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Development and application of the Ga/Ge-geothermometer for sphalerite

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Monograph Series on Mineral Deposits 25: 15—30; Gebrüder Borntraeger, Berlin-Stuttgart, 1985

Development and Application of the Ga/Ge-Geothermometer

for Sphalerite from Sediment-hosted Deposits

PETER MÖLLER

Abstract
The element pairs Al-Ga and Si-Ge show a close geochemical coherence in both rocks and their asso-
ciated Solutions. The temperature dependence of the Al/Si ratio, and by analogy the Ga/Ge ratio, in
equilibrated Solutions provides means of monitoring the temperature of hydrothermal Solutions at
their source rather than at the site of deposition. Ga/Ge ratios in sphalerites closely reflect those of
parental Solutions. Determinations of Ga/Ge in sphalerites from various Variscan and Alpine sediment-
hosted Pb-Zn deposits indicate temperatures of 180—270 °C in the source regions of the ore Solutions.
Fluid inclusion temperatures for the same deposits ränge from being equivalent to being /''-T00oC
lower. The observed temperatures differences are interpreted to reflect variable degrees of mixing of
hot parental ore fluids with cool near-surface waters.

Zusammenfassung
Die Elementpaare Al/Ga und Si/Ge zeichnen sich durch ein enge geochemische Kohärenz in Gesteinen
und deren fluiden Phasen aus. Die Temperaturabhängigkeit der Al/Si-Verhältnisse in Gleichgewichts­
lösungen und in Analogie zu diesen, der Ga/Ge-Verhältnisse, sind ein gutes Hilfsmittel, die Temperatur
der hydrothermalen Lösungen in ihrem Herkunftsbereich — d.h. vor Eintritt in den Lagerstättenraum
— zu erfassen. Es wird angenommen, daß die Ga/Ge-Verhältnisse in den Sphaleriten denen der paren­
talen Lösungen entsprechen. Messungen der Ga/Ge-Verhältnisse in Sphaleriten aus verschiedenen
variskischen und alpinen Pb-Zn-Lagerstätten in Sedimenten weisen auf Temperaturen von 180—270 °C
für die initialen Lösungen hin. Homogenisierungstemperaturen von mehrphasigen Flüssigkeitsein­
schlüssen ergeben sich als gleich bzw. bis zu 100°C niedriger im Vergleich mit den Ga/Ge-Tempera-
turen. Diese Unterschiede der beobachteten Temperaturen werden als das Ergebnis einer variablen
Zumischung von kälteren oberflächennahen Wässern erklärt.

1. Introduction

The source of the metal ions is one of the crucial points in discussions on the origin of
hydrothermal and sedimentary Pb-Zn deposits. From a knowledge of the initial temper­
ature of metal-bearing fluids and of the geothermal gradient for lead-zinc deposits in

0341-6356/85/0025-0015 $ 4.00
© 1985 Gebrüder Borntraeger, DT000 Berlin ■ D-7000 Stuttgart
16 P. Möller

sedimentary basins it is possible to deduce the probable depth and pressure in the source
region. Such information provides some insight into processes by which metal-bearing
fluids are generated.
Chemical methods of temperature measurements are known from studies of geo­
thermal fluids. Such fluids are saturated with quartz at >100°C(Mahon 1966; Fournier
& Rowe 1966) and chalcedony at <100°C (Arnorsson et al. 1982). The Si02-aq con-
centrations in geothermal waters turn out to be a reliable measure of temperature at
depth (Ellis & Mahon 1977; Arnorsson et al. 1982). Another temperature estimate is
derived from the temperature-dependent constants of alkali feldspar equilibria (Ellis &
Mahon 1977; Fournier & Truesdell 1973).
(1) log Kx = [Na+]/[K+]
When dealing with ore minerals the only fluid phases still available are in fluid inclu-
sions. Such fluids may not be representative of the initial metal-bearing liquid since the
possibility of mixing with near-surface waters cannot be excluded. Therefore, the tem­
perature of the initial fluid may be higher than that indicated by the pressure-corrected
homogenization temperature of multi-phase fluid inclusions.
In this paper the application of the Ga/Ge ratio in sphalerite as a measure of temper­
ature up to 300 °C will be discussed. Since Ga and Ge are coherent with Al and Si,
respectively (Hörmann 1969; Burton & Culkin 1969), the concentrations of Ga and Ge
in solution are expected to be related to those of Al and Si, respectively (Möller et el.
1983).

2. Estimation of Al/Si Ratio in Solution as a Function of Temperature

2.1 Stahle Equilibria
It is convenient to show the stability of geothermal Al-bearing mineral phases in terms of
(1) dissolved silica activity and the equilibrium ratio log (aAl3+)/(aH+)3, or in (ii) activity
diagrams of two relevant equilibrium ratios of the type log (Me1+)/(H ): at constant silica
content where i indicates the charge of Me-ions such as Na+, K+, Ca2+, Mg2+, Al3+, Fe3+.
Helgeson et al. (1969) and Giggenbach (1981) published such activity diagrams for
geothermal Systems in the temperature ränge up to 300 °C. According to Giggenbach
(1981) the following stable mineral equilibria are relevant at quartz Saturation:
(2) KAlSi308 + 2 H+ i? KAIjS^Ojo(OH)2 + 2 K+ + 6 Si02
microcline muscovite quartz
(3) 3 NaAlSi308 + 2 H+ 7t NaAlgSijOjo(OH)2 + 2 Na+ + 6 Si02
albite paragonite quartz
(4) 2 KAlgSigO^OH)-, + 2 H+ + 3 H20 7t 3 Al2Si2Os(OH)4 + 2 K+
muscovite kaolinite
 Ga/Ge-Geothermometer for Sphalerite from Sediment-hosted Deposits 17

(5) 2 NaAljSijOjo (OH)2 + 2 H+ + 3 H20 ^ 3 Al2Si2Os (OH)4 + 2 Na+

albite kaolinite
2 KAl3Si3Oj0(OH)2 + 15 Mg2+ + 3 Si02 + 24 H20
muscovite quartz
(6) 7t 3 Mg5Al2Si3Oj0(OH)8 + 28H+ + 2 K+
chlorite
In agreement with Giggenbach (1981) the montmorillonites — the most important
group of hydrothermal alteration products (Browne 1978) — are not considered, because
of some inconsistencies of thermodynamic results.

2.2 Fluid Composition

Any general discussion of the actual equilibria is limited by the high variability of the
composition of the hydrothermal Solutions. Barnes (1979) has suggested that typical
hydrothermal Solutions have 0.03 to 7 M CI“ concentrations with pH values generally one
unit acidic, pH^j. Primary fluid inclusions in hydrothermal minerals show homogen-
ization temperatures below 300 °C (Large 1977; Barnes 1979). Freezing point data of
inclusion fluids indicate total concentration of salts in Solutions in the ränge of > 1 to
<50 wt% NaCl equivalents (Roedder 1979). Roedder (1979) quotes ranges of 0.1 to
5 wt% NaCl in ‘normal hydrothermal’ Solutions and 15 to 20 wt% in inclusions from
Mississippi Valley-type deposits. Na+/K+ ratios in inclusion fluids vary considerably from
0.4 to 21 in ‘normal hydrothermal’ deposits to 16 to 40 in Mississippi Valley-type
deposits (Roedder 1979), whereas geothermal spring waters show ratios between 5 and
20 (Ellis & Mahon 1977).
In subsequent calculations an average Chemical composition of the ore fluids as given
in Table 1 is assumed. Chloride anions are used to provide electroneutrality. Chemical
complex formation in Solution will be neglected.
Using the respective equilibrium constants of Table 2, the Si02 • aq and the total
concentration of Al species in hydrothermal Solutions saturated with respect to quartz
(Si02) and gibbsite (Al(OH)3) are calculated and presented in Fig. 1 and 2, respectively.

Table 1. Main constituents of the assumed hydrothermal fluid to be used in the estimation of (Alt/Si)j:
ratio.

ionic strength (25 °C): 1.55 M

true ionic strength (estimated after
concentration of ions/M Helgeson 1969)

Na K+ Mg2+ Ca2' er 100 200 300

1 0.1 0.05 0.1 1.4 1.55 1.3 1.0

18 P. Möller

Table 2a. Compilation of thermodynamic data used in the calculation of (Alt/Si)j: ratios (a Helgeson
1969; b Arnorsson et al. 1982; c calculated from data reported by Helgeson 1969 and
Helgeson at al. 1979).

log K at temperatures of
reaction Ref. 100 °C 200 °C 300 °C

NaAlSi308+ 4H++ 4H20 = Na++Al3++ 3H4Si04 a +1.48 -0.41 -1.59

KAlSijOgt- 4H++ 4H20 = 1K++ Al3++ 3H4Si04 a -0.32 -1.57 -2.38
NaAljSijO 10(OH)2 + 10H+ = Na+ + 3A13+ + 3H4Si04 c +12.12 +2.87 -2.33
KAl3Si3O10(OH)2 + 10H+ =; K++ 3A13+ + 3H4Si04 a +7.97 +0.93 -3.31
A12S12Os(OH)4 + 6H+ = 2A13+ + H2Q + 2H4Si04 a +2.27 -1.72 -4.02
MgsAl2Si3O10(OH)8 + 16H + = 5Mg 2+ = 2A13+ + 3H4Si04 + 6H 20 a +52.08 + 36.23 +27.24
S102 + 2H20 = H4Si04 a -3.08 -2.35 -1.94
h2o = h+ + oh- a -12.26 -11.30 -11.39
aioh2+ = ai3+ + oh- b -9.82 -11.50 -14.00
Al(OH)2 = AlOH 2++ OH“ b -9.23 -10.69 -12.92
Al(OH)3 = Al(OH)2 + OH“ b -7.59 -7.69 -8.39
Al(OH)4= Al(OH)3 + OH“ b -4.84 -2.34 +0.58

Table 2b. Compilation of activity coefficients used in the calculation of (Alt/Si)f ratios after the
procedure described by Arnorsson et al. 1982.

activity coefficient y-values at temperatures of

100 0/°c 200 0/° C 300 0/°C

7A13+ -1.46 -1.81 -2.53

7Al(OH)2+ -0.98 -1.19 -1.64
7Al(OH)2 -0.30 -0.34 -0.41
7Al(OH)° 1.0 1.0 1.0
7Al(OH)4 -0.33 -0.37 -0.46
7Na+ -0.35 -0.40 -0.50
7k+ -0.40 -0.46 -0.59
7Mg2+ -0.75 -0.91 -1.23
7Ca2+ -0.91 -1.11 -1.52

The solubility of silica (Fig. 1) appears to be essentially independent of the pH of aqueous

Solutions in most of the geologically interesting environments (Holland & Malinin 1979)
and in the interesting pH ränge of 4 to 7. Furthermore, the dissolved silica content is
virtually independent of both the concentration of dissolved salts (Chen & Marshall 1982;
Marshall & Chen 1982) and pressure (Fyfe et al. 1978; Holland & Malinin 1979) in the
temperature ränge of 0 to 300 °C.
The total Al solubility, Alt, depends on the presence of the various Al species.
 Ga/Ge-Geothermometer for Sphalerite from Sediment-hosted Deposits 19

quartz
Si02 (qz) + 2H20 - H4Si04(aq)

^^300°C
i(NJ -2 ------^-200°C
— ^ioo°c
o "" ^ 25°C
i/i -4
Fig. 1. Quartz solubility at 1 atm (after Helge-
son 1969; Giggenbach 1981) — sw = sea water o -6 -
(after Turekian 1969).
3 4 5 6 7 8 9 10
pH ------

Fig. 2. Gibbsite solubility at 1 atm (after Hel-

geson 1969). Fach curve is composed of Seg­
ments representing various indicated Al-species
in solution. Equilibrium constants for dissocia-
tion of Al-OH species are given in Tab. 2. The
curve for 200 °C and 300 °C is only of theoret-
ical value, because under these temperatures
gibbsite is not stable in contrast to boehmite
(Giggenbach 1981).

pH

(7) Alt = AKOH)® + Al(OH)2 + Al(OH)2+ + Al3+ + Al(OH)4

The ion pair AKOH)® predominates in the pH ränge of interest at higher temper­
atures and causes the flat parts of the curves in Fig. 2. Al(OH)® determines the minimum
solubility of the Al-bearing solids (Baes & Mesmer 1981). The hydrolysis of aqueous ions
generally increases with temperature. In the pH ränge of interest AKOH)® and AKOH)^
are the most likely species.
Using the respective data from Table 1 and 2, the (Alt/Si) ratio in the fluid phase,
(Alt/Si)£, as a function of temperature of hydrolysis is calculated for the equilibria (2) to
(6) (Fig. 3).
The low (Alt/Si)f ratios under isothermal conditions indicate low Alt concentration
in the Solutions. Thus the feldspar-mica-quartz assemblages are generally associated with
20 P. Möller

the least Alt-concentrations in the fluids. Which of these equilibria (2) to (6) dominates
in a given System depends on the concentration levels of the respective alkali or alkaline
earth metals and pH of the geothermal fluid. Since no aluminium-bearing mineral should
be thermodynamically stable with solubilities exceeding that of kaolinite, all mineral
equilibria of mica and feldspars with montmorillonites and quartz should fall into the
calculated field between the mica and kaolinite curves in Fig. 3. The muscovite-chlorite-
quartz equilibrium (6) crosses the equilibria (2) to (5). The thermodynamic data for
equilibria (2) to (5) have been compared with the experimentally determined equilibrium
constants and show good agreement (Helgeson et al. 1978).

log (Alt/Si)f
Fig. 3. Plot of log (AL/Si)f vs. temperature. All necessary data for calculation of the indicated mineral-
ogical equilibria are summarized in Tab. 2. The Chemical composition of the solution with respect to
alkali and alkaline earth elements is given in Tab. 1. Curves (a) and (b) demonstrate the effect of
mixing initial fluids of 260 °C and subsurface water of 100 °C (b) or surface water of 0 °C (a); figures
along curve (a) and (b) indicate mixing ratios. Effects of supersaturation of Al-species are not consid-
ered. Open circles (o) represent analytical results for geothermal waters at the earth’s surface (Fyfe
et al. 1978; Arnorsson et al. 1982). The actual temperature of the fluid indicated by x on curve (b) is
given by (x). Further discussion in the text.

Some (Alt/Si)f values of geothermal fluids (Fyfe et al. 1978; Hem 1969; Arnorsson
et al. 1982) are represented in Fig. 3. Since most of these fluids undergo boiling near the
earth’s surface, their temperature at the time of collection may be considerably lower
than that at their source. They all show characteristic deviations of the theoretically
expected log (Alt/Si)f ratios to higher values. For example, the water sample (X) in
Fig. 3 (Arnorsson et al. 1982) shows Si02-and Na+/K+-temperatures of ~260°C, and the
analytical log (Alt/Si)f ratio is found to be —3.2. If this solution equilibrated according
to eq. (2)—(6), then the expected log(Alt/Si)f should fall in the vicinity of zero. Since
cooling of the solution by boiling seems to affect the Si02*aq concentration only negli-
 Ga/Ge-Geothermometer for Sphalerite from Sediment-hosted Deposits 21

gibly (Ellis & Mahon 1977), it must be assumed that Alt concentration has been drastical-
ly reduced. Düring cooling supersaturation of the fluid with respect to Al species is by
Orders of magnitude greater than in case of Si02-aq. For this reason rapid cooling by
boiling of fluids seems to cause selective removal of most probably metastable Al-bearing
species from solution (Pa£es 1978).

3. Relationship of (Alt/Si)f to (Ga/Ge)f

From the average Ga/Al and the Ge/Si ratios in magmatic and metamorphic rocks and
Sediments average atomic ratios for all rock types of 9 • IO-5 for (Ga/Al)r and 3 • IO-6
for (Ge/Si)r have been derived (Tab. 3). Changes of the (Al/Ga)r and (Si/Ge)r ratios
during alteration of rock-forming minerals seem to be insignificant. The most probable
temperature-dependant averages of Ga/Ge ratios in hydrothermal Solutions (Ga/Ge)f, are
then defined by
(8) (Ga/Ge)f = (Alt/Si)f • [(Ga/Al)r/(Ge/Si)r]
with
(9) (Ga/Al)r/(Ge/Si)r = 30
f, r indicate ‘fluid’ and ‘rock’, respectively.
With the help of eq. (8) (Alt/Si)f values are converted into a (Ga/Ge)f scale (Fig.4).
Some available Ga/Ge ratios for hydrothermal waters are indicated and will be discussed
in Chapter 5.

Fig. 4. Plot of log (Ga/Ge)f 2 log (Ga/Ge)^^ vs. temperature. This plot is deduced from Fig. 3 by ap-
plying eq. (8). Curves (a) and (b) demonstrate the effect of mixing initial fluids of 260 °C and sub-
surface water of 100 °C (b) or surface water of 0 °C (a). Open circles represent published Ga/Ge ratios
of hydrothermal waters (6 Gjibels et al. 1980; o Björnson et al. 1972). The thermal brines from Ice-
land (o) are considered to have interacted with lava in a hydrothermal convection System on the Mid-
Atlantic Ridge.
22 P. Möller

Table 3. Ga/Al- and Ge/Si ratlos in various rock types, Sediments and fluids (a) after Burton & Cul-
kin 1969; b) after Hörmann 1969).

Rock type Atomic Ratio

Ga/Ala Ge/Sib

Averages:
granites 9 x 10“s 4 x 10'6
basalts 9 x 10“s 5 x 10“6
metamorphic rocks 1 x 10"4 2 x 10“6
Sediments
— arenaceous 9 x IO-5 2 x IO“6
— argillaceous 9 x 10~s 3 x 10“6
— carbonates 1 x IO“4

average for listed rock types 9 x 10“s 3 x 10'6

fluids:
sea water 1 x 10“3 8 x 10“6
river water 1 x 10“4 4 x 10“6

Ocean water and river water (Burton & Culkin 1969; Hörmann 1969; Turekian 1969)
show ratios slightly above 1. These ratios are much too high with respect to equilibria
with feldspars, mica or kaolinite. These high ratios may be the result of interaction with
omnipresent metastable aluminosilicates. The Ga/Al and Ge/Si atomic ratios in river
water agree quite well with those in rocks (Tab. 3), but the Ga/Ge is different because the
Al/Si ratio in ocean water is higher than in the fluids from hydrolysis reactions at equiv-
alent temperatures.

4. Relationship of (Ga/Ge)f Ratio to (Ga/Ge)sph Ratio

A Ga/Ge-geothermometer can be expected to work reliably only in mineral which accu-

mulate both, Ga and Ge. Sphalerite is known to be enriched in Ga and Ge due to mineral
Solution distribution factors exceeding unity and provides an ideal choice. Assuming the
Doerner-Hoskins (1925) distribution law is operative, the number of moles of the element
i, a;, in the sphalerite after the amount on Zn2+ ion removal from the fluid, b, is given by

1 - (l-b)Mi)
(10) aria:
b
where a; 0 is the initial number of moles of the element i in the fluid and \(i) is the
distribution coefficient of the element i. Applying eq. (10) to both elements, Ga and Ge,
the Ga/Ge ratio in sphalerite is represented by
 Ga/Ge-Geothermometer for Sphalerite from Sediment-hosted Deposits 23

'Ga\ //Ga\ = l-(l-b)MGa)

(11) 'Ge^ sph/ \Ge/ f,o 1 -(1 -b)^Ge)

ratio in initial fluid

The X values are not known. If both X values are equal, the (Ga/Ge)^ ratio will be
always proportional to the respective ratio in the ore fluid. If, however, the X values are
different, then deviations from the proportionality arise. Fractionation of the elements
increases as the differente between the two X values becomes greater. Conversely, the
fractionation decreases as the degree of Zn2+ precipitation increases. Fig. 5 shows that in

Fig. 5. Calculated Ga/Ge fractionation during crystallization

of sphalerite. The various curves are representative for the
assumed ‘X(Ga), X(Ge)’ values. The Ordinate represents the
mean Ga/Ge ratio in sphalerite normalized to the initial
Ga/Ge ratio in the ore-forming solution. If all Zn2+-ions are
removed from the fluid, the mean (Ga/Ge)^^ ratio is equal
to the initial Ga/Ge ratio of the ore fluid. Large fractionations
should be expected only at low degrees of Zn2+ removal from
solution.

case of 60% Zn2+ ion removal from fluids, all assumed sets of distribution factors lead
to less than 20% change in the mean Ga/Ge ratio in sphalerite. Until the distribution
factors become known, the fractionation will be assumed to be negligible and it follows
that
(Ga/Ge)f = (Ga/Ge)^
Thus Fig. 4 may be used to find estimates of the probable temperature of the initial
metal-bearing fluids.
24 P. Möller

5. Mixing of Waters from Different Sources

If waters from different sources mix, the new Ga/Ge ratio may be calculated from
[Ga]
1+7
(12) (I) =( Ga\ [Ga]h
Ge/, [Ge]
1+7
[Ga],
where 7, the mixing ratio of volumes, is defined by:

(13)

The subscript-free and h-subscripted quantities indicate the admixed water and the initial
ore fluid, respectively.
Eq. (12) does not consider phase separations due to resulting supersaturations of
Al-species and Si02 • aq.
Mixing of fluids with different (Ga/Ge)£ ratios caused by different temperatures, but
equal specific heats, results in the mixing temperature, Tj^ :
vT + vhTh = 7T + Th
(14)
v + vh 7+1
Using the eq. (12) and (14), the curves (a) and (b) in Fig. 3 and 4 have been calcu­
lated. They show the corresponding changes of temperature and the log(Ga/Ge)Sph in
cases where initial fluids of 260 °C mix with sea water of 0°C and subsurface water of
100 °C, respectively. Depending on the (Ga/Ge)f value of the admixed waters the (Ga/Ge)m
ratio shifts to lower (Ga/Ge)^. Admixture of 3—5 parts of low temperature solution
seems not to invalidate the evaluation of initial temperatures from (Ga/Ge)sph ratios,
taking into account that analytical errors are of a factor of 2 or Alog(Ga/Ge)Spll ~0.3.
Admixture of 3 parts of 100 °C subsurface or 0 °C sea water to fluids of 260 °C leads
to supersaturation of Al species of about 1000. This extreme supersaturation in Alt will
induce Separation of Al-Ga-bearing phases. Some supersaturation in Alt with respect to
feldspar solubility is maintained because of the presence of much more soluble, but
thermodynamically less stable intermediate phases such as chlorites, montmorillonites,
illites etc.
Any drop of temperature causes supersaturation of Si02-aq and Alt (Fig. 1 and 2).
Silica is quite well retained in solution, probably in colloidal form (Krauskopf 1956).
Since Alt is not, the (Alt/Si)f and (Ga/Ge)£ ratios are observed to be lower than expected
(Fig. 3 and 4). Consequently, if mixing occurs the (Ga/Ge)^ ratio (Fig. 4) indicates a
temperature lower than that of the initial fluid. Such reasoning explains the analytical
results on (Ga/Ge)£ ratios of geothermal waters. The three samples plotting at higher
temperatures than those indicated by the Ga/Ge ratio demonstrate the loss of Ga together
with Al from the fluids. The indicated temperatures are derived from the Si02-aq Con­
tents of the solution after cooling.
 Ga/Ge-Geothermometer for Sphalerite from Sediment-hosted Deposits 25

6. Comparison of Ga/Ge Temperatures with Homogenization Temperatures

of Fluid Inclusions

Where homogenization temperatures of fluid inclusions in sphalerites or its cogenetic

minerals such as calcite, quartz or baryte are available, they have been related to the
(Ga/Ge)sph ratio of samples from the same locality (Fig. 6). Tab. 4 summarizes the neces-
sary geological and Chemical Information on Variscan and Alpidic deposits, either hosted
in carbonates or sandstones/shales. With the exception of the sphalerites from the vein
type mineralizations of Andreasberg/Germany, it was not possible to determine Ga und
Ge and the homogenization temperature on the same sample material. Therefore, the
field for each deposit in Fig. 6 results from extreme individual values.

Fig. 6. Relationship between (Ga/Ge) ratios in sphalerite and temperatures of homogenization in

sphalerite or cogenetic minerals (such as calcite or quartz). For details see Tab. 4. Figures in brackets
indicate the number of (Ga/Ge)^^ ratios used to define the fields of each deposit. Grosses represent
data of determinations of homogenization temperatures and of Ga/Ge which were obtained on the
same sample. The heavy solid line represents the mean of the feldspar-mica-quartz equilibria shown in
Fig. 4. The respective Ga/Ge-temperature is given on the Ordinate to the right.

Before going into details it is obvious that both temperature scales show a common
trend. However, when superimposing Fig. 4 and 6, it can clearly be seen that all analytical
data fall on or below the three phase equilibria of feldspar-mica-quartz. Remembering
that the (Ga/Ge) ratios indicate the temperature of the initial Solutions in their source
regions, (Ga/Ge) temperatures may be expected to be somewhat higher than the tem­
peratures of homogenization of primary fluid inclusions. Even when mixing with sub-
surface or surface waters is absent, the temperature at the site of ore deposition should
be equal or somewhat lower than that in the source region of the metal supplying fluid.
However, if mixing with low T waters occur, a rather drastic fall in temperature would

3 Monograph Series No. 25

 ts)
o\

Table 4. Compilation of temperature information on some sediment-hosted Pb-Zn deposits in Europa. Temperatures are homogenization tem-
peratures of fluid inclusions in minerals as indicated.

Type of Age of Spread of Temperature

Locality References
mineralization host rock Ga/Ge ratios information °C

Bleiberg/Kreuth, Austria carbonate-hosted Triassic 0.022-0.57 (10) 100* Kappel & Schroll 1982

Monte Narba, Italy discordant veins Silurian 2-15 (9) 105-140 Valera 1974
in blackshales (Qz> Tistl 1981

Monte di Ferm, discordant veins Ordovician 5-39 (3) 195-252 Tistl 1981
Italy in graywackes (Qz)
and sandstones

Tynagh, Eire

P. Möller
hosted in shaly Carbonifer. 0.24-4 (6) 150-190* Rüssel, priv. comm.
carbonates

Wiesloch, Germany fracture fillings Triassic <0.05-0.4 (7) <90 Ganz 1981
in Muschelkalk (Cc)
Bad Grund, Germany vein in slate Devonian 2-4.9 (9) 130-160 (Qz) Behr & Horn 1984
123-140(ZnS) Adeyemi 1982
Andreasberger veins in slates Devonian 0.77-3.63 (7) 95-160 Horn, priv. comm.
Gangrevier, Germany (ZnS)
Ramsbeck, Germany vein in slates Devonian 1.18-1.37 180-200 Koschinski 1979
(ZnS) Grassegger, priv. comm.

* petrological evidence
 Ga/Ge-Geothermometer for Sphalerite from Sediment-hosted Deposits 27

be the result. This has been discussed in Chapter 5 and is demonstrated in Fig. 4 by
curves (a) and (b). The changes in (Ga/Ge)^ ratio due to dilution are negligible at
mixing ratios < 5. Thus, if an admixture of cool subsurface or surface waters occurs, the
temperature of homogenization is expected to be much lower than that derived from the
(Ga/Ge)sph ratio, which provides a reliable lower estimate of the initial temperature. It is
a lower estimate only because of the unknown changes of Ga concentrations during
cooling of the fluids.
For convenience it is suggested to read the model temperatures between the two
feldspar-mica-quartz equilibria. The ränge of uncertainty is then +10 °C and —40 °C, if
only equilibria with thermodynamically stable mineral phases are considered.
Samples plotting along the feldspar-mica-quartz equilibrium line may indicate the
correct temperature of the initial fluid, e.g. Ramsbeck and Mt. di Ferm (Fig. 6). This
criterion is, however, not sufficient, because the mixing model allows samples to plot
near this line, if the admixed volume of cooler waters is very large. The rather wide spread
of (Ga/Ge)sph ratios for Bleiberg/Kreuth, for instance, indicafes that at this locality the
initial fluid showed temperatures of at least 180 °C. Thus water from deep seated but
unknown origin (Schroll 1983; Koppel 1983) may have mixed with large amounts of
subsurface waters of about 100 °C.
For vein type mineralizations of Bad Grund and Andreasberg (Ga/Ge)^ point to
temperatures of the initial fluids above 220 °C, which must have mixed with waters less
about 130°C in Order to yield the observed homogenization temperature. More exact
information could be obtained after pressure correction of the homogenization tem­
peratures.
The (Ga/Ge)sph ratios for Ramsbeck agree best with measured homogenization
temperatures, thereby indicating that no significant mixing occurred.

7. Conclusion

The combination of (Ga/Ge)^ and homogenization temperatures complement each

other and help to evaluate important Steps in the ore-forming process. The uncorrected
homogenization temperature in primary inclusion is near to the real temperature during
ore formation. The Ga/Ge temperature on the other hand, indicates the temperature
which more closely approximates the initial fluid in the source region which supplied at
least some of the metal ions to the ore deposit.
The temperature of the initial fluids in the ränge of 180—270 °C lead to a source
depth of about 6—11 km in sedimentary basins when geothermal gradients between
25—30°C/km are assumed. The ränge of temperature of 180—270 °C characterizes the
beginning of greenschist-facies metamorphism. Thus, in the absence of anomalous geo­
thermal gradients, the metal-bearing fluids seem to be generated by hydrolysis of alumino-
silicates among other minerals at depths of about 8 km at temperatures of about
200—250 0C and lithostatic pressures of about 2.5 kbar during chloritization of feldspars
and mica. The fluids ascend along tectonically generated pathways. Since carbonate sedi­
28 P. Möller

ments are quite permeable for near-surface waters, mixing of fluids from two different
sources may be expected and leads to a wide ränge of temperatures within which ore-
forming processes have taken place. Some vein type ore deposition may form while the
initial fluids ascend along fractures. Fluid-mixing may predominate during the formation

Fig. 7. Schematic cross section through a

sedimentary basin illustrating the formation
of sediment-hosted Pb-Zn deposits.

of karst fillings or metasomatic replacement bodies in solidified and unsolidified car-

bonate Sediments (Fig. 7). In slates mineralization at temperatures much closer to those
of the initial fluids are likely to occur because in general mixing with surface waters will
be minor.

Acknowledgements

The author is indected to Prof. H.-J. Schneider, Berlin, Prof. G. Friedrich, Aachen, Prof.
H.-W. Walther, Hannover, and Prof. W.Turfar, Marburg, who supplied most of the samples.
I thank Prof. M. J. Rüssel, Strathclyde, and Dr. E.E. Horn, Göttingen, for their private
Communications on temperatures of ore deposition. The help of Dr. P. Dulski, Dr. J. Luck,
and W. Szacki in running the analyses is greatfully acknowledged. Critical comments by
Prof. G. K.Muecke, Halifax, considerably improved the manuscript.

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Address of the author: Prof. Dr. Peter Möller, AG Geochemie, Hahn-Meitner-Institut für Kernfor­
schung Berlin GmbH, Glienicker Straße 100, D-1000 Berlin 39.

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