Fluid inclusion study of tin-mineralized greisens

and quartz veins in the Penouta apogranite

(Orense, Spain)*
J. MANGAS

Department of Geology, Faculty of Marine Sciences, University of Las Palmas de Gran Canaria, Campus de
Tafira, 35017 Las Palmas de Gran Canaria (Spain)
AND

A. ARRIBAS
Directorate-General XI1, Science, Research and Development, Commission of the European Communities,
Rue de la Loi 200, B-11149Brussels, Belgium

Abstract
The Penouta deposit is associated with a small Hercynian apogranite stock that intrudes
Precambrian-Cambrian gneisses of the Oflo de Sapo Formation. Tin ore occurs as disseminations of
cassiterite in the apogranite and as greisenized zones and quartz veins which traverse both the alkaline
leucogranite and the surrounding metamorphic country rocks.
A fluid-inclusion study, utilizing microthermometric, crushing tests and Raman spectroscopic
techniques on quartz from an intragranitic vein and a greisen of the host rock, indicates that the
evolution of fluids was similar in both samples and occurred in the three main stages: The first stage is
characterized by complex CO2 (CO2-N2-CH4-H2S) and complex CO2 aqueous (H20-NaC1-CO2-N2-
CH4-H2S) fluids of low salinity (T,n ice > - 6 ~ homogenization temperatures between 250 and
410 ~ homogenization pressures below 900 bars, and thermobarometric trapping conditions with
temperatures below 700 ~ and pressures below 3250 bars. These fluids were probably responsible for
the greisenization of the apogranite and wall rocks, and the precipitation of cassiterite. The second
stage is represented by low-salinity aqueous solutions (H20-NaC1) with Tm ice/> - 4 . 5 ~ trapped at
homogenization temperatures between 110 and 300 ~ and homogenization pressures below 100 bars.
This stage can be correlated with kaolinization. The third stage is characterized by higher salinity
aqueous fluids (Tin ice i> -16.5 ~ containing Na + and other cations, trapped at homogenization
temperatures between 100 and 130 ~ and homogenization pressures below 5 bars. These fluids can be
associated with the epigenetic or supergene phases of the orebody.
KEYWORDS: fluid inclusions, thermobarometry, apogranite, greisen, quartz veins, cassiterite.

Introduction consist of Hercynian granites and a monotonous,

TH E Sn-W metallogenic province of the Iberian late Precambrian-Cambrian, flyschoid marine
Peninsula is one of the most important in the sequence 'Schist-Greywacke Complex',
Ordovician and Silurian rocks are also present.
Hercynian orogenic belt of Europe. The deposits
extend from Galicia through the north of Portugal Although there are stratabound deposits, some of
to the southwest of Spain. They are located which related to volcanism, the most important
exclusively in the Hesperic Massif and a large deposits are related to the syn- to late-tectonic
number of them are in the Central Iberian Zone. Hercynian granites. The latter include the follow-
The predominant Central Iberian Zone rocks ing types: disseminated cassiterite in apogranite,
stanniferous pegmatites and quartz veins with
* This paper was presented at the ECROFI X cassiterite, wolframite and scheelite.
Conference. See the following two papers and the Cassiterite, less commonly columbite and tan-
Mineralogical Magazine for June 1990. talite are disseminated in the apical parts of many
Mineralogical Magazine, June 1991, Vol. 55, pp. 211-223
(C) Copvrieht the Mineraloeical Societv
212 J. MANGAS AND A. ARRIBAS
tin-albitized granites, which represent the final seem to be volcano-sedimentary in nature
stages of the magmatic evolution. The granites (Capote, 1983).
often show intense and complex post-magmatic The most important igneous rocks comprise an
alteration, with albitization, muscovitization, Upper Ordovician-Silurian orthogneiss, the
greisenization and kaolinization developing on a albite granite of Penouta and the late granodior-
large and small scale. The emplacement of these ites; the latter related to the Hercynian orogeny.
apogranites is generally conditioned by regional After the emplacement of the youngest grani-
tectonics, and thus they usually appear as dykes toids, a series of strike-slip faults with N-S and
with varying morphology or small intrusive N40~ strike were formed which displace all
stocks. Frequently associated with these ore- earlier structures.
bodies are tin pegmatites and peribatholith vein
deposits.
Typical disseminated tin orebodies include
Penouta deposit
Penouta and Laza (Orense), Golpejas (Sala-
manca), TorreciUa de los Angeles (Trasquil6n) The Penouta deposit is associated with a small
and Portezuelo-Cafiaveral (Cdceres). Their para- Hercynian apogranite stock that intrudes
genesis generally consists of quartz, albite, potash Precambrian-Cambrian gneisses of the OIlo de
feldspar, muscovite, cassiterite, columbite, tanta- Sapo Formation (Fig. 2A). The apogranite is
lite, tapiolite, ilmenite, rutile, apatite and, occa- discordant to the host rocks, since the foliation of
sionally gold and fluorite (Arribas, 1979). the apogranite does not coincide with the schist-
Despite the economic importance of these osity of the wall rocks. Tin ore occurs as
deposits, there have been very few fluid-inclusion disseminations of cassiterite in the apogranite and
studies; only Golpejas has received detailed as greisenized zones and quartz veins which
investigation (Mangas, 1981; Mangas and traverse both the alkaline leucogranite and
Arribas, 1984). This paper presents the physico- adjoining metamorphic rocks (Fig. 2A,B, Fig. 3).
chemical characteristics of the fluids which gave The leucogranite shows quartz, albite, micro-
rise to the mineralization and to the alteration cline and muscovite as essential minerals with
found in the Penouta orebody, using microther- cassiterite, tantalite, zircon and garnet as access-
mometfic, crushing test and Raman spectro- ory minerals. The quartz forms sub-circular
metric analyses. porphyroblasts with annular alignments of small
plagioclase inclusions. The plagioclase is albite
(4% anorthite), and together with microcline and
muscovite, shows a flow texture (Fig. 2C,D). The
Regional geology
microcline occurs as large crystals with albite
The Penouta tin deposit is located in the inclusions and rims of later albite (Fig. 2C). At
eastern part of Orense province (Spain) and times, this feldspar is completely kaolinized.
1.5 km from Penouta (Fig. 1). From the geotec- Small cassiterite crystals, ranging in size from 0.03
tonic point of view, the orebody is located in the to 0.04 mm are distributed among and within the
extreme west of the West-Asturian zone, since it muscovite and feldspar (Fig. 2D).
is found within the antiform in whose core the Greisenization of the granite cupola extends
porphyroids of Ollo de Sapo outcrop. outwards along fractures into the country rocks
The oldest rocks in the area are the Viana (Fig. 2A and Fig. 3). During this process, quartz,
Series and overlying Ollo de Sapo Formation; muscovite and cassiterite formed; the cassiterite
both of Upper Precambrian or Lower Cambrian crystals measuring 0.05 to 0.5 mm. Later, the
age. The Viana Series consists of gneisses, mica Penouta granite gave rise to a swarm of N-S
schists, quartzites, amphibolites and calcsilicate trending quartz veins of variable dip. The margins
rocks which originally corresponded to pelitic of these veins are characterized by muscovite,
sandy platform sediments of variable depth. The feldspar and large cassiterite crystals with tapio-
OIlo de Sapo Formation is composed of porphyr- lite inclusions (Fig. 3). During the final phase of
itic gneisses with large potash feldspar crystals alteration, the leucogranite and its host rocks
found within schist matrix containing quartz, were kaolinized.
feldspar and mica. The structure of the anticline The main economic interest of the deposit is
of O11o de Sapo extends from the north coast of represented by the disseminated Sn-Ta mineral-
Galicia, disappearing below the Tertiary of the ization which diminishes laterally and in depth.
Duero River Basin in the province of Zamora, The greisenized zones and veins are relatively
and continuing on through the Central Belt. Its unimportant. Kaolin constitutes a minor mineral
origin is still under discussion, though these rocks resource.
 TIN-MINERALIZED GREISENS 213

1 2 :5 Km.
I I 9

Gneisses~ migmatites and qucrzites, lViana Series)

Intercalations of marbles and anphybolites.
Porphyritic gneisses. "Gila de S o p o " Formation.

Late granodiorite.

C o a r s e - grained ortogneiss.

Fine-grained ortogneiss.
Alkaline leucogronite with greisen zone.
Penouta deposit.
Quaternary

.................... Normal. contact ~ Fault

Discordant contact Anticline of phase 1"
Intrusiv contact --,t__~-. Synclinal 00 , 1"
9 Schistosity of phase T ~ =t~= ~ Anticline ts t= "rr

II II , Tr ~ + ~ Synclinal , , 1T
" Flow plane ~ Intersection lineation

FJ6.1. Geological map of the Viana del Bollo zone showing location of the Penouta orebody (adapted from lglesias
and Varea, 1981).
214 J. MANGAS AND A. ARRIBAS

Fro. 2. A, Penouta open-pit. Intrusive contact between Penouta apogranite and Ollo de Sapo Formation gneisses.
B, sample of mineralized quartz vein. Cassiterite is found towards the edges of the vein together with muscovite and
quartz. C, Thin section of the Penouta albitic granite (x 25 Crossed Nicols). Microclinc rimmed by albite is observed
in centre of photograph. D, Thin section x63 (Crossed Nicols). Cassiterite appears disseminated in the apogranite,
here next to muscovite.

From the petrological standpoint, the Penouta Department of Geology at the University of
deposit shows three principal stages: magmatic, Salamanca (Spain). Raman spectrometric
hydrothermal (greisen and quartz veins) and measurements were made at room temperature
supergene, and corresponds to the so-called using a M.O.L.E.-type microprobe at C R E G U ,
'alkaline microgranites with columbite and tanta- Nancy (France) (Dhamelincourt etal., 1979). The
lite' mineralizations (Arribas, 19~/9). At present, exciting radiation was the 514.5 nm green line
the orebody is not mined. from a 5-W Spectra Physics ionized argon laser.
The photomultiplier was an RCA 31034 type
cooled to - 2 0 ~ The presence of CO2, CH4, N2
and H2S in the gas part of the inclusions was
Fluid inclusions
checked using a 1-W laser beam, referring to the
Description of inclusions. The fluid inclusion following lines, respectively: 1388cm- 1,
study was undertaken using microthermometry, 2915 cm - l , 2331 cm -1, and 2611 cm - l .
crushing tests and Raman spectroscopy. Three Observations show that the quartz is crossed by
samples were analysed: an intragranitic vein a large number of microfractures of varying
(P34), a greisen (Pl15) and an exogranitic vein strike, dip and extension, representing repeated
(P42), (Fig. 3). fracturing, healing and recrystallization.
Microthermometric studies of fluid inclusions Different quartz grains with distinctive shapes
were performed on 300 9m-thick plates using a and orientation are seen. In the grains, the
microscope equipped with a UMK50 Leitz objec- inclusions are generally pseudosecondary or
tive and a Chaixmeca cooling and heating stage secondary in character (Roedder, 1984). In addi-
(Poty et al., 1976). Crushing test analysis was tion, a smaller number of inclusions appear
carried out on a crushing stage designed by the isolated or in groups; these are interpreted as
 T I N - M I N E R A L I Z E D GREISENS 215
P42

_ _ PEGMoAvpLITES ~ G N E I S S E S "011o de Sopo" F O R M A T I O N ~ ~ ]

~ _ GREISENS ~ ~

~ /'4" + + + + + + + + + +
~ + ~ ,r++++++t++++++++++++++++*

_ ..+*+++++++++'>.+.. /++++++++++++++++++++++++
~+
+ + + + + + + + + + + + + + + + ~+ x
// Ii~- + + + + + + + + + + + + + + + + + + + + + + + +
/.-4 + + + + + + + + + + + 9 //+ + + + + + + + + + + + +
~ + + + + + + + + + + + + + ~'% + + + + + + + + + t + +
~ + + + § + + + + +++++++++++ ++ + + + + + + + + + +++++
/~ + + + + + + + + + + + + + + + + + + + +
~- + + + + + + + + + + + + + + + + + + + + + + + + + +

>+'-g-"+"~++++++++++++++++++++++++++ ALKALINE LEUCOGRANITE -+++++++++

- + + + + 4- + + + 4- + + + + + + + + + + + + + + + + + + ++++++++++
+ + + + 4- + + 4- 4- + + + 4- + 4- 4- + + + + 4- + 4- 4- + 4- + +
+ + + + + + + + + + + + + + + + 4- p 34 + + + + + + + + + +
I ~m. + + + + + + 4- + 4" 4- + + 4- 4- + + 9 4- 4- + 4- 4- + + + +

Fro. 3. Scheme of Fig. 2A, where the location of samples taken for fluid inclusion study is shown.

primary (Roedder, 1984). The abundance of fluid groups and fractures containing type 1 inclusions
inclusions and mineral impurities is highly vari- (Fig. 4B).
able giving rise to transparent, translucent and
opaque areas in the quartz. Inclusion morphology Type 3: low salinity, aqueous inclusions ( H 2 0 . -
is equally varied, ranging from 5 to 50 gm in size. NaCl). These show one (H20 L) or two phases
Based on the estimated composition of the (H20 L + H20 V) at room temperature in which
trapped fluid using microthermometric, crushing the vapour bubble occupies 2 to 20% of the total
test and Raman data, and the volume of the fluid inclusion volume. These inclusions appear in all
phases at room temperature, four types of inclu- the samples and are fracture controlled (Fig. 4C).
sions have been defined (Fig. 4A, B, C and D):
Type 4: mixed salt, aqueous inclusions (HeO-
Type 1: complex, CO2 aqueous inclusions ( H 2 0 - NaC1 and other salts). These show one (H20 L)
NaCI-COz-N2-CH4-H2S). These show two or two (H20 L + H 2 0 V) at room temperature in
(mainly H20 L + CO2 V) or three phases (mainly which the vapour bubble occupies ~<5% of the
H20 L + CO2 L + CO2 V) at room temperature total inclusion volume. These inclusions are
(T ~ 20~ The carbon-rich phases (CO2 L + comparatively scarce and are always secondary in
CO2 V) occupy />20% of the total volume of character (Fig. 4D).
inclusions. The volumetric proportion of CO2 L
relative to CO2 L + CO2 V (Flc) is/>30%. These
inclusions which are the most representative of M i c r o t h e r m o m e t r i c results
the Penouta orebody, appear in all the samples
and are found distributed in microfractures, More than 200 fluid inclusions have been
isolated, or in groups (Fig. 4A and B). studied in samples P34 and Pl15. The microther-
mometric results are summarized in Table 1 and
Type 2: complex, CO2 inclusions (CO2-N2-CH 4- described below.
H2S). These inclusions are one (CO2 L/CO2 V) Melting temperatures for solid CO2 in type 1 nd
or two phases (mainly CO2 L + Co2 V) at room 2 inclusions, and clathrate melting temperatures
temperature and the Flc data are t>30%. These for type I inclusions show that the carbonic phase
inclusions are rare in samples P34 and P42, and contains CO2 and other gases (Swanenberg,
are not seen in sample Pl15. They appear near 1979). Fluid salinities estimated from final ice
216 J. M A N G A S AND A. ARRIBAS

Fro. 4. A, A three-phase fluid inclusion in the centre of photo, containing mainly liquid H20, liquid CO2 and
gaseous CO2. B, Distributions of groups of type 1 and 2 inclusions. C, Type 3 aqueous inclusion containing water
and water vapour. D, Distribution of type 4 aqueous inclusions in healed fracture planes.

TABLE 19 Microthermometric results, Penouta deposit. No = total number of inclusions studied; Tm CO2 =
temperature of final melting of CO2 solid (~ Tm clat. = clathrate melting temperature (~ Th CO2 =
temperature of homogenization of CO2 liquid and vapour phases (~ Th = temperature of total homogenization
(~ G and L = homogenization into gaseous and liquid states, respectively. Salinity, expressed in terms of weight
per cent NaCl equivalent. The maximum frequency in the results is underlined.

SAMPLES Type of N ~ Tm T m ciat Salinity T h c o 2 and Type Th and type

CO T mic e
inclusion 2
of ho ~oqenization of ho m oqenizatioo
P 34 I 36 -56.6/-68.5 -2/-6 8/15 <8.5 17/27 L and G 260/410 L and G
-4.5 8.5 7._! 23.5 L and25.5 G 325 L and 385 G

Intragrani- 2 12 -571-59 -- 17/26 L and G

tic vein -57.5 22 L and G
3 47 -~ 0.5/-4.5 -- 1.5/7 11D/3DD L
-3.3 6.3 165 L

4 9 -- -15.51-I 6.5 -- >19 115/130 L

9 -16 . 19.__5 . 120 L

P 115 I 40 -57/-59 -2.5/-5 9.5/11 < 7 16/21 L a n d G 250/320 L

. -6__8 . -3.3 io.6 5.4 19.5 L and S 265 L

Greisen 3 68 -- 0/-4 -- 0/6 -- 110/288 L

9 -2.'7 . ._..aa
4 185 L

4 6 -- -9.5/-I 1.5 -- >I 3.7 -- IOO/120 L

-I 0.5 9 14.5 , 115 L
 TIN-MINERALIZED GREISENS 217
melting temperatures (To ice) in type 3 inclusions tions were present (13.5 and 19 wt.% eq. NaCI).
(Potter et al., 1978) and final clathrate melting These contained various cations and were trapped
temperature (Tm clat) in type 1 inclusions (Col- at temperatures of approximately 100~ in the
lins, 1979) are low (>/8.5 wt.% eq. NaCI). In the quartz.
type 4 inclusion the initiation of ice melting varied
between - 2 2 and - 5 0 ~ and thus indicates the
presence of not only Na + but minor amounts of
Results of the crushing test
other cations (Crawford et al., 1979). Salinity
estimates, based on T,, ice values for the system
Crushing of quartz grains from the edge and
NaCI-H20 (Potter el al., 1978), range between
core of the veins was carried out in anhydrous
13.5 and 19 wt.% eq. NaC1.
glycerine, about five tests being performed on
Homogenization temperatures for the non-
each sample. The observations reveal the con-
aqueous part of type 1 and 2 inclusions indicate
stant presence of CO2 fluids. In accordance with
variable densities between 0.15 and 0.85 g/cm 3
the classification proposed by Leroy (1978), the
(Angus et al., 1976). However, using the
liberated gas intensity in all the tests reaches high
diagrams of Swanenberg (1979), it is deduced that
to very high values (Fig. 5). Sample P34 shows
the X(CH4) in the CO2 phase is lower than 0.1 for
low to very high releases, due to the quartz having
Tm CO2 > - 5 9 ~ and for Flc data >30%. In the
clear and transparent areas, where the number of
same way, the density of the non-aqueous part of
inclusions is low compared to the translucent
type 1 and 2 inclusions that homogenize into the
areas.
gas and liquid state ranges between 0.25 and
0.75 g/cm 3. Temperatures of total homogeniza-
tion for all inclusion types vary between 100 and
410~ Type 1 inclusions homogenize into the Raman spectroscopic analyses
liquid and gaseous state high temperatures (250--
410~ whereas type 3 and 4 inclusions homo- Raman spectroscopic analyses have been made
genize into the liquid state at lower temperatures for seven inclusions characteristic of the deposit:
(100-300 ~ five type 1 inclusions (sample P34, fluid inclusions
Some type 1 and 2 inclusions decrepitated at nos. 2, 41 and 42; sample Pl15, fluid inclusions
temperatures between 200 and 300~ before nos. 13 and 33), one type 2 (sample P34, fluid
total homogenization. With reference to the inclusion no. 19), nd one type 3 (sample P34, fluid
T-salinity graph of Bodnar (1983), the density of inclusion no. 9). The physical and microthermo-
the Penouta type 1 inclusions varies between 0.5 metric properties of these inclusions are shown in
and 0.85 g/cm 3, type 3 inclusions between 0.8 and Table 2. The analyses were carried out solely on
1 g/cm 3 and type 4 inclusions beween 1 and the vapour phase part of the type 1 and 2
1.1 g/cm 3. inclusions. Calculation of the molar fractions
The microthermometric results described (Table 3) indicates the presence of significant
above suggest that the fluid inclusions trapped in CO2 with minor N2, CH4 and H2S.
quartz samples P34 and Pl15 are evidence of From the Raman and microthermometric
continuous hydrothermal evolution. At an early results, bulk composition, densities and isochores
stage, circulation and trapping of carbonic and were calculated for each of the inclusions using
low salinity, carbonic-aqueous fluids containing the program of Debussy and Ramboz [CREGU
N2, CH4 and H2S, took place, This was followed and CRPG, Nancy, France] (Ramboz et al.,
by progressively more aqueous fluids and a steady 1985). These are summarized in Table 3. The
decrease in volatile content. Thus, in sample P34 results show that for samples P34, the type 1
(intragranitic vein) there is a transition between inclusions though having different homogeniza-
complex CO2 aqueous inclusions which homo- tion temperatures, and homogenizing into differ-
genize into the gaseous state at temperatures ent states, have a similar global composition.
ranging between 340 and 410 ~ and those which Moreover, there are no significant differences in
homogenize into the liquid state between 260 and the global composition of the type 1 inclusions
340~ Subsequently, weakly saline aqueous from the intragranitic vein (P34) and the greisen
solutions containing less than 7 wt.% eq. NaC1 quartz (Pl15). The ratio H20 > CO2 > NaCI >
appeared with homogenization temperatures N 2 ~ C H 4 is seen throughout.
from 300 to 100 ~ However, below 180 ~ very Type 2 inclusions have the composition CO2 >
dilute aqueous fluids with salinities between 0 and N2 > CH4 > H2S. By comparison, the type 3
4 wt.% eq. NaC1 were also trapped. During the inclusions are predominantly aqueous and con-
final stages of fluid evolution, more saline solu- tain no detectable volatiles in the vapour phase.
218 J. MANGAS AND A. A R R I B A S
TABLe 2. Physical characteristics of the fluid inclusions analysed by Raman microprobe and corresponding
microthermometric data. Abbreviations as for Table 1. No. = refcrence number of fluid inclusion; % vol. = volume
per ccnt of liquid (L) and vapour (G) phases, at room tempcrature (T = 20 ~

C H A R A C TE RISTICS MICROTHERMOMETRIC DATA

SA M P L E S N ~ F.I. Type Phases % Vol Size Tmco 2 Tin. Tm Thco Th

ic e cla t 2
(~m)
P34 2 I H20 L 85 20 -58.2 -3 9.6 22 G 308 L

CO 2 G 15

P34 41 I H20 L 60 10 -57.7 -3.2 9.6 -- 382 G

C02G 40
P34 42 1 H20 L 60 20 -57 -4.5 9.5 25.3 L 328 L

CO 2 G 40
P115 13 1 H 0 L 60 20 -5B.2 -4,4 10.6 18.9 G 288 L
2
CO 2 G 40

P115 33 I H 0 L 70 15 -58.2 -3.2 11.2 18.8 G 282 L

2
CO 2 G 30

P34 19 2 CO 2 -- 15 -57.8 . . . . 19.1 L --

P34 9 3 H20 L 95 10 -- -1.9 . . . . 244 L

H20 G 5

Thermobarometric trapping conditions and Furthermore, the minimum trapping conditions

discussion for the type 1 complex CO2 aqueous inclusions
(nos. 13 and 33 from greisen quartz; sample P l l 5 )
The trapping conditions of the inclusions are considered to be 280 ~ and 1000 bars, for the
studied by Raman microprobe were estimated type 3 aqueous inclusion no. 9 (P34) estimated
using the experimental data for H20 (Fisher, P - T conditions are 300 ~ and 100 bars.
1976), CO2 (Bergman, 1982) and In conclusion it may be stated that during the
HzO-CO2-NaC1 (Gehrig, 1980), since there are formation of the intragranitic quartz vein and
no data for the real system greisen quartz, the evolution of the fluids was
H20-NaC1-CO2-N2-CH4-HzS. The volatile con- similar, and occurred in three main stages:
tent of type 1 and 2 inclusions was simplified Stage I. This is characterized by the trapping of
assuming X c o 2 = Xco,_ + XN2 + XCH4 + XH,s. In complex CO2 fluids (CO2-N2-CH4-H2S) with
the P - T diagram of Fig. 6, the isochores for the densities between 0.25 and 0.75 g/cm 3, and com-
inclusions were projected onto the equilibrium plex CO2 aqueous fluids (H20-NaCI-CO2-N2-
curves for the compositions calculated by Raman CH4-H2S) with salinities <8.5 wt.% eq, NaCI,
microprobe. densities from 0.5 and 0.7 g/cm 3, bulk homogen-
The minimum thermobarometric conditions ization into the gaseous state at temperatures and
for the complex CO2 aqueous inclusions (nos. 2, pressures below 700 ~ and 3250 bars, respect-
41 and 42 in the intragranitic vein and nos. 13 and ively. Subsequently, the trapping of higher
33 in the greisen) correspond to 300-380 ~ and density complex CO2 aqueous inclusions which
30(01000 bars. homogenize into the liquid state occurred at
In sample P34, since the type I and 2 inclusions temperatures and pressures below 400~ and
appear primary and decrepitate in the same 2000 bars, respectively. A t this stage, the density
temperature interval (between 200 and 300 ~ of the aqueous solutions increases, and the
they are assumed to be contemporaneous. concentration of CO2-CH4-Na-H2S decreases as
Therefore, as a first approximation, the intersec- the temperature drops. For the Penouta Mine, a
tion of the isochores for those type 1 and 2 spatial and temporal relationship between greis-
inclusions which homogenize into the liquid yield enization and tin mineralization has been
trapping conditions of 400~ and 2000bars. observed.
 TIN-MINERALIZED GREISENS 219
5
P34-I s F P34-2 P 115-I
N ~
3 3k ~ 3

11- ~ ~ J ~ 1

1 2 3 4 5 I 2 3 4 5

PI15-2 P 42-I ~i-] P 42-2

N_
~

I [ I I ' I I i I [ ~ l l I
1 2 3 4 5 1 2 3 4 5 1 2 3 4 5

I
Flo. 5. Diagrams showing the results of crushing-test analyses. 1, Edge of vein and 2, core of vein. No = number of
crushing-test analyscs; I, liberated gas intensity, using the classification of Leroy, 1978.

Given the mineral paragenesis of the samples that the inclusions are contemporaneous with
chosen for the study and the apparent contempor- greisenization. However, since different solutions
aneity of the type 1 and 2 inclusions, this implies are present during the early stage of mineraliz-

TABLE3. Chemical compositions obtained by Raman microprobe spectrometry. Inclusions numbered as in Table 2
and Fig. 6. Analysts: C. Kostolanyi and J. Dubessy (C. R.E.G.U., Nancy, France). Zi = mole fraction of gas species
i in the non-aqueous fluid phase, expressed in terms of mol %; Xi = mole fraction of species i in the inclusion, in
mol % ; d = bulk density of the inclusion in g/cm 3.

RAMAN SPECTROSCOPY

MOLE FRACTION BULK COMPO51TION AND DENSITY

No F . I . Type Z Z ZCH Z
CO 2 N2 4 H 28 XH20 XNaCl XCO 2 XN2 XCH 4 XH2 S d

2 1 96.41 2,BO ~.98 -- 94.84 0.59 4.52 0,03 0,02 -- 0.90

41 I 97.37 1.69 0.94 -- 92.73 0.58 6.55 0.08 0.04 -- 0.88
42 I 98~ 1.15 0.47 0.15 83.96 0.80 14.97 0.17 0.06 -- 0.85
13 I 94.90 2.75 2.35 -- 90.52 0.96 8,29 0,16 0.14 -- 0.71
33 I 95.39 2.32 2.28 -- 92.74 0.58 6.52 0.09 0.69 -- 0.78
18 2 96.94 2.37 0.47 0.23 . . . . 96.94 2.37 0.47 0.23 0.75
9 3 -- 98.87 1.13 . . . . . . . . 0.B4
220 J. MANGAS AND A. A R R I B A S
P
|

3000

2500

20O0

1500

1000

50(1

100 200 300 400 500 600 700

Th ~
P
bars 20o0 F.I n~33 @
9 . ~13
150"

1000

500

100 200 300 400 500 600

Th ~

Fro, 6. Pressure-temperature diagram. Equilibrium curves and isochorcs corresponding to the inclusions in samples
P34 and Pll5 for Raman spectroscopic analyses (Tables 2 and 3). 1, CO2; 2, H20; 3, 5.5% mol CO2 and 2.5% eq.
NaCl; 4, 6.5% mol CO2 and 2% eq. NaCI; 5, 15% tool CO2 and 2.5% eq, NaCI; 6, 7.5% tool CO~ and 2,5% eq,
NaCI. The upper circle shows the intersection between type 1 inclusion which homogenizes into the gaseous state
and type 2 inclusion. The lower circle shows the intersection between type 1 inclusions which homogenize into the
liquid state and type 2 inclusion.

ation, it cannot be determined precisely which authors for granite greisenization and associated
fluids are responsible for the alteration, and tin mineralizations (Scherba, 1970; Naumov and
which relate to the transport and precipitation of Ivanova, 1971; Tugarivov and Naumov, 1972;
cassiterite. Despite this uncertainty, if the results Charoy, 1979; Ramboz, 1980; Mangas, 1981 and
obtained for Penouta are compared with those of 1987; Thomas, 1982; Roedder, 1984; Dubessy
other tin deposits, the following conclusions may et al., 1987; Cathelineau et al., 1988; Durisova,
be deduced: 1988).
1. Estimated trapping temperatures for the first 2. Estimated trapping pressures (300-
stage 250-700 ~ are consistent with the thermal 3250 bars) are typical for orebodies associated
conditions (200-650~ calculated by various with granitic intrusions, where repeated fractur-
 T I N - M I N E R A L I Z E D GREISENS 221
ing of the granite permits changes in pressure, eq. NaCl) with homogenization temperatures
composition and temperature for each phase of below 130 ~ These are thought to be related to
fracture opening and sealing (Charoy, 1979; the epigenetic or supergene phases of the ore-
Ramboz, 1980; Thomas, 1982). body. The differences in composition and salinity
3. The fluids are of primarily low salinity, for the second and third stages could be a result of
carbonated sodium chloride solutions mixing between magmatic fluids with formational
(<8.5 wt.% eq. NaC1). Such low salinities are waters. However, to confirm this hypothesis, it
characteristic of the fluids associated with greisen- would be necessary to carry out isotopic studies.
ization (Beus, 1967; Scherba, 1970; Charoy, 1979; The evolution and physico-chemical character-
Durisova, 1978; Ramboz, 1980; Mangas, 1981 istics of the fluids of the Penouta deposit are
and 1987; Thomas, 1982; Roedder, 1984 and similar to those described for the greisen and
Dubessy et al., 1987). Likewise, the presence of quartz veins of the Golpejas apogranite (Mangas
CO2 in the mineralizing solutions is common and Arribas, 1984; Mangas, 1981, 1987).
although the absolute concentration may be However, the pressure conditions of greiseniza-
variable (Goncharov and Vorontsova, 1976; tion and precipitation of cassiterite are different.
Ramboz, 1980; Mangas, 1981 and 1987; Roedder, Thus, at Golpejas, pressures are estimated to be
1984; Dubessy et al., 1987). less than 900 bars. This may reflect different
Thus, the residual tin that did not crystallize levels of emplacement, since at Golpejas the
with the Penouta apogranite, together with that orebody consists of several sheets of mineralized
which was released during alteration, could be albitic granite, while at Penouta there is a small
transported: (a) in the form of complexes of the granitic stock. These different morphologies indi-
type Na{K Sn m(CO3)n (C1,OH)p} and Na K cates distinct emplacement depths, the Golpejas
{Sn(C1, OH)n} (Scherba, 1970); (b) CI- and granite being intruded at a higher level that the
O H - complexes in aqueous solutions at tempera- Penouta granite.
ture around 350~ (Jackson and Helgeson,
1985); and (c) as chloride complexes between 500
and 600 ~ at low oxidation states (Dubessy et al., Conclusion
1987). The solubility of cassiterite in NaC1 fluids The greisenization and tin mineralization at the
increases with increasing temperature, oxygen Penouta mine was caused by essentially aqueous
fugacity and salinity (Eadington, 1983; Eugster fluids with some volatiles (CO2, Nz, CH4 and
and Wilson, 1985; Jackson and Helgeson, 1985). H2S). Saliuities were below 8.5 wt.% eq. NaC1,
Hence the precipitation of cassiterite will take densities between 0.5 and 0.8 g/cc, temperatures
place as a result of sharp decreases in pressure, below 700 ~ and pressures below 3250 bars. The
temperature, oxygen fugacity and salinity, or as tin was probably transported as aqueous, chloride
indicated by Volosov et al. (1981), Halley et al. and/or carbonate complexes. Consequently,
(1984), Jackson and Helgeson (1985), and changes in the physico-chemical conditions (i.e.
Sushchevskaya et al. (1985), due to pH increases temperature, pressure, density, composition and
at temperatures between 30t3 and 500 ~ concentration) were enough to cause destabiliza-
Stage H. The second stage is characterized by tion of the tin complexes and give rise to the
low salinity, aqueous inclusions (<7 wt.% eq. precipitation of cassiterite. Thee changes
NaC1), trapped at temperatures less than 300 ~ occurred when the mineralizing fluids reacted
and pressures below 100bars. Also present with the host rocks or mixed with non-magmatic
during Stage II are very low salinity fluids, with fluid.
values <4 wt.% eq. NaCI, at homogenization Kaolinization of Penouta was probably gener-
temperatures between 110 and 180~ These ated by aqueous solutions with salinites <7 wt.%
fluids are thought to be responsible for the eq. NaC1, densities between 0.8 and 1 g/cm3,
kaolinization at Penouta. This is in general homogenization temperatures between 100 and
agreement with the work of Charoy (1979), 300~ and homogenization pressures less than
Jackson et al. (1977) and Bristow (1977) who, 100 bars.
having studied the kaolin deposits of SW England
(United Kingdom) and Brittany (France), con-
clude that kaolinization was due to circulation of Acknowledgements
low salinity, aqueous fluids (2 and 3 wt.% eq. The work was supported by grants from the Geology
NaC1) at temperatures below 200~ pH is Department (Salamanca), the Ministry of Universities
estimated to be 4--4.8. and Research and the Polytechnical University of the
Stage Ill. The third stage is represented by Canary Islands. We thank B. Poty for access to the
higher salinity aqueous inclusions (>13.5 wt.% laboratories at C.R.E.G.U. (Nancy, France). We also
222 J. M A N G A S A N D A. A R R I B A S
acknowledge C. Kosztolanyi for his help with the behaviour of U and Sn-W as exemplified by hydro-
Raman analyses and J. Dubessy for providing the thermal deposits in France and Great Britain, and
computer programs to calculate bulk composition, solubility data. Bull. Mindral., 110, 261-81.
density and isochores from Raman spectroscopic data. Durisova, J. (1978) Geothermometry in the minerals
We gratefully acknowledge A. Weisbrod, C. Leroy and from the tin-ore deposit (G.D.R.) by means of gas-
J. Dubessy for their advice on all aspects of thermobaro- liquid inclusions. Z. Angew. Geol. D.D.R., 20,
metric interpretation and the management and staff of 352-63.
the Penouta mine for permission to work on their - - (1988) Diversity of fluids in the formation of ore
property. Finally, we would like to thank Jean P. assemblages in the Bohemian Massif (Czechoslo-
LeGrow for her translation work. vakia). Bull. Mindral., 111,477-92.
Eadington, P. J. (1983) A fluid inclusion investigation of
ore formation in a tin-mineralized granite, New
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