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Germanium Distribution and Isotopic Study in Sulphides from MVT-Related

and VMS-Remobilised Ore Deposits

Conference Paper · August 2015

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Germanium Distribution and Isotopic Study in
Sulphides from MVT-Related and VMS-Remobilised Ore
Deposits
Rémi Belissont, Marie-Christine Boiron
GeoRessources, Université de Lorraine, Vandœuvre-lès-Nancy, France

Béatrice Luais
Centre de Recherches Pétrographiques et Géochimiques, Université de Lorraine, Vandœuvre-lès-Nancy, France

Philippe Muchez
Geodynamics and Geofluids Research Group, KU Leuven, Leuven, Belgium

Daniel PS de Oliveira
Laboratório Nacional de Energia e Geologia, Alfragide, Portugal

Manuel Muñoz
Institut des Sciences de la Terre, Université Joseph Fourier, Grenoble, France

Abstract. Germanium is a critical element in many

modern economies and requires a better understanding Tsumeb
Kipushi
of its geological cycle. Advances in LA-ICP-MS and MC- Barrigão
ICP-MS allow acquiring large dataset of in situ Ge in
minor/trace element contents and detect small isotopic hydroxy-sulphates
variations, respectively. Applying these techniques on Ge-sulphides
contrasted Ge-bearing ore deposits helps to better
Ge in sulfosalts
understand Ge distribution in ore minerals, incorporation
Tsumeb (supergene)
mechanisms, and give further insights into Ge enrichment
log(aS2)

and deposition processes. The results showed that

monovalent elements (Cu, Ag, Tl) enhance the
incorporation of Ge and related trace metals in sphalerite
and chalcopyrite via coupled substitutions. The broad
range of δ74Ge measured in sphalerite from Saint-Salvy
indicates low-T isotopic fractionation related to sphalerite
precipitation during fluid cooling.
Keywords. Germanium, sulphides, isotopes, MVT, VMS.
1 Introduction
Germanium is increasingly demanded due to its major
applications in modern high-tech devices for sustainable
energy and communication economies. Its strategic
importance and scarcity in most geological environments
require a better understanding of the Ge geological cycle
in ore deposits.
The chalcophile and organophile behaviours of Ge in
low-T near-surface processes result in significant
enrichments in low-T sediment-hosted Pb–Zn deposits
(MVT, SHMS) and coal. Accordingly, these deposits are
the most important substrate for Ge production.
In sulphidic ore deposits, Ge occurs as a trace to
major component in many sulphides with sphalerite-
derivative structure. For instance, sphalerite, the most
studied and economic Ge host, can contain up to 2500
ppm Ge in the Saint-Salvy deposit, French Massif
Central (Belissont et al. 2014). Chalcopyrite can reach
more than 6000 ppm Ge in the Barrigão deposit, Iberian
Pyrite Belt, Portugal (Reiser et al. 2011). Finally, Ge
occurs in tenth of per cent in renierite and germanite in
the Kipushi deposit, Central African Copperbelt, D.R.
Congo (Heijlen et al. 2008).
Miss.–Valley
Saint-Salvy
Ge in ZnS Apex mine
Pyrenees ZnS deposits
(post–metamorphism)
Ge in coal
and Fe–Ni Ge in silicates, oxides,
hydroxides and arsenates
log(aO2)
Figure 1. Schematic diagram of Ge behavior in different
geologic environments as related to oxygen and sulphur
activities. Modified from Bernstein (1985).
Recent advances in LA-ICP-MS and MC-ICP-MS
techniques allow performing in situ spot analyses of
trace elements down to (and often below) the ppm level,
and detecting small stable isotope variations with
enhanced precision and reproducibility, respectively. Our
study aims at understanding the physical-chemical
conditions triggering the enrichment, partitioning and
isotopic fractionation of Ge in ore deposits.
2 Targeted ore deposits
Based on natural observations, experimental and
thermochemical data, Ge distribution is mainly related to
sulphur and oxygen activities, and temperature (Fig. 1).
Our study focuses on distinct Ge-bearing sulphidic ore
deposits such as sphalerite from the Saint-Salvy deposit
(France), chalcopyrite from the Barrigão deposit
(Portugal) and Ge-sulphides from the Kipushi deposit

Strategic metals: their sources, and ore-forming processes 683

 (D.R. Congo).
The Saint-Salvy Zn–Ge–Ag vein-type deposit is
located on the S border of the Sidobre granite massif,
SW of the French Massif Central. The vein system is
hosted by the western part of the Cambrian–Silurian
schist unit. The ore body is 3 km long and lies along a
sub-vertical ENE–WSW strike slip fault (Cassard et al.
1994). The mineralisation occurs as decametric veins of
massive sphalerite and metric lenses of implosion-
collapse breccias filled with siderite, quartz, and
sphalerite. Ore deposition occurred during the Lias-
Dogger transition under an extensional strike-slip
regime, from high-salinity (H2O–NaCl–CaCl2, 23–25
wt.% NaCl eq.) and low-T (80–140 °C) fluids (Munoz et
al. 1994).
The Barrigão Cu–Sn–Ge vein-type deposit is located
within the SE part of the Iberian Pyrite Belt (Portuguese
side), only 10 km SE from the Neves Corvo world-class
VHMS deposit. The orebody consists of two metric-
thick fault-related vein systems extending over 1800 m
(Reiser et al. 2011). The economic breccia-type ore
mainly consists of coarse-grained chalcopyrite and
tennantite–tetrahedrite in a gangue of quartz, carbonates
and black shale fragments. Late Cu-rich fault-related
veins of this region originate from the remobilisation of
the VHMS via post-depositional low-grade regional
metamorphism during the Variscan orogeny.
Chalcopyrite deposition is associated to temperatures of
260–300°C and a wide range of fluid salinities (2–25
wt.% NaCl eq.; Mateus et al. 2003).
The Kipushi vein-type Cu–Zn–(Ge–Pb) deposit is
located in the SE part of the Central African Copperbelt
along the Lufilian orogenic belt. The ore lenses are
situated on the northern flank of an anticline, along the
subvertical NE-directed Kipushi fault. The
mineralisation forms a pipe-like orebody, irregular to
elliptical in cross-section, trending 28°NE, 20–60 m
thick on its 200–600 m length, and dipping 70°NW
(Intiomale 1982). The mineralisation consists of
chalcopyrite, sphalerite, pyrite, bornite, and chalcocite,
with lesser amounts of galena, arsenopyrite, tennantite
and renierite. Sulphide deposition occurred at
temperatures of ~290–380°C by the mixing of metal-
bearing fluids with a H2S-rich reservoir (Heijlen et al.
2008).
3 Analytical techniques and methods
3.1 Major elements by SEM and EPMA
Preliminary analyses were carried out using a Jeol
J7600F scanning electron microscope (SEM) in order to
study major/minor element distribution within the
studied minerals. Back-scattered electron images and X-
ray maps were recorded in EDS mode for major
elements and WDS mode for minor/trace elements.
Major/minor element analyses and maps were
performed using a Cameca SX100 EPMA equipped with
five WDS. Peak calibration on each element was carried
out using reference materials. The beam current was of
100 ηA with an accelerating voltage of 25 kV. Peak
counting times were scaled from 10 to 60 s (reduced by
half for background counting) depending on the element.
684 MINERAL RESOURCES IN A SUSTAINABLE WORLD • 13th SGA Biennial Meeting 2015. Proceedings, Volume 2
3.2 Trace elements by LA-ICP-MS
LA-ICP-MS is designed to perform fast in situ spot
analyse for a wide range of trace elements (e.g., Ge, Ga,
In, Sn; Cook et al. 2009). The analyses were carried out
at GeoRessources–Nancy (France). The instrument is
composed of a 193 ηm MicroLas Pro ArF Excimer
coupled with an Agilent 7500c quadrupole ICP-MS.
The procedure for analysing sphalerite is detailed in
(Belissont et al. 2014). Laser ablations are performed
using a constant 5 Hz pulse rate of 90 mJ. Data were
collected during a 30 ms dwell time per channel to
enhance the number of counts for trace elements.
Specific areas of the sample plates were ablated with 32–
60 µm spot diameters. The following isotopes were
monitored: 57Fe, 64Cu, 66Zn, 71Ga, 74Ge, 75As, 107Ag,
111
Cd, 115In, 118Sn, 121Sb and 208Pb. Data reduction were
carried out using Iolite software with the internal
standard method (i.e., Zn content for sphalerite, Cu
content for chalcopyrite and tennantite–tetrahedrite).
External calibration was performed with the synthetic
polymetallic sulphide material MASS-1 (Wilson et al.
2002). Limits of detection (3σ criterion) and uncertainty
(σ/√n) depend upon the ablation spot diameter and the
analysed element. Minimum LOD are usually lower than
1 ppm for the trace elements analysed at ablation spot
diameters from 32 to 60 µm.
3.3 Ge isotopes by MC-ICP-MS
Stable isotope variations of metals are new tracers of
sources and fate of metals as well as characterising ore-
forming fluids and their evolution (Asael et al. 2012;
Gagnevin et al. 2012). Bulk Ge isotopic measurements
were carried out using multicollector ICP-MS systems at
the CRPG-Nancy (France). The GV Instruments
Isoprobe were used for sphalerite from Saint-Salvy and
the Thermo Scientific Neptune Plus for Barrigão and
Kipushi samples.
Chemical procedures used to purify Ge from the
samples follow the analytical methods for iron
meteorites and sulphide minerals (Luais 2007; Luais
2012). About 10–30 mg of selected grains is digested in
Teflon vials using HNO3 7N at 60°C and Ge is isolated
using an AG-50W-X8 cation-exchange resin.
Analytical settings for measuring Ge isotopes have
been described by Luais et al. (2000) and Luais (2007,
2012). The multi-collection system simultaneously
measures 70Ge, 72Ge, 73Ge and 74Ge for isotopic ratio
calculations, 68Zn for interference corrections on 70Ge,
and 69Ga and 71Ga for external mass bias corrections.
Samples were analysed at 50 to 500 ppb Ge dilution. Ge
isotope ratios are measured using the sample-standard
bracketing method and expressed in the δ unit with
respect to the NIST 3120a Ge standard as (x = 72 to 74):
Measurements of external JMC and Aldrich Ge
standards give long-term reproducibility better than 0.15,
0.20 and 0.25‰ for δ72Ge, δ73Ge and δ74Ge, respectively.
3.4 Synchrotron-based µ-XRF mapping 4A) reveals a clear correlation between the content in
monovalent elements (Cu, Ag) and tri- and tetravalent
Micro-XRF maps were performed at the BM23 beamline ones (e.g., Ge, Ga, Sb). The binary plot (Fig. 4B)
of the European Synchrotron Radiation Facility (ESRF, indicates that Ge and related trace metals incorporation
Grenoble, France). The storage ring was operated at 6 occurs via coupled substitution with monovalent
GeV in multibunch mode with a ~200 mA current. X- elements assuring charge balance such as 3Zn2+ Ge4+
rays are monochromatised with a fixed-exit double- + 2(Cu,Ag)+. Direct substitutions occur for divalent
crystal Si(111) monochromator and focused into an elements such as Zn2+ (Fe,Cd)2+.
incident beam of ~3×3 µm2 using two mirrors in the
Kirkpatrick-Baez geometry. XRF data were collected
with a Vortex silicon-drift energy-dispersive settled 90°
to the incident beam of 11.3 keV in order collect Ge, Cu
and Fe K lines. Dwell-time was adjusted to 1 s with a
typical step-size of 10 µm.

4 Results and discussion

4.1 Ge content and distribution

Germanium occurs in various concentrations in the

studied deposits (Fig. 2). The most notable average Ge
concentrations occur in sphalerite for Saint-Salvy and Figure 3: A. Synchrotron-based µ-XRF maps of Cu and Ge in
chalcopyrite for Barrigão, with 780 and 1100 ppm, sphalerite from Saint-Salvy. Ge and Cu are both enriched in
sector zoning. Ge is depleted in rhythmic bands. B. EPMA map
respectively. The tennantite–tetrahedrite series contains
of Ge in chalcopyrite (Cp) and tennantite (Tn) from Barrigão.
only ~15 ppm. In the Kipushi deposit, Ge averages only Former crystal faces and minute relics are visible.
220 ppm in chalcopyrite and 6 ppm in bornite. Ge
content histogram for sphalerite exhibits an intense mode
under 1 ppm, with a long tail stretching up to 5900 ppm.

Figure 4. A. PCA of LA-ICP-MS data in sphalerite from

Saint-Salvy and Kipushi. B. Sum of Ge plus related tri- and
Figure 2. Histograms of Ge content in the main host minerals tetravalent vs monovalent metals. *Tl data only for Kipushi.
at Saint-Salvy, Barrigão and Kipushi.
PCA of LA-ICP-MS data in chalcopyrite (Fig.5A)
show a strong anticorrelation of Ge and related trace
4.2 Zoning patterns
elements with Fe, indicating they substitute in the Fe
Sphalerite from Saint-Salvy (Fig. 3A) is inclusion-free, tetrahedral site via the coupled substitutions 3Fe3+
supra-millimetric, and displays superimposed rhythmic 2(Sn,Ge)4+ + (Cu,Ag)+. In tennantite–tetrahedrite, PCA
bandings and sector zonings. Element maps and suggests the direct substitution Fe2+ (Pb,Cd,Zn)2+ and
statistical analyses point out clustering and sectorial show that Ge and Ag are enriched towards tennantite and
enrichment of Cu, Ge, Ga and Sb in [111] planes due to tetrahedrite end-members, respectively. Ge4+ (53 m) can
crystal controls (Belissont et al. 2014). substitute As3+ (58 m) than Sb3+ (76 m).
Chalcopyrite from Barrigão (Fig. 3B) shows complex
patchy zonings of Ge due to hydrothermal overprints and
tennantite replacement (Reiser et al. 2011).
Ge-bearing sulphides from Kipushi do not exhibit
large-scale chemical patterning. However, the scare
observable zoning patterns observable in sphalerite more
likely result from a huge number of micro- and/or nano-
inclusions of Cu–Ge-rich clusters.

4.3 Incorporation mechanisms

Figure 5. PCA of LA-ICP-MS data in chalcopyrite (A) and
Principal component analysis of merged LA-ICP-MS the tennantite–tetrahedrite solution series (B) from Barrigão.
data in sphalerite from Saint-Salvy and Kipushi (Fig.

Strategic metals: their sources, and ore-forming processes 685

 4.4 Ge isotopes and deposition process
Sphalerite from Saint-Salvy yields a broad range of
δ74Ge values, from about –2 to +1‰, compared to upper
mantle/crust rocks (and iron meteorites) compositions
(Luais, 2007, 2012), which is characteristic for low-T
isotopic fractionation. δ74Ge correlates with δ34S (Fig. 6)
along a mixing trend. Considering ab initio fractionation
coefficients αsph–sol(T) (Li et al. 2009) and the T range of
80–140°C involved for sphalerite deposition at Saint-
Salvy (Munoz et al. 1994), the observed range of δ74Ge
most likely results from variations of αsph–sol due to
temperature decrease during the cooling of the
mineralising fluid through time and precipitation.
Figure 6. Bulk δ74Ge vs bulk δ34S for sphalerite from Saint-
Salvy. In situ SIMS analyses have shown no correlation of δ34S
with the zoning types (Belissont et al. 2014).
Preliminary δ74Ge for renierite from Kipushi yield an
average of +1.48±0.15‰. Renierite and germanite from
the Tsumeb Cu–Zn–Pb deposit (Namibia) have been
analysed for comparison, they yield δ74Ge values of -
0.36±0.09 and 0.00±0.08‰, respectively. The Kipushi
and Tsumeb deposits are similar in many points, but
hotter temperatures at Tsumeb (350–450°C, Melcher
2003) may explain the smaller Ge isotopic fractionation
compared to Kipushi (290–380°C, Heijlen et al. 2008).
5 Concluding remarks and future work
In sphalerite from Saint-Salvy and Kipushi, monovalent
elements (Cu, Ag, Tl) enhance the incorporation of tri-
and tetravalent (including Ge) metals via coupled
substitution in the Zn tetrahedral site. Ge is preferentially
enriched in chalcopyrite rather than in the tennantite–
tetrahedrite series due to greater affinity for tetrahedral
Fe3+ than As3+ and Sb3+. Incorporation of Ge also occurs
via coupled substitutions with monovalent elements (Cu,
Ag) and to a lesser extent, divalent element (Zn, Pb).
The broad range of δ74Ge in sphalerite from Saint-
Salvy is due to low-T isotopic fractionation. We can
argue that sphalerite deposition occurred in open system
due to fluid cooling.
Enhanced work is on-going for the deposits of
Barrigão and Kipushi deposits, where a variety of Ge-
bearing sulphide minerals co-exist. We assess this will
provide valuable information on Ge elemental parti-
tioning and isotopic fractionation, as well as further
insights into ore deposition processes.
686 MINERAL RESOURCES IN A SUSTAINABLE WORLD • 13th SGA Biennial Meeting 2015. Proceedings, Volume 2
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Acknowledgements
The authors thank D Cassard and C Lerouge (BRGM–
France) for supplying the Saint-Salvy sample material.
This work has been supported by the French National
Research Agency through the national program
“Investissements d’avenir” with the reference ANR-10-
LABX-21– LABEX RESSOURCES21 and the INSU-
CESSUR (CNRS) project.
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