sion and crystallization. The following statements are
therefore made: Ži. P does not significantly control
F–OH exchange for both phases, Žii. T extrapola-
tions beyond the thermometer experimental domain
could reliablely be made, Žiii. experimental data
obtained for crystal–vapor F–OH exchange equilib-
rium can be extended to crystal–melt–vapor equilib-
rium and crystal–melt equilibrium. Under vapor-
saturated conditions, melt and vapor ratios Ž f H 2 O r
f HF . should be equal at equilibrium. Under vapor-ab-
sent conditions, Ž f H 2 O rf HF . ratio should be con-
strained by a solid phase assemblage Že.g., Clemens
and Vielzeuf, 1987. andror a silicate melt ŽMunoz,
1984.. Although experimental data on F speciation in
silicate melt indicate that HF is a minor species
ŽSchaller et al., 1992., it is assumed here that
Ž f H O rf HF . syst is proportional to the F contents of
2
the melt.
5. Petrogenetic implications
Except for highly peraluminous granitoids for
which a crustal origin is usually proposed, the large
 R. Sallet r Lithos 50 (2000) 241–253
volume of intermediate to acid granitoids within
batholiths may not be entirely explained through the
evolution by crystal fractionation of mantle derived
basaltic rocks. To a large extent many granitoids,
particularly those that are not directly related to
subduction processes, must originate through the
melting of lower crustal rocks ŽClemens and Vielzeuf,
1987.. Even granitoids related to subduction pro-
cesses contain a component of lower crustal rocks
` and Ben Othman, 1980.. The close associa-
ŽAllegre
tion of mafic and intermediate rocks within large
granitic batholiths with variable mixing and mingling
rates shows the interaction through underplating of
mantle derived basalts and crustal melts.
The calcalkaline granitoids are typically related to
the water-saturated partial melting of a subducted
oceanic crust and the mantle above it with a possible
participation of the lower crust ŽWyllie, 1984.. The
low F contents, even within the more evolved granitic
and rhyolitic terms, are thus explained by the nature
of the magma source. The low F content of sec-
ondary micas within the hydrothermaly altered zones
of porphyry Cu deposits ŽMunoz, 1984. indicate that
the derived fluids are not F rich, too.
The high-K calcalkaline granitoids are commonly
associated with late-orogenic episodes ŽBatchelor and
Bowden, 1985.. They display an alkalinity, Rb and F
contents that are intermediate between calcalkaline
and the alkaline silica-saturated granitoids. These
features are compatible with a pronounced participa-
tion of crustal melts induced by basaltic underplat-
ing. Fluorite is commonly present as late stage sub-
solidus phase.
The high-silica alkaline granites and equivalent
topaz rhyolites ŽChristiansen et al., 1983a. are re-
lated to post-orogenic processes. They are strongly
enriched in lithophiles elements and in F. Their
origin is better understood by the high temperature
vapor-absent melting of biotite andror amphibole in
F-bearing, high-grade, crustal rocks ŽCreaser et al.,
1991; Skjerlie and Johnston, 1993.. Fluorite is
widespread as a magmatic phase as well as a mag-
mato-hydrothermal phase ŽChristiansen et al., 1983a;
Huspeni et al., 1984; Webster et al., 1987; Congdon
and Nash, 1988; Price et al., 1992; Nash, 1993;
Webster and Duffield, 1994..
Peraluminous granitoids, mainly formed during
continental collision ŽBatchelor and Bowden, 1985.,
249
are related to the wet melting of metasedimentary
rocks. Experimental data on H 2 O-saturated, low-
temperature, low-pressure melting of metapelitic
compositions supports this inference ŽIcenhower and
London, 1995.. Nevertheless, other experiments have
shown that vapor-absent, high-temperature, mid- to
high-pressure melting of metapelites and metalumi-
nous protoliths can also produce peraluminous melts
˜ Douce and Johnston, 1991; Patino
ŽPatino ˜ Douce and
Beard, 1995.. According to experimental data, the
partition coefficient for F between micas and melt
are lower for wet, low-temperature, low-pressure
conditions, than for dry, high-temperature, mid- to
high-pressure, conditions ŽPatino ˜ Douce and John-
ston, 1991; Skjerlie and Johnston, 1993; Icenhower
and London, 1997.. Thefore, peraluminous melts
generated under H 2 O-saturated conditions in the up-
per crust should initially be richer in F than peralu-
minous melts produced in the mid- to lower crust
under vapor-absent conditions. The wide range of F
contents observed within peraluminous granitoids is
thus explained by the diversity of the source rocks as
well as by the nature of the melting process.
In the constructed biotite–apatite geothermometer
grid ŽSallet, 1988b; Sallet and Sabatier, 1996. ŽFig.
3., experimental data on the F and on the H 2 O
effects on the solidus temperatures of granitic rocks
ŽManning, 1981; Webster et al., 1987; Scaillet et al.,
1995. allow the Ž f H 2 O rf HF . syst ratio of melts and
fluids to be constrained. This ratio, together with the
solidus temperatures, decrease in the order: calk-al-
kaline, high-K calcalkaline, and high-silica alkaline
associations ŽFig. 3.. Nevertheless, biotite vapor-ab-
sent melting experiments ŽPeterson et al., 1991;
Skjerlie and Johnston, 1993. show that the biotite
stability field is enlarged as the biotite IVŽF. de-
creases: the more F-enriched is the protolith biotite,
the higher the melting temperatures and the F con-
tents of residual micaceous assemblages. In Fig. 3, a
field with high temperatures and Ž f H 2 O rf HF . syst con-
ditions prevailing during the partial melting of crustal
protholiths can be constrained. As for the melt phase,
such high-temperatures represent near-liquidus tem-
peratures. The contrasted F abundances of the typical
magmatic associations may be thus related to that of
the protolith composition. High-K calcalkaline and
high-silica alkaline melts result from high-tempera-
ture, dry-melting of F-bearing, lower crustal rocks.
250 R. Sallet r Lithos 50 (2000) 241–253
The Ž f H 2 O rf HF . syst ratio during cooling and crystal-
lization is somewhat buffered ŽFig. 3.. Calcalkaline
melts form from wet melting of mantle and metalu-
minous crustal rocks. The increase of Ž f H 2 O rf HF . syst
during cooling may be interpreted according to the
oceanic slab water input. Peraluminous granitoids are
produced from the wet or dry melting of variable
crustal protoliths — meta to peraluminous — with
compositions varying thus between the calcalkaline
and high-silica alkaline associations.
6. Conclusions
F appears to be a valuable petrogenetic tool.
Whole rock, biotite and apatite F contents allow Ži.
to discriminate magmatic associations Žii. to consider
mantle vs. crustal contributions and dry vs. wet
melting processes Žiii. to determine the temperatures
and Ž f H 2 O rf HF . syst ratios of biotite–apatite F–OH
exchange. These consistent results suggest that the
hydrothermally calibrated IVŽF. parameter and bi-
otite–apatite thermometer may be successfully ap-
plied to magmatic conditions.
Acknowledgements
I would like to thank J.P. Hogan, and J. Ruiz, for
their useful reviews of early drafts, B. Charoy and
J.M. Montel for journal review, H. Remy and M.
Fialan from Camparis for assistance during microp-
obe analyses and H. Sabatier, A. Nobreza and G.
Melo, Jr. for their cooperation. This research was
partly supported by grants from the Brazil’s National
Council for Science and Technology ŽCNPq. and
from the Sao ˜ Paulo State Research Foundation
ŽFAPESP..
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