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![Page 1: Mineralogy and geochemistry of indium-bearing polymetallic vein-type deposits: Implications for host minerals from the Freiberg district, Eastern Erzgebirge, Germany](https://reader037.fdocuments.us/reader037/viewer/2022100409/575074211a28abdd2e92e7a0/html5/thumbnails/1.jpg)
www.elsevier.com/locate/oregeorev
Ore Geology Reviews
Mineralogy and geochemistry of indium-bearing polymetallic
vein-type deposits: Implications for host minerals from
the Freiberg district, Eastern Erzgebirge, Germany
Thomas Seifert *, Dirk Sandmann
Department of Economic Geology and Petrology, Institute of Mineralogy, TU Bergakademie Freiberg, Brennhausgasse 14,
D-09596 Freiberg, Germany
Received 1 April 2003; accepted 15 April 2005
Available online 27 October 2005
Abstract
Located at the northwestern border of the Bohemian Massif in the European Variscides, the Erzgebirge is one of the most
important Sn–W–Mo, Ag, Cu–Zn–Pb–In, U, and Bi–Co–Ni metallogenetic provinces in Europe. The ca. 1100 silver-base metal
veins in the Freiberg metamorphic core complex are characterized by two principal types of late-Variscan polymetallic vein-type
mineralization: (1) Quartz-bearing As(–Au)–Zn–Cu(–In–Cd)–Sn–Pb–Ag–Bi–Sb polymetallic sulphide association (dkbT ore-
type), and (2) Carbonate- or quartz-bearing Ag–Sb polymetallic sulphide association (debT and deqT ore-type). High indium
concentrations in the Freiberg silver-base metal vein district and other base metal and tin-polymetallic deposits suggest that the
Erzgebirge is among the largest In-enriched ore provinces known worldwide. The first modern geochemical bulk ore and
microprobe analyses addressing In distribution in the Freiberg district are presented in this paper and are compared with
published data.
Polymetallic veins in the Freiberg district show a wide range of In concentrations up to 0.15 wt.% with an average of 176 ppm
(n =82). The dkbT ore-type veins in the dFreibergT (up to 1560 ppm In, mean 253 ppm, n =36), dMuldenhuttenT (up to 785 ppm In,
mean 284 ppm, n =10), and dBrandT ore fields (up to 638 ppm In, mean 156 ppm, n =15) occur the highest In resources in the
Freiberg district. Two types of In concentration can be distinguished, based on microanalytical study. The first type was found in
sphalerites of the Zn–Sn–Cu sequence (as presented in one of the figures in this article) which show In contents up to 0.38 wt.%,
significant Cd up to 1.11 wt.%, and Ga contents up to 0.17 wt.%. Iron-rich sphalerites (mean 12.9 wt.% Fe, n =202) from a
representative Ag-base metal vein are characterized by In contents between 0.03 and 0.38 wt.% (mean 0.16 wt.% In, n =202). A
negative correlation exists between (Zn+Fe) and Cd, and (Zn+Fe) with In, reflecting structural substitution of In and Cd in
sphalerite. The second type of In enrichment was identified as microscopic Zn–Cu–Sn–In–S grains in pyrite of a Cu-rich dkbT vein.Quantitative electron images of these grains (up to 6 Am) shows high levels of Zn (5.6 to 52.8 wt.%), Cu (4.1 to 19.6 wt.%), Sn (0.3
to 17.2 wt.%), and In (1.3 to 2.9 wt.%). In the ternary (Cu+Ag)–(Sn+In)–(Zn+Fe) diagram, compositions of the Zn–Cu–Sn–In–S
phase in a representative Cu-rich dkbT ore-type sample fall along a linear compositional trend between Fe–Cu–In-rich sphalerite
(Zn0.76Fe0.11Cu0.06In0.01S) and the ideal fields of petrukite and sakuraiite (Cu0.29Zn0.08Fe0.32In0.02Sn0.13S). Both types of In
enrichment support that the In-mineralization is associated with the Zn–Sn–Cu sequence (dindium stageT) of the dkbT ore-typeassociation. Based on mineralogical, geochemical, isotopic, fluid inclusion, age relationships and structural data, the high In
concentrations in base metal veins in the Erzgebirge may indicate an influence of fluids expelled from magmas during
emplacement of post-collisional lamprophyric and rhyolitic dikes. The high In concentration of Cd- and Fe-rich sphalerites
0169-1368/$ - s
doi:10.1016/j.or
* Correspondi
E-mail addr
28 (2006) 1–31
ee front matter D 2005 Elsevier B.V. All rights reserved.
egeorev.2005.04.005
ng author.
ess: [email protected] (T. Seifert).
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T. Seifert, D. Sandmann / Ore Geology Reviews 28 (2006) 1–312
from Ag-base metal and Sn-polymetallic deposits in the Erzgebirge is an additional argument for a genetic link between these
mineralization stages. Such evidence is significant for exploration of magma-affiliated In deposits in post-collisional settings.
D 2005 Elsevier B.V. All rights reserved.
Keywords: Freiberg; Erzgebirge; Germany; Indium; Ag-rich base metal veins; Sn greisen and veins; Late-Variscan; Post-collisional lamprophyric
and rhyolitic magmatism
1. Introduction
A wide variety of indium-bearing ore deposits is
described in the literature (cf. Schwarz-Schampera
and Herzig, 2002). Polymetallic base metal vein depos-
its and granite-related tin–tungsten-base metal deposits
(vein-, stockwork-, and greisen-type ore bodies) are
among the most important hosts for In-bearing miner-
alization. A world-class reference area for both deposit
types is the Erzgebirge–Krusne hory metallogenetic
province in the central part of the Saxo-Thuringian
zone of the Variscan orogen (Fig. 1).
The elements indium and germanium were discov-
ered in 1863 and 1886, respectively at the Bergakade-
mie Freiberg, from ores of the local Freiberg district
(eastern Erzgebirge, Saxony, Germany). Silver-rich
polymetallic vein-type deposits were mined from
about 1168 to 1969 in an area of approximately
35�20 km. During the study for the source of thallium
Fig. 1. The position of the Erzgebirge in the European Variscides (modified
Thuringian Zone; Tep-Barr = Tepla-Barrandian Zone.
in local ores of the Freiberg mining district, Reich and
Richter (1863a,b) observed an indigo-blue line with the
spectroscope which did not correspond to any known
element. They then isolated the new material as chlo-
ride, oxide hydrate, and metal. Because of this charac-
teristic colour, the new element was named indium.
According to Reich and Richter (1864), only the Frei-
berg sphalerite showed significant In contents of about
0.1 wt.%. Winkler (1865) measured an In content of
0.0448 wt.% in sphalerites from the polymetallic sul-
phide veins of the Freiberg district.
In 1885, an unknown mineral was found at the
Himmelsfurst mine in the southern part of the Freiberg
district. Weisbach (1886) named this new mineral
argyrodite (dArgyroditT). The discovery vein was
named therefore dArgyrodit SpatT. Clemens Winkler
in Weisbach (1886) inspected this mineral and found
75 wt.% Ag and 18 wt.% S, but 7 wt.% could not be
identified. After long and difficult analyses he discov-
from the compilation of McKerrow et al., 2000). Saxo-Thur = Saxo-
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T. Seifert, D. Sandmann / Ore Geology Reviews 28 (2006) 1–31 3
ered the element germanium in 1886. This element had
already been predicted in 1872 by D. Mendelev as
dEkasiliziumT, when setting up his periodic system of
the elements. According to Winkler (1886), the Frei-
berg argyrodite (Ag8GeS6) has an average composition
of 74.72 wt.% Ag, 6.93 wt.% Ge, 17.13 wt.% S, 0.66
wt.% Fe, and 0.22 wt.% Zn.
Hydrothermal Ag-rich base metal vein-type deposits
(Fig. 2) were mined in the Eastern Erzgebirge (Freiberg
district), Central Erzgebirge (Marienberg, Annaberg,
and Hora Sv. Kateriny districts), and Western Erzge-
birge (Johanngeorgenstadt, and Schneeberg districts)
from the early Middle Ages to the 20th Century (cf.
Baumann et al., 2000). The Freiberg vein field was one
of the largest base metal districts in Europe with a
production of more than 5000 t of silver metal from
Fig. 2. Simplified geology of the Erzgebirge (Saxony, Germany; Bohemi
epizonal metamorphic rocks to non metamorphic Upper Carboniferous rock
the end of the 12th Century to the end of the 19th
Century, as well as small-scale mining of copper and
tin. Uranium exploration from the Russian mining
company dSAG WismutT was active from 1945 to
1950, and resulted in the production of about 10 t of
U metal mined from the southern part of the district
(Seifert et al., 1996a). From 1950 to 1969 about 95,000
t of Pb metal, 59,000 t of Zn metal, and 251 t of Ag
metal were produced. Germanium, In, Cd, Bi, Au, Tl,
and pyrite were concentrated as by-products (unpub-
lished material of the dVEB Bergbau-und Huttenkom-
binat Albert FunkT, Freiberg). Residues from Zn
smelting averaging 0.35 wt.% Cd, 0.1 wt.% In, 150
g/t Tl, and 28 g/t Ge were leached with sulphuric acid
for recovery of Cd and In. From 1965 to 1972 about
470 t of Cd metal and an unknown quantity of In metal
a, Czech Republic). Erzgebirge Northern Border Zone = Cambrian
s; CSL = Central Saxonian Lineament.
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Table 1
Representative indium concentrations of late-Variscan silver-rich polymetallic veins and polymetallic vein- and greisen-type ores in the Erzgebirge and worldwide deposits for comparison
Deposit type District/deposit
(geological unit)
Ore-type Associated magmatic
rocks
Mining products Mineral/bulk ore n Range
[wt.%]
Average
[wt.%]
Ref.
Hydrothermal Ag-rich
base metal veins
Freiberg (Erzgebirge) kb A-type rhyolites and/or
mica-lamprophyres
Pb, Zn, Ag, Cu,
Sn, Ge, Cd, In, Au
Sphalerite (high-Fe) 212 0.02–0.5 0.1 1
" " kb " " Sphalerite (high-Fe) 37 0.001–0.5 0.1 2
" " kb " " Sphalerite (high-Fe) 141 0.001–0.5 0.1 3
" " kb " " Sphalerite (high-Fe) 12 0.03–0.3 0.09 4
" " eb " " Sphalerite (moderate
to high-Fe)
4 0.001–0.1 0.03 2
" " eb " " Sphalerite (moderate
to high-Fe)
8 0.03 3
Hydrothermal barite–
fluorite–sulfide veins
Freiberg (Erzgebirge) fba Unknown Pb, Zn, Ag Sphalerite (low-Fe,
dSchalenblendeT)7 V0.001 2
" " fba " " Sphalerite (low-Fe) 10 b0.0005–0.01 0.005 4
Hydrothermal Ag-rich
base metal veinsaMarienberg (Erzgebirge) Zn–Cu–As–
Sn–Pb–Ag (kb)
Mica-lamprophyres Ag, Cu, Zn, Sn Sphalerite (high-Fe) 25 0.01–0.8 0.3 5
Hydrothermal Ag-rich
base metal veins
Wolkenstein
(Erzgebirge)
As–Zn–Cu–Sn–Ag
(kb)
Mica-lamprophyres Sn, Ag Bulk-ore-samples 2 0.01–0.02 6
" Jachymov (Krusne hory,
Czech Republic)
Zn–Cu–Sn (kb) Mica-lamprophyres Ag, U, (Sn) Sphalerite (high-Fe) 0.2 7
" Turkank zone, Kutna
Hora (Bohemian massif,
Czech Republic)
Zn–Cu–As–
Sn–Pb–Ag
Mica-lamprophyres Ag, Pb, Zn Sphalerite (high-Fe) 23 0.02–0.13 0.1 8
" " " " " Stannite Up to 0.002 9
" " " " " Sphalerite (high-Fe) 4 0.1–0.2 0.14 10
Hydrothermal Ag-rich
base metal veins
Pohled, Havlıcklv
Brod (Bohemian massif,
Czech Republic)
Zn–Cu–As–
Sn–Pb–Ag
Lamprophyres (?) Ag, Pb, (Zn) Sphalerite 27 0.01–0.2 0.08 11
" Saint-Martin-la-Sauvete
(Loire, France)
Zn–Pb–Cu–
Ag–Bi
Unknown Zn, Pb, Ag Sphalerite 37 0.02–1.05 0.4 12
" Keno Hill
(Yukon, Canada)
Pb–Zn–Cu–Ag Lamprophyres and/or
quartz–feldspar–
porphyry-dikes
Ag, Pb, Zn, Cd Sphalerite
(low-to moderate-Fe)
11 b0.001–0.01 0.002 13
" Coeur d’Alene
(Idaho, USA)
Pb–Zn–Cu–Ag Lamprophyres (?) Ag, Pb, Zn, Cu, Au Sphalerite
(low-to moderate-Fe)
59 Up to 0.04 0.01 14, 15
" Fukoku (Honshu, Japan) Cu–Zn–Ag Granitic and ultramafic
intrusive rocks (?)
Cu, Zn, Ag Sphalerite 0.2–0.8 16
Hydrothermal Ag-rich
base metal veins
Omodani
(Honshu, Japan)
Cu–Zn–Pb–Ag Rhyolitic rocks Cu, Zn, Pb, Ag Sphalerite 0.2–0.8 16
" Toyoha
(Hokkaido, Japan)
Pb–Zn–Cu–
As–Sn–Ag
Rhyolite–dacite Zn, Pb, Cu, Ag, In Bulk-ore-samples 0.014 17, 18
" " " " " Sphalerite 0.04–8.8 2.5 17, 18
" " " " " Stannite 0.04–9.8 17, 18
" " " " " Kesterite 0.1–16.5 17, 18
T.Seifert,
D.Sandmann/Ore
GeologyReview
s28(2006)1–31
4
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" Carguaicollu
(Andes, Bolivia)
Pb–Zn–Ag Dacite Pb, Zn, Ag, In Bulk-ore-samples 0.002 18
" Pulacayo (Uyuni
district, Bolivia)
Pb–Zn–Ag–Cu–Bi Dacites ? Cassiterite 0.04–0.06 19
Sn-polymetallic
sulfide skarn
Oelsnitz (Vogtland) Zn–Cu–Sn Granitoides Sn, Cu Sphalerite 0.4–1.0 20
Sn-polymetallic
sulfide skarn
Jachymov (Krusne
hory, Czech Republic)-
Plavno shaft
Sn–Zn–Cu Postkinematic granites/
rhyolites, lamprophyres
Sphalerite 0.2–0.3 21
" Pohla-Globenstein
(Erzgebirge)
Sn–W–Zn–Cu–Fe Lamprophyres Fe, Zn, (Sn, In) Bulk-ore-samples 0.004–0.01 (0.03 Cd) 22
Sn-polymetallic
sulfide vein-like
metasomatites
Annaberg
(Erzgebirge)-
dBriccius mineT
Zn–Cu–Sn–Ag Different types of
postkinematic granites,
mica-lamprophyres
Cu, Sn, Ag Sphalerite 1 1.0 5
" " " " " Bulk-ore-sample 1 0.3 6
Sn-polymetallic
greisen- and vein-type
Geyer (Erzgebirge)-
‘Rohrenbohrer’
exploration mine
Sn–Zn–Cu Different types of
postkinematic granites
and rhyolites
Sn, Cu Sphalerite (high-Fe) 19 0.04–1.2 0.4 23
" " " " " Cassiterite 52 0.0005–0.07 0.007 23
" Ehrenfriedersdorf
(Erzgebirge)-dWestfeldTSn-veins Different types of
postkinematic granites
Sn, W Cassiterite 68 0.003–0.007 0.005 24
" Ehrenfriedersdorf
(Erzgebirge)-dSaubergTSn-greisen Different types of
postkinematic granites
Sn, W Cassiterite 9 0.007 24
" Pobershau and Marienberg
(Erzgebirge)
Sn-polymetallic-veins Different types of
postkinematic granites
and rhyolites,
mica-lamprophyres
Sn, Cu, Ag Cassiterite 24 0.003–0.06 0.02 5
" Altenberg (Erzgebirge) Sn-greisen Granites with
A-type affinity
Sn Cassiterite 2 0.002–0.02 4
" " " " " Bulk-ore-samples 46 0.001–0.004 0.002 25
" Zeidelweide (Altenberg
district, Erzgebirge)
Sn-greisen Granites with
A-type affinity (?)
Sn Bulk-ore-samples 6 0.002–0.007 0.003 25
Sn-polymetallic
greisen- and vein-type
Lowenhainer greisen
zone (Altenberg district,
Erzgebirge)
Sn-greisen Granites with
A-type affinity (?)
Sn Bulk-ore-samples 23 0.001–0.005 0.002 25
" Cınovec (Krusne
hory, Czech Republic)
Sn-polymetallic-grei-
sen
Granites with
A-type affinity
Sn Sphalerite (high-Fe) 8 0.5–2.5 1.1 26
" " " " " Bulk-ore-samples 3 0.001–0.003 0.002 25
Sn-polymetallic greisen Muhlleithen (Erzgebirge) Sn–As–Cu Lamprophyres and
rhyolitic dikes with
A-type affinity
Sn Cassiterite 2 0.002–0.005 4
W vein-type Pechtelsgrun (Erzgebirge) W–Mo–Zn Granite W Sphalerite (high-Fe) 1 0.02 4
" " " " " Sphalerite (high-Fe) 4 0.05 4
(continued on next page)
T.Seifert,
D.Sandmann/Ore
GeologyReview
s28(2006)1–31
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Table 1 (continued)
Deposit type District/deposit
(geological unit)
Ore-type Associated magmatic
rocks
Mining products Mineral/bulk ore n Range
[wt.%]
Average
[wt.%]
Ref.
n-polymetallic greisen Vaulry (Massif
Central, France)
Sn–W–As–Cu–Mo–
Ag
Leucogranite Sn, W Bulk-ore-samples 0.0005 27
n-polymetallic veins Charvier (Massif
Central, France)
Cu–Zn–Sn–Bi–Ag Granites Sn, Cu Sphalerite Up to 0.8 28
n-polymetallic vein-
and greisen-type
Mt. Pleasant (New
Brunswick, Canada)
W–Mo–Sn–Bi–Zn–
Cu–F
A-type granites Sn, W, Mo, Zn, Pb, Cu,
(In)
Sphalerite 126 b0.01–6.9 1.2 29
" " " " Stannite 20 0.07–2.2 0.64 29
" " " " Chalcopyrite 39 0.01–0.5 0.16 29
" " " " Cassiterite 0.004–0.009 29
" " " " Bulk-ore-samples 250 0.002–N0.02 0.013 30
n-polymetallic veins Pravouvmiyskoe
(Komsomolskoe district,
Russian Far East, Russsia)
Sn–As–Cu–Zn Granitoides Sn Sphalerite 4 0.16–1.0 0.36 31
" " " " Sphalerite Up to 2.4 32
" " " " Chalcopyrite 71 0.01–0.75 0.13 31
" " " " Cassiterite 82 0.0005–0.002 0.001 31
" " " " Bornite 18 0.003–0.36 0.02 31
n-polymetallic veins Lifudsin (Russian
Far East, Russsia)
Sn–Zn–Cu–W–Pb Unknown Sn, W Sphalerite 0.03 33
" " " " Chalcopyrite 0.05 33
" " " " Cassiterite 0.008 33
n–W-base metal
greisen-type
Deputaskoe (Russian
Far East, Russia)
Sn–As–W Alaskite porphyry,
diorite and rhyolite
dikes (?)
Sn, W Cassiterite 0.003 34
" Zn–Cu–As " " Sphalerite 0.2–0.3 34, 35
" Zn–Sn–Cu–Pb " " Sphalerite 0.02–0.04 34, 35
" " " " Stannite 0.08–0.09 34, 35
olymetallic-Sn veins Goka (Honshu, Japan) Cu–Zn–Sn–Pb–As Granodiorite
porphyry (?)
Sn Sphalerite Up to 1.9 36
" " " " Unknown Zn–Cu–Fe–
In–Sn–S mineral
Up to 20.2 36
Ikuno (Honshu, Japan) Zn–Cu–As–Sn–Pb–
Ag
Rhyolites and/or
andesites (?)
Cu, Zn, Pb, Sn, Ag, Au Sphalerite 0.04–1.6 16
Akenobe (Honshu, Japan) Cu–Zn–Sn–Ag Felsic volcanics Cu, Zn, Sn, Ag Sphalerite 0.3–0.5 37, 16
" " " " Roquesite-bearing
sphalerite
Up to 5 37, 16
Bolivar (Andes, Bolivia) Bi–Pb–Zn–Cu–Ag–
Sn
Dacite porphyry dome Pb, Sn, Ag, Zn, (Bi) Bulk-ore-samples 0.002 18
Huari Huari
(Potosi, Bolivia)
Zn–Ag–Sn–Sb Unknown Zn, Ag, (In) Sphalerite (high-Fe) 1.0 19
San Luis (Berenguela
district, Bolivia)
Zn–Cu–Sn Rhyolite, rhyodacite and
dacite domes and dikes
Zn, Ag, Pb, Cu Sphalerite Up to 0.4 38
" " " " Stannite Up to 0.4 38
T.Seifert,
D.Sandmann/Ore
GeologyReview
s28(2006)1–31
6
S
S
S
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" Colquechaca
(Aiquile area, Bolivia)
Pb–Zn–Ag–
Sn–Bi
Volcanics Cassiterite 0.02–0.1 39
Cu–Mo-porphyry Bingham (Utah, USA) Pb–Zn–Cu–
Sb–Ag–Au replace-
ments of
limestone
Quartz-monzonite Cu, Mo Sphalerite 54 0.0005–0.04 0.006 40
" " " " " Chalcopyrite 28 0.0005–0.1 0.003 40
Cu-porphyry Central district
(New Mexico, USA)
Base metal
rich ores
Calc-alkaline
granodiorite to
quartz-monzonite
Cu Sphalerite 83 0.0005–0.12 0.007 40
Volcanic-hosted
massive sulfide
Kidd Creek
(Ontario, Canada)
Zn–Pb–Ag–
(Cu)
Felsic volcanics (?),
mafic–ultramafic flows
(?)
Cu, Zn, Pb, Ag, Sn Sphalerite 9 0.006–0.2 0.06 41, 42
" " " " " Chalcopyrite 5 0.001–0.04 0.02 41, 42
" " Cu–(Zn) " " Chalcopyrite 4 0.03–0.07 0.04 41, 42
" Neves Corvo (Iberian
Pyrite Belt, Portugal)
Cu–Zn–Sn Felsic volcanics (?),
granites (?)
Cu, Zn, Sn, Pb, Ag Cu–Sn-bulk ore Up to 0.065 43
" " " " " Cassiterite 0.005–0.015 43
" " " " " Sphalerite 0.09–0.3 43
" " " " " Tennantite 0.06–0.2 43
" " " " " Stannite 0.2–3.0 43
Epithermal Au–Ag veins Prasolov (Kuril Island
Arc, Russia)
Au-base metal Andesite–dacite–rhyolite
dome
Sphalerite 10 0.4–4.7 1.5 44
Active magmatic system Kudryavyi volcano
(Kuril Island Arc, Russia)
Zn-, Cd-, Cu-,
Ag-, Te-,
In-enriched high-
temperature
fumarolic system
(500–900 8C)
Basaltic andesite Sphalerite 12 1.8–14.9 5.9 44
Active magmatic system Merapi volcano
(Java, Indonesia)
Se-, Re-, Bi-, Cd-,
Au-, Cu-, In-, Pb-,
W-, Mo-, Cs-, Sn-,
Ag-, As-, Zn-,
F-enriched fumarolic
system (500–900 8C)
Andesite Sphalerite 10 0.005–0.03 0.02 45
n =number of analyses.
References:
1—Tolle (1955), 2—Baumann (1957), 3—Baumann (1964), 4—Hoang (1984), 5—Seifert (1994), 6—Th. Seifert (unpublished data, 2001), 7—Bernardova and Poubova (1965), 8—Novak and
Kvacek (1964), 9—Hak et al. (1964), 10—Hak et al. (1983), 11—Hak and Johan (1962), 12—Johan (1988), 13—Boyle (1965), 14—Fryklund and Flechtner (1956), 15—Leach et al. (1998), 16—
Shimizu and Kato (1991), 17—Kooiman and Ruitenberg (1992), 18—cf. Schwarz-Schampera and Herzig (2002), 19—Putzer (1976), 20—Doering et al. (1994), 21—Hak et al. (1979), 22—
Schuppan (1995), 23—Jung (1992), 24—Binde (1984), 25—W. Schilka (unpublished data, 1989), 26—Novak et al. (1991), 27—Bouladon (1989), 28—Picot and Pierrot (1963), 29—Sinclair et al.
(2005—this volume), 30—Irrinki and Kooiman (1995), 31—Gavrilenko and Pogrebs (1992), 32—Semenyak et al. (1994), 33—Zabarina et al. (1961), 34—Ivanov and Rozbianskaya (1961), 35—
Ivanov and Lizunov (1960), 36—Murao and Furuno (1990), 37—Murao and Furuno (1991), 38—Legendre (1994), 39—Fesser (1968), 40—Rose (1967), 41—Cabri et al. (1985), 42—Hannington
et al. (1999a,b), 43—Schwarz-Schampera (2000), 44—Kovalenker et al. (1993), 45—Kavalieris (1994).a Included Sn-polymetallic sulfide vein-like metasomatites (similar to the dBriccius mine,T Annaberg).
T.Seifert,
D.Sandmann/Ore
GeologyReview
s28(2006)1–31
7
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Table 2
Late-Variscan magmatic events and mineralization in the Erzgebirge
(modified after Seifert, 1994, 1999 and Forster et al., 1998)
T. Seifert, D. Sandmann / Ore Geology Reviews 28 (2006) 1–318
were produced by the Freiberg mining and smelter
company. Since 1969, all base metal and Ag mining
activities were closed down. There are, however, still
ore reserves of about 4,868,500 t of ore (averaging
3.2 wt.% Pb, 4.5 wt.% Zn, 1.7 wt.% As, and 72 g/t
Ag) in the central and southern part of the Freiberg
district.
Indium, cadmium, and other trace metals in sphaler-
ites from different ore-types of the Freiberg district
have been analyzed in the past by optical emission
spectroscopy (e.g., Tolle, 1955; Baumann, 1957,
1964). This method is essentially semi-quantitative,
lacking accuracy and precision. However, most analyt-
ical data of In contents in tin and base metal ores from
the Erzgebirge and other mining districts have been
produced by this technique (Table 1). In this study,
we present the first modern and comprehensive geo-
chemical bulk and microprobe analyses of representa-
tive ore samples from the polymetallic sulphide veins in
the Freiberg district.
2. Regional geology
The Erzgebirge (Saxonian Erzgebirge and Bohemian
Krusne hory) is part of the metamorphic basement of
the internal Mid-European Variscides on the NW-bor-
der of the crystalline Bohemian Massif core complex
(Fig. 2). It represents an antiformal megastructure with
a large core composed of medium-to high-grade meta-
morphic mica schists and gneisses with intercalations of
eclogite (Schmadicke, 1994; Rotzler, 1995; Sebastian,
1995). The peak P–T conditions in the Gneiss–Eclogite
unit were dated by Willner et al. (1997) and Tichomir-
owa (2001) at 340 and 330 Ma, respectively. According
to these authors and age data of the post-kinematic
magmatism in the Erzgebirge (Seifert, in press), an
extremely fast tectonic exhumation of the Erzgebirge
complex between 340 and 330 Ma can be postulated.
The polymetallic sulphide veins of the base metal
deposits in the Erzgebirge are hosted by ortho-(Freiberg
district) and paragneisses (Marienberg, Annaberg, and
Hora Sv. Kateriny districts), mica schists (northern part
of the Freiberg district, Johanngeorgenstadt), and sub-
ordinately by postkinematic granites (Schneeberg and
eastern part of the Freiberg district, Fig. 2).
Late Variscan acidic and lamprophyric (sub)volca-
nics intruded into the Erzgebirge metamorphic core
complex and the older stage of postkinematic granite
intrusions. The evolution of the postkinematic magma-
tism is related to late- and post-collisional extension on
the NW-borderline of the Bohemian Massif. The post-
collisional magmatism is controlled by deep fracture
zones (cf. Seifert and Kempe, 1994) and is associated
with different types of tin and polymetallic sulphide
mineralization (Table 2). The intrusion of Permo–Car-
boniferous lamprophyric dikes in the Erzgebirge indi-
cates mantle-induced high-energy and fluid pulses
during the Late Variscan. It is important to realize
that the large base metal deposits and lamprophyric
dikes are affiliated and occur together at cross-cutting
deep fault zones (Freiberg, Marienberg, and Annaberg
districts; cf. Seifert, 1994, 1999).
3. Geology and mineralogy of polymetallic sulphide
veins in the Freiberg district
The polymetallic vein-type deposits in the Freiberg
district are subdivided into certain mining areas (ore
fields) including the North (Obergruna, Kleinvoigtsberg,
Mohorn), Central (Halsbrucke, Freiberg, Muldenhut-
ten), and South sub-district (Zug, Brand–Erbisdorf=
Brand). The Ag-base metal veins of the Central and
South sub-district are mainly hosted by orthogneisses
(dFreiberg gneissT and dBrand gneissT; Fig. 3). In the
southern part of the South sub-district (dHimmelsfurstTmine; Table 3), the ore veins crosscut garnet-bearing
mica-schists. South of this mica-schist zone, no ore
veins were identified (Gotte, 1956; Baumann, 1957).
In the North sub-district, the veins are mainly hosted
by mica-schists and paragneisses, partly with intercala-
tions of meta-black-shales (Muller, 1901; Baumann et
al., 2000). Minor occurrences of the Freiberg veins are
hosted by dred gneissesT, gabbros, and Permo–Carbon-
iferous granites, rhyolites and lamprophyres (Fig. 3).
Approximately 1100 polymetallic sulphide veins were
mined up to 800 m depth. According to Baumann and
Hofmann (1967), the Freiberg ore vein system is devel-
oped within the paracrystalline joint system. The so-
called dFreiberg vein networkT is characterized by two
(NNE–SSW to N–S and E–W to ENE–WSW) shear
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Fig. 3. Schematic geological map of the Freiberg district and sample locations. Geology compiled by Baumann (1964), modified on the basis of data
from Seifert (1999) and Tichomirowa (2001). dFreiberg gneissT and dBrand gneissT are classified as orthogneisses. Sample locations are as follows
(numbers are explained in Table 3): a=4, 5; b=6, 7; c=8 to 10; d=11, 12; e=16, 17; f=21, 22; g=23 to 27; h=29, 30; i=31, 32; k=33 to 35;
m=38 to 40; n =44, 45; o=46 to 50; p =53, 54; q=60, 61; r =79, 80; s=81, 82.
T. Seifert, D. Sandmann / Ore Geology Reviews 28 (2006) 1–31 9
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Table 3
Mineralogy of polymetallic sulfide ore samples
No. in
Fig. 3
Sample
no.
Ore fielda Location (mine, vein, level) Description
[Level 0=addit] Main ore minerals Gangue
minerals
Ore
type
1 52827 Obergruna Gesegnete Bergmannshoffnung, Helmrich, 1. sl, gn, py, asp, cp,
fg, pyrg, arg
qtz, ca eq
2 52853 Obergruna Gesegnete Bergmannshoffnung, Traugott, 0. gn, sl, cp, asp qtz eq
3 982 Kleinvoigtsberg Alte Hoffnung Gottes, Bestandigkeit, 5. sl, asp, gn, py, asp ca, qtz eq
4 1057 Kleinvoigtsberg Alte Hoffnung Gottes, Christliche Hilfe, 14. sl, gn, py, asp, cp qtz eq
5 1431 Kleinvoigtsberg Alte Hoffnung Gottes, Christliche Hilfe, 14. asp, py, sl, gn, cp, arg qtz, ca eq
6 1109 Kleinvoigtsberg Alte Hoffnung Gottes, Gottes Segen, 4. sl, py, gn, asp, cp qtz, ca eq
7 1397 Kleinvoigtsberg Alte Hoffnung Gottes, Gottes Segen, 6. sl, gn, py, asp, cp qtz, ca eq
8 1168 Kleinvoigtsberg Alte Hoffnung Gottes, Heinrich, 13. sl, py, asp, gn, fg, pyrg,
ag, can, stan, cp, cst
qtz eq
9 1173 Kleinvoigtsberg Alte Hoffnung Gottes, Heinrich, 13. py, sl, asp, gn, cp qtz eq
10 1175 Kleinvoigtsberg Alte Hoffnung Gottes, Heinrich, 14. py, sl, asp, gn, cp qtz eq
11 1279 Kleinvoigtsberg Alte Hoffnung Gottes, Peter, 10. py, sl, asp, gn, cp qtz, ca eq
12 1281 Kleinvoigtsberg Alte Hoffnung Gottes, Peter, 10. py, sl, gn, asp, cp, pyrg ca, qtz eq
13 53104 Mohorn Erzengel Michael, Unbenannt, 0. sl, gn, cp, stan, asp, fg,
pyrg, arg
ca, qtz eq
14 53089 Mohorn Erzengel Michael, Wolfgang, 0. py, gn, sl, fg, cp, stan, asp – eq
15 5404 Halsbrucke Beihilfe, Unbenannt, 350-m level. sl, gn, cp, asp ca kb
16 50171 Freiberg Himmelfahrt, Christian, 6. py, gn, sl, cst, cp, asp qtz, ca kb
17 8 Freiberg Himmelfahrt, Christian, 13. asp, sl, gn, cp, py qtz kb
18 258 Freiberg Himmelfahrt, Clemens, 2. sl, py, gn, stan, cp, asp qtz, ca kb
19 50071 Freiberg Himmelfahrt, David, 0. py, asp, sl, gn, cp qtz, ca kb, younger
debT veinlet20 3006 Freiberg Himmelfahrt, Dreifaltigkeit, 11. py, sl, gn, stan, cp, asp qtz kb
21 198 Freiberg Himmelfahrt, Friedrich, 8. asp, py, gn, sl, cp ca, qtz kb
22 208 Freiberg Himmelfahrt, Friedrich, 12. asp, py, sl, gn, cp qtz, ca kb
23 50100 Freiberg Himmelfahrt, Frisch Gluck, 5. asp, py, sl qtz, ca kb
24 50105 Freiberg Himmelfahrt, Frisch Gluck, 5. gn, clst, nm, asp, sl, cp ca eb
25 50106 Freiberg Himmelfahrt, Frisch Gluck, 5. asp, sl, py, gn, cst, stan, cp qtz kb
26 222 Freiberg Himmelfahrt, Frisch Gluck, 6. sl, asp, py, gn, cp qtz kb
27 279 Freiberg Himmelfahrt, Frisch Gluck, 17. sl, py, gn, cp, asp qtz kb
28 2658 Freiberg Himmelfahrt, Gluckstern, 11. asp, sl, gn qtz kb
29 402 Freiberg Himmelfahrt, Gotthold, 14. sl, gn, cp, asp qtz kb
30 402 SL* Freiberg Himmelfahrt, Gotthold, 14. sl, gn, cp, asp – kb
31 352 Freiberg Himmelfahrt, Gottlob, 12. sl, py, asp, gn ca, qtz kb/eb
32 50005 Freiberg Himmelfahrt, Gottlob, unknown. py, sl, asp, gn, cp qtz, ca kb
33 410 Freiberg Himmelfahrt, Hauptstollngang, 1/2 10. sl, py, gn, cp qtz kb
34 420 Freiberg Himmelfahrt, Hauptstollngang, 14. py, gn, asp, cp, stan, sl qtz kb
35 422 Freiberg Himmelfahrt, Hauptstollngang, 14. sl, gn, py, cp qtz, ca kb
36 50023 Freiberg Himmelfahrt, Johann, 0. sl, asp, py, gn, cp qtz, ca kb
37 457 Freiberg Himmelfahrt, Jupiter, 6. sl, py, asp, gn, cst,
stan, cp
qtz kb
38 50042 Freiberg Himmelfahrt, Kirschbaum, 1/2 1. sl, py, gn, asp, cst,
stan, cp, arg
qtz, ca kb
39 50042 GL* Freiberg Himmelfahrt, Kirschbaum, 1/2 1. gn, sl, cp – kb
40 229 Freiberg Himmelfahrt, Kirschbaum, 13. sl, py, gn, cp ca, qtz kb
41 50032 Freiberg Himmelfahrt, Kirschzweig, 5. sl, gn, py, cp, asp qtz, ca kb
42 2461 Freiberg Himmelfahrt, Krieg und Frieden, 2. py, gn, asp, cp, sl qtz, ca kb
43 51052 Freiberg Himmelfahrt, Riemer, 8. sl, py, gn, cp, asp qtz kb
44 50083 Freiberg Himmelfahrt, Schwarzer Hirsch, unknown. sl, py, po, asp, gn, stan, cp qtz, ca kb/eb
45 50094 Freiberg Himmelfahrt, Schwarzer Hirsch, 8. sl, py, asp, gn, cp, cst qtz kb
46 P 1–4 SL* Freiberg Himmelfahrt, Wilhelm, 1. sl, gn qtz kb
47 P 1–7 GL* Freiberg Himmelfahrt, Wilhelm, 1. gn, sl – kb
48 P 1–10 Freiberg Himmelfahrt, Wilhelm, 1. py, sl, gn, cp, asp qtz, ca kb
49 P 3–4 GL* Freiberg Himmelfahrt, Wilhelm, 1. gn, asp, sl – kb
50 50160 Freiberg Himmelfahrt, Wilhelm, 2. py, sl, asp, gn, cp ca, qtz eb/kb
T. Seifert, D. Sandmann / Ore Geology Reviews 28 (2006) 1–3110
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No. in
Fig. 3
Sample
no.
Ore fielda Location (mine, vein, level) Description
[Level 0=addit] Main ore minerals Gangue
minerals
Ore
type
51 50192 Freiberg Markgraf Otto, Otto, unknown. asp, sl, gn, cp qtz kb
52 50137 Freiberg Rudolph, Kunstschachtabteufen, 1. sl, gn, asp, cp ca, qtz kb
53 50330 Muldenhutten Morgenstern, Abendstern, unknown. asp, sl, gn, cp qtz kb
54 50378 Muldenhutten Morgenstern, Abendstern, 1. asp, sl, py, cp, gn qtz, ca kb (eb?)
55 50397 Muldenhutten Morgenstern, Laura, 5. sl, cp, gn, py, asp, spb, wf qtz, ca kb
56 50394 Muldenhutten Morgenstern, Ludwig, 5. sl, gn, asp, py, cp, fg, spb qtz kb
57 50423 Muldenhutten Wernerstolln, Unbenannt, 0. asp, cp, sl, py, gn, spb ca, qtz,
(bar)
kb
58 50451 Muldenhutten Friedrich, 3-Konige, 0. sl, gn, py, cp, asp, arg qtz kb
59 50473 Muldenhutten Friedrich, Hoffnung, 2. sl, cp, gn, stan, asp, spb, wf qtz kb
60 50441 Muldenhutten Schieferleite, Unbenannt, 0. sl, gn, asp, py, cp, stan, spb qtz kb
61 50450 Muldenhutten Schieferleite, Unbenannt, 0. gn, py, asp, cp, sl qtz kb
62 50437 Muldenhutten Schieferleite, Weißer Lowe, 0. cp, sl, py, gn, asp, wf,
cst, spb, mo
qtz kb
63 52289 Zug Alte Mordgrube, Braun, 0. sl, gn, py, asp, cp,
stan, fg, cst
ca, qtz kb/eb
64 50121 Zug Beschert Gluck, Carl, 4. py, gn, fg, sl, cp, asp,
stan, fg
ca, qtz eb
65 6001 Zug Beschert Gluck, Ludwig, 0. gn, sl, py, asp, pr,
pyrg, cp, stan
ca eb
66 52262 Zug Junge Hohe Birke, Jung Tobias, 2. sl, gn, py, stan, cp,
asp, fg, cst
qtz kb
67 52215 Zug Junge Hohe Birke, Junge Hohe Birke, 7. sl, py, gn, cp, asp qtz kb
68 1499 Brand Himmelsfurst, Alte Rose, 1/2 14. sl, py, asp, gn, cp qtz, ca kb
69 6004 Brand Himmelsfurst, Concordia, 8. sl, py, asp, gn, cp ca, qtz eb/kb
70 1530 Brand Himmelsfurst, Daniel, 1/2 14. py, sl, asp, gn, cp, mo qtz, ca kb
71 51540 Brand Himmelsfurst, Jupiter, 7. sl, gn, py, cp, asp, fg qtz, ca kb
72 1669 Brand Himmelsfurst, Lade des Bundes, 1/2 14. sl, gn, py, cp, asp qtz kb
73 1675 Brand Himmelsfurst, Leopold, 3. sl, gn, asp, cst, stan, cp ca eb
74 1715 Brand Himmelsfurst, Samuel, 1/2 14. sl, cp, gn, stan, asp, fg ca kb
75 1730 Brand Himmelsfurst, Schweinskopf, 12. gn, py, sl, asp, cp, fg qtz kb
76 51568 Brand Himmelsfurst, Seidenschwanz, 2. py, sl, gn, asp, stan, cp, fg qtz, ca kb with
younger debTcarbonate
veinlet
77 54256 Brand Himmelsfurst, Silberfund, 15. gn, asp, py, sl ca, qtz eb/kb
78 3886 Brand Reicher Bergsegen, Adler, 15. sl, gn, stan, cp ca kb with
younger
debT carbonateveinlet
79 51763 Brand Reicher Bergsegen, Simon Bogners Neuwerk, 0. sl, py, asp, gn, stan, cp qtz, ca kb/eb
80 4384 Brand Reicher Bergsegen, Simon Bogners Neuwerk, 12. sl, py, gn, cp, asp qtz, ca kb
81 4428 Brand Reicher Bergsegen, Sonne und Gottes Gabe, 15. py, sl, gn, cp, stan, asp qtz, ca kb
82 4428 GL* Brand Reicher Bergsegen, Sonne und Gottes Gabe, 15. gn, sl, stan, cp – kb
Notes: *—visually separated from gangue minerals.a Brand=Brand–Erbisdorf.
Minerals: ag—native silver; arg—argentite; asp—arsenopyrite; can—canfieldite; clst—clausthalite; cp—chalcopyrite; cst—cassiterite; fg—freiber-
gite; gn—galena; mo—molybdenite; nm—naumannite; po—pyrrhotite; pr—proustite; py—pyrite; pyrg—pyrargyrite; sl—sphalerite; spb—schap-
bachite; stan—stannite; wf—wolframite; qtz—quartz; ca—carbonate; bar—barite.
Ore types: eq—dedle QuarzformationT (noble quartz formation); kb—dkiesig-blendige BleierzformationT (pyritic lead formation); eb—dedleBraunspatformationT (noble carbonate formation).
Table 3 (continued)
T. Seifert, D. Sandmann / Ore Geology Reviews 28 (2006) 1–31 11
systems, and spatial associated fissure veins. The min-
eralized dcentral shear fault zoneT shows a NNE–SSW
striking distance of about 14 km. This steeply dipping
shear vein is characterized by ore lenses with a thickness
of up to 10 m (Baumann, 1957, 1960), and was mined in
the central and southern district. In the mining area of the
important dHimmelfahrtTmine (northeastern of the town
of Freiberg) it is called dHauptstollengang StehenderT
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T. Seifert, D. Sandmann / Ore Geology Reviews 28 (2006) 1–3112
(Fig. 3, locality k: samples 33–35). The adjacent
dWilhelm StehenderT (NNW–SSE) is a typical fissure
vein with a thickness of up to 2 m and a 308 to 508dipping to West (Baumann, 1960; Fig. 4A; Fig. 3, local-
ity o: samples 46–50). To North (Obergruna, Klein-
voigtsberg, Mohorn; Fig. 3), brecciated Ag-rich
polymetallic-quartz shear veins with a thickness of up
to 2 m are common (Muller, 1850, 1901; Fig. 4B). In
the South sub-district (Brand-Erbisdorf; Fig. 3) Ag-rich
base metal veins with a thickness of up to 2 m were
mined up to 750 m depth (Muller, 1901; Baumann et
al., 2000).
The base metal veins of the Freiberg district are
characterized by two principal types of late-Variscan
polymetallic sulphide mineralization (Fig. 5):
(A) Quartz-bearing As(–Au)–Zn–Cu(–In–Cd)–Sn–Pb–
Ag–Bi–Sb polymetallic sulphide vein-type mi-
neralization [according to Muller (1850, 1901):
dkiesig-blendige BleierzformationT=pyritic lead
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Fig. 5. Mineral sequences of the Freiberg and Marienberg districts (based on Muller, 1850, 1901; Oelsner, 1930; Baumann, 1964; Seifert, 1994).
dkbT ore-type= dkiesig-blendige BleierzformationT (pyritic lead formation); debT ore-type= dedle BraunspatformationT (noble carbonate formation);
duqkT ore-type=uranium–quartz–calcite formation; dhmbaT ore-type=hematite–barite sequence; dbaflT ore-type=barite–fluorite sequence.
T. Seifert, D. Sandmann / Ore Geology Reviews 28 (2006) 1–31 13
formation (dkbT ore-type)] with arsenopyrite, py-
rite/marcasite (minor native Au), pyrrhotite, most-
ly Fe-rich sphalerite, stannite, chalcopyrite,
cassiterite, tetrahedrite, bornite, and galena (Fig.
Fig. 4. A. Polymetallic sulphide vein (dkbT ore-type) hosted by Freiberg orthogmine, level 1, Freiberg ore field. Mineralogical characteristics of selected poly
sulphide vein (deqT ore-type); sphalerite-breccias (sl) are cemented by dmilkyTBergmanns HoffnungT mine, Obergruna, North subdistrict. C. Representativ
copyrite vein of the dkbT ore-type (sample 222; bulk analyses show 1030 ppm I
D. Photomicrograph of Fe-rich sphalerite (grey) with dchalcopyrite diseaseTdFriedrichTmine, dHoffnungT vein, level 2, Muldenhutten ore field; scale bar=
(stan), chalcopyrite (cp), and cassiterite (cst), and a galena microveinlet (gn). S
dBraunT vein, level 0, Zug, Brand ore field; scale bar=30 Am. F. Chalcopyrite
and calcite (ca); representative for polymetallic veins of the Cu-rich dkbT oremine, dAbendsternT vein, level 1, Muldenhutten ore field. G. Back-scattered el
in galena (gn). Sample 50473 (Cu-rich dkbT ore-type with significant Ag, Bi, Slow-In, high-Ag vein with sphalerite (sl), arsenopyrite (asp), pyrite (py) inter
dkbT and debT characteristics (sample 51763, bulk analyses show 1.1 ppm In
dReicher BergsegenT mine, dSimon Bogners NeuwerkT vein, level 0, Brandsphalerite (sl), chalcopyrite (cp), and carbonates (ca); debT ore-type sample 531
vein, level 0, Mohorn, North subdistrict; scale bar=50 Am. K. Polymetalli
sphalerite (sl), pyrite (py), rhodochrosite (rdc), and calcite (cal). dHimmelsfurst
by carbonate (ca); chalcopyrite (yellow grains) is the youngest ore mineral. Sam
dAdlerT vein, level 15, Brand ore field; scale bar=300 Am. M. Massive In-rich
chalcopyrite (dkbT ore-type) crosscut by an debT ore-type carbonate veinlet (c
4C, D, E). Quartz is the main gangue mineral, with
rare carbonate (calcite, dolomite, siderite, rhodo-
chrosite; Fig. 4F). High Ag contents of the poly-
metallic sulphide veins in the central and southern
neiss. dHimmelfahrtT vein (NNW–SSE strike direction), dReiche ZecheTmetallic veins in the Freiberg district (B–M): B. Brecciated polymetallic
quartz (qtz). dTraugottT vein (NNE–SSW strike direction), dGesegnetee In-rich sphalerite(sl)–arsenopyrite(asp)–pyrite(py)–galena(gn)–chal-
n). dHimmelfahrtTmine, dFrisch GluckT vein, level 6, Freiberg ore field.structures (yellow). Sample 50473 (bulk analyses show 667 ppm In),
30 Am. E. Photomicrograph of sphalerite (sl) with inclusions of stannite
ample 52289 (bulk analyses show 95 ppm In), dAlte MordgrubeTmine,
(cp), arsenopyrite (asp), and sphalerite (sl) intergrowth with quartz (qtz)
-type (sample 50378; bulk analyses show 236 ppm In). dMorgensternTectron image showing matildite/schapbachite (AgBiS2) inclusions (spb)
n, and In bulk ore contents; see Table 4, sample 59). H. Representative
growth with quartz (qtz) and carbonate (ca). Transitional ore-type with
). Typical miargyrite (AgSbS2) and argentite inclusions in sphalerite.
ore field. I. Freibergite (fg) and pyrargyrite (pyrg) intergrowth with
04 (bulk analyses show 0.5 ppm In). dErzengelMichaelTmine, unnamed
c debT-type vein hosted by mica-rich gneisses with typically Ag-rich
Tmine, Brand ore field. L. Brecciated Fe-rich sphalerite (sl) is cemented
ple 3886 (bulk analyses show 638 ppm In). dReicher BergsegenTmine,
sphalerite ore (sl) with microscopic inclusions of galena, stannite, and
a). dReicher BergsegenT mine, dAdlerT vein, level 15, Brand ore field.
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Table 4
Geochemical bulk analyses of polymetallic sulfide ore samples
No. in
Fig. 3
Sample
no.
Ore type Zn Pb Cu As Au Hg Tl Se Te Ag Sb Bi Sn Mo W Sc In Cd Ge Ga Mn
wt.% wt.% wt.% wt.% ppb ppb ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm
1 52827 eq 21.6 4.0 0.2 0.7 835 10191 1.47 b3 0.1 5950 3220 9 b700 b1 b1 2.7 0.6 1031 2.7 11.0 3467
2 52853 eq 1.9 5.3 b0.1 b0.1 300 669 2.29 b5 b0.1 6220 4790 6 b500 b1 b1 0.6 0.4 155 0.6 0.7 214
3 982 eq 10.2 0.8 0.1 1.1 b15 198 0.39 b3 b0.1 1730 982 4 b400 b1 1 1.7 30 472 0.8 4.9 14920
4 1057 eq 13.0 4.3 0.2 1.8 142 78 1.90 b3 b0.1 364 237 b2 b300 b1 b1 4.0 6 1148 1.3 10.9 2737
5 1431 eq 11.2 1.2 0.2 11.7 9040 62 0.75 b3 0.2 869 1440 10 b400 b1 b1 2.1 2 813 7.2 9.2 2024
6 1109 eq 8.4 4.6 0.1 2.4 468 172 0.70 b3 b0.1 1020 634 3 b300 b1 b1 0.7 19 547 1.4 4.1 2606
7 1397 eq 13.1 4.3 0.1 3.4 275 538 1.19 b3 0.3 559 322 8 b300 b1 b1 2.0 1 593 2.2 7.0 1245
8 1168 eq 10.1 1.9 0.2 4.7 4800 156 0.40 24 0.1 10200 1000 b2 2800 b1 b128 0.6 0.9 699 4.1 6.1 1311
9 1173 eq 8.3 0.2 b0.1 2.9 441 176 0.55 b3 b0.1 632 371 2 b200 b1 b1 2.4 3 721 1.7 5.0 1272
10 1175 eq 5.9 0.1 0.1 2.5 400 98 0.25 b3 b0.1 1250 644 b2 b300 b1 b1 1.2 b0.1 481 2.4 3.6 1820
11 1279 eq 6.3 2.3 0.1 3.6 429 46 0.63 b3 b0.1 230 145 3 b200 b1 b1 2.3 0.3 422 0.7 5.2 1454
12 1281 eq 4.4 1.2 0.1 0.6 192 118 5.21 b3 0.4 218 288 4 b100 7 b1 0.4 0.5 281 0.6 3.5 1313
13 53104 eq 18.7 1.6 0.4 b0.1 4740 1079 1.05 b5 0.2 6080 5170 5 b1000 b1 b1 3.5 0.5 1492 1.3 11.5 467
14 53089 eq 2.6 3.6 1.4 0.3 4270 16436 1.44 115 0.2 19000 21400 12 b3400 b1 b15 b0.4 0.7 209 0.6 2.6 117
15 5404+) kb 35.2 3.1 0.2 b0.1 186 b1000 0.50 4 b0.2 96 25 44 b100 b1 b1 0.3 1560 3451 0.3 n.a. 6734
16 50171 kb 3.0 4.9 0.1 0.4 5 494 7.78 b3 b0.1 240 127 4 8700 7 10 0.8 12 271 0.6 2.8 1030
17 8 kb 4.0 4.0 1.7 12.8 b90 72 1.85 51 1.4 1430 168 1306 b300 b1 b1 0.6 76 374 5.5 2.5 553
18 258 kb 20.5 2.4 1.3 0.1 b2 143 1.76 b3 0.1 188 41 92 13000 b1 22 0.2 400 2537 0.4 13.1 2519
19 50071 kb, younger
debT veinlet5.1 3.8 0.1 9.2 853 625 1.56 28 0.5 257 357 21 b300 b1 b1 1.3 143 447 4.6 4.5 4264
20 3006 kb 0.5 0.3 0.2 b0.1 24 34 0.52 9 0.2 41 6 32 1200 b1 4 0.4 9 51 0.2 12.4 2100
21 198 kb 0.8 4.0 0.1 22.8 b21 27 2.02 18 0.3 134 320 70 b400 4 b1 2.8 4 135 6.4 7.3 1713
22 208 kb 6.8 3.1 0.1 12.7 b100 56 1.83 b3 0.8 88 705 110 b40 7 b1 0.8 39 568 4.2 5.3 1733
23 50100 kb 0.9 b0.1 b0.1 34.1 b250 24 0.12 b4 b0.1 b5 1370 b2 b800 b1 b40 b0.1 13 83 12.4 1.8 219
24 50105 eb 0.1 2.2 0.1 0.1 258 1139 0.19 9960 b0.1 3750 9 41 b200 9 b1 0.1 8 10 44.9 b0.1 8505
25 50106 kb 3.4 3.3 0.2 16.1 b120 268 1.61 b3 0.1 328 1140 4 3400 b1 b1 0.3 61 374 5.9 3.6 1506
26 222 kb 36.4 0.5 0.3 3.5 b37 192 0.73 55 0.2 101 30 31 b600 b1 b1 b0.2 1030 3548 1.3 5.6 1771
27 279 kb 32.7 2.5 1.2 0.1 b2 279 0.33 b3 0.2 204 16 126 b500 b1 b1 0.7 397 3976 0.3 7.1 1621
28 2658 kb 0.7 b0.1 b0.1 21.9 b19 97 0.23 6 0.6 b5 238 b2 b400 b1 b1 0.3 13 109 10.8 1.7 193
29 402 kb 25.5 4.2 0.8 0.2 b2 96 3.12 42 2.7 1420 11 1896 b400 b1 b1 1.7 301 3657 0.6 9.1 973
30 402 SL+) kb 42.2 7.2 0.6 0.3 b13 3000 2.62 58 6.8 1320 11 3310 b500 b2 b5 b0.1 453 4919 0.2 n.a. 1080
31 352 kb/eb 22.8 0.1 b0.1 0.7 77 136 0.96 b3 0.1 126 83 6 b300 b1 b1 0.8 1 1929 0.5 5.9 20175
32 50005 kb 9.2 1.2 0.1 1.5 39 435 1.43 11 0.4 71 107 5 b200 56 b1 0.9 26 573 1.2 4.0 2595
33 410 kb 23.6 3.7 0.4 b0.1 b2 77 0.30 47 0.6 206 64 36 b300 b1 12 5.6 473 2453 0.6 19.5 2918
34 420 kb b0.1 3.5 0.6 2.3 2300 216 1.86 48 1.0 531 375 403 1600 6 b1 0.4 20 5 1.6 6.4 60
35 422 kb 5.2 3.6 0.1 b0.1 b2 95 0.69 8 0.2 40 21 19 b100 b1 b1 0.9 36 633 0.2 4.0 1902
36 50023 kb 10.9 3.9 0.1 6.1 b31 1189 3.60 12 b0.1 111 332 b2 b300 b1 b1 4.3 527 860 2.9 16.0 1843
37 457 kb 32.9 2.5 0.5 2.5 b20 263 0.80 b3 0.2 222 128 14 7900 b1 b1 1.0 40 2139 0.9 9.9 2015
38 50042 kb 14.5 3.9 0.2 0.8 149 182 2.51 b3 0.2 88 83 7 5900 1 11 2.0 52 1052 0.7 12.4 1864
39 50042GL+) kb 0.7 6.0 b0.1 b0.1 b9 2000 0.47 1 1.0 839 998 4 3400 b2 b1 0.2 3 165 b0.1 n.a. 153
40 229 kb 42.1 0.2 0.3 b0.1 36 933 1.69 b3 b0.1 55 15 13 b500 b1 b1 2.2 403 4322 0.4 22.0 1313
41 50032 kb 37.4 1.3 0.4 0.2 b2 1229 0.92 b3 0.2 76 21 5 b500 b1 b1 2.4 286 2922 0.4 14.2 1631
T.Seifert,
D.Sandmann/Ore
GeologyReview
s28(2006)1–31
14
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42 2461 kb b0.1 5.5 0.1 1.1 b21 229 2.66 b3 2.8 3070 1880 5 b400 8 b1 0.2 0.2 8 0.9 0.9 2996
43 51052 kb 32.4 2.4 0.3 b0.1 100 2172 0.67 23 b0.1 54 17 23 b300 b1 b1 0.8 724 3879 0.4 11.4 1992
44 50083 kb/eb 30.0 2.0 0.5 4.5 102 1028 0.40 b3 0.5 200 268 48 3000 b1 b1 b0.1 833 3854 1.6 7.6 2807
45 50094 kb 17.5 1.9 0.2 2.1 542 241 0.36 b3 0.1 48 210 45 b300 b1 b1 b0.1 329 2468 1.2 9.4 1053
46 P 1–4 SL+) kb 46.2 0.5 0.8 b0.1 734 b1000 0.30 9 0.2 386 24 b600 b2 5 b1 0.8 195 3459 b0.1 n.a. 8295
47 P 1–7 GL+) kb 1.1 6.0 b0.1 b0.1 b7 b1000 3.73 1 1.2 1000 1040 14 b300 b2 b1 0.2 b0.2 106 b0.1 n.a. 176
48 P 1–10+) kb 3.9 3.0 0.2 b0.1 b2 b1000 0.30 1 0.1 95 51 0.5 b100 b2 b1 0.2 6 337 0.4 n.a. 2739
49 P 3–4 GL+) kb 0.4 5.8 b0.1 1.8 b23 b1000 4.44 1 1.0 2590 2530 17 b1200 b2 b1 b0.1 0.2 57 b0.1 n.a. 560
50 50160 eb/kb 8.6 0.4 0.2 2.5 88 645 1.33 b3 0.1 b5 121 b2 b200 b1 b1 1.7 40 792 1.6 5.0 9447
51 50192 kb 3.5 4.6 0.1 10.9 b21 166 1.53 b3 b0.1 319 713 b2 b300 b1 b1 1.9 2 297 7.1 5.7 1599
52 50137+) kb 14.3 3.7 0.1 2.2 90 b1000 0.50 4 1.0 187 173 53 181 b1 b1 1.6 654 1413 0.3 n.a. 3210
53 50330 kb 4.1 0.3 0.3 7.2 1930 672 0.31 b3 0.3 43 273 26 b300 b1 b1 0.4 117 451 3.6 1.7 877
54 50378 kb/eb 5.8 0.7 2.1 10.0 1700 531 1.22 9 0.2 118 222 105 b300 b1 b1 2.5 236 861 4.8 7.1 1166
55 50397 kb 20.3 2.1 7.1 0.1 b2 864 1.94 23 0.4 601 38 506 b200 b1 288 0.6 785 2915 0.5 4.0 1915
56 50394 kb 9.7 4.9 1.7 4.7 669 280 4.12 43 2.9 886 485 657 b300 20 b1 0.7 77 950 3.3 4.7 580
57 50423 kb 5.2 3.2 6.0 10.4 1770 512 4.75 80 0.7 2440 360 3073 b400 3 b1 2.2 482 890 5.6 4.1 2232
58 50451 kb 10.9 4.4 3.5 0.4 84 1619 0.29 5 0.2 424 100 14 b200 b1 b1 0.2 3 862 0.3 3.5 773
59 50473 kb 26.2 4.1 5.9 0.3 190 1223 2.34 41 3.1 1145 27 1919 6200 4 672 0.4 667 4004 0.5 5.1 809
60 50441 kb 13.6 4.6 0.9 4.3 2370 587 4.31 153 36.5 4670 126 8201 2000 b1 b1 2.0 272 1826 3.8 6.3 1461
61 50450 kb 0.3 5.7 0.3 0.6 94 679 0.23 b3 b0.1 671 750 b2 b200 1 b1 0.5 0.5 110 0.5 0.5 216
62 50437+) kb 5.4 4.4 6.6 0.2 1340 2000 2.70 62 33.3 2850 101 5530 1500 113 5210 1.8 197 484 0.3 n.a. 965
63 52289 kb/eb 18.1 4.0 0.2 1.1 b22 376 2.01 b3 0.2 1000 1140 8 b300 b1 b1 0.7 95 1662 0.8 8.1 989
64 50121 eb 1.8 3.2 0.7 0.4 b121 293 1.75 34 b0.1 16900 1300 5 b1800 b1 b4 1.5 0.4 120 0.8 4.3 29630
65 6001 eb 1.8 4.4 0.2 1.2 253 39 3.09 b4 b0.1 9300 3930 b2 b800 b1 b1 3.6 b0.1 101 0.8 6.4 53180
66 52262 kb 15.2 3.7 0.7 b0.1 b18 113 0.96 b3 b0.1 874 717 13 5900 b1 b1 0.2 167 1495 0.3 10.7 2555
67 52215 kb 20.5 4.9 0.9 0.3 b5 288 1.04 15 0.1 909 720 194 b300 b1 b1 0.6 303 2227 0.5 7.1 1304
68 1499 kb 11.1 0.9 0.1 3.3 767 152 0.66 b3 0.1 185 358 b2 b300 b1 b1 1.3 101 1024 1.4 25.5 2063
69 6004 eb/kb 6.0 0.3 0.1 4.9 1700 547 0.51 b3 b0.1 5700 1460 b2 b400 b1 b1 0.6 0.9 254 0.8 3.0 26592
70 1530 kb 18.0 0.7 0.1 5.4 b20 164 3.57 b3 0.3 63 125 8 b300 122 b5 1.0 54 1259 2.2 9.0 1346
71 51540 kb 7.3 4.4 0.2 0.1 893 543 2.21 b3 b0.1 3060 1350 b2 b300 b1 b1 0.8 15 673 0.3 4.6 1240
72 1669 kb 30.1 4.3 0.8 0.6 87 107 0.64 b3 0.4 408 36 315 b500 b1 b1 b0.1 277 3682 0.5 5.0 1246
73 1675+) eb 6.3 3.5 b0.1 0.1 b2 b1000 1.40 2 0.4 1550 1510 3 1200 b1 b1 0.5 8 633 0.2 n.a. 5631
74 1715 kb 8.3 3.9 6.1 0.1 b5 69 1.21 b3 b0.1 1350 1060 11 2600 b1 b1 b0.1 443 1459 0.7 5.4 2823
75 1730 kb 2.0 5.9 0.1 0.2 b5 51 2.27 b3 b0.1 1710 1590 223 b300 b1 b1 b0.1 16 256 0.4 3.2 1647
76 51568 kb with younger debTcarbonate veinlet
25.9 4.4 0.5 0.8 863 166 2.11 b3 b0.1 1560 1190 8 5200 b1 b1 0.6 b0.1 1541 0.6 9.0 2994
77 54256 eb/kb 1.4 4.3 b0.1 2.1 b24 99 2.80 b3 0.6 2230 2520 9 b400 b1 b1 0.3 4 119 0.7 1.5 670
78 3886 kb with younger
debT carbonate veinlet
36.6 0.4 0.3 b0.1 b30 225 0.52 b3 0.1 64 b0.8 18 2300 b1 5 0.2 638 3384 0.4 6.0 3613
79 51763 kb 21.5 2.3 0.3 6.3 b28 408 1.09 b3 b0.1 2410 1040 11 2700 b1 b5 0.3 1 971 4.3 8.0 4625
80 4384 kb 28.6 4.1 0.2 0.1 b5 188 1.27 b3 0.1 221 99 31 b300 b1 b1 b0.1 161 2282 0.3 5.6 1463
81 4428 kb 6.9 4.1 1.1 0.2 b17 207 4.30 b3 0.3 1110 948 345 3800 b1 b1 b0.1 66 1180 0.7 3.3 1600
82 4428 GL+) kb 0.6 5.9 0.1 b0.1 b10 b1000 5.89 1 1.2 1880 2060 699 2200 b2 b2 b0.1 6 186 0.1 n.a. 523
Methods: Zn, As, Au, Se, Ag, Sb, Sn, W, Sc by INAA; Pb, Cu, Bi, Mo, Cd, Mn by ICP-OES; Tl, Te, In, Ge, Ga by ICP-MS; Hg by cold vapor FIMS.+) Deviation: Hg by INAA; Se and Bi by ICP-MS.
n.a. — not analyzed.
T.Seifert,
D.Sandmann/Ore
GeologyReview
s28(2006)1–31
15
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T. Seifert, D. Sandmann / Ore Geology Reviews 28 (2006) 1–3116
part of the Freiberg district are often associated
with matildite-(AgBiS2) inclusions in galena (Fig.
4G). The transitional ore-type between dkbT anddebT ore-type characteristics (Fig. 4H) shows mi-
croscopic inclusions of miargyrite (AgSbS2) and
argentite (Ag2S) in sphalerite.
(B) Carbonate- and quartz-bearing Ag–Sb polymetal-
lic sulphide vein-type mineralization [according to
Muller (1850, 1901): dedle Braunspatforma-
tionT=noble carbonate formation (debT ore-type),and dedle QuarzformationT=noble quartz forma-
tion (deqT ore-type)] with arsenopyrite, pyrite/mar-
casite, low- and high-Fe sphalerite, chalcopyrite,
galena, freibergite, jamesonite, boulangerite, stib-
nite, freieslebenite, miargyrite, pyrargyrite, ste-
phanite, polybasite, argentite, and native silver
(Fig. 4I). Silver-rich carbonate- and quartz-bearing
polymetallic veins occur in the South and North
sub-district (Fig. 3). The base metal sulphides and
Ag-minerals of the deqT ore-type (North district)
show a dense to fine-grained intergrowth with
milky quartz. The South sub-district is typical for
carbonate-bearing Ag-rich polymetallic sulphide
veins of the debT ore-type. These ores are charac-terized by a frequent occurrence of Ag-minerals,
and Ag-rich sphalerite (Muller, 1901) which is
cemented by rhodochrosite and calcite (Fig. 4K,
L). The high Ag contents within sphalerite ores are
related to argentite- andmiargyrite-inclusions. The
dkbT ore-type veins are crosscut by debT ore-typemineralization (Fig. 4M).
In the Freiberg district, gneisses, mica-schists, and
amphibolites are rarely significant altered in a distance
of more as 2 m from the ore veins. The wall rock
alteration zone of the dkbT veins is characterized by
silification, sericitization, and more or less occurrence
of disseminated sulphides (mostly pyrite and arsenopy-
rite; Rosler and Kuhne, 1970). The zone of propylitic
alteration appears at a greater distance from the veins.
The alteration zones of the debT veins typically show
muscovitization and carbonatization (Rosler and
Kuhne, 1970).
4. Sampling and analyses
4.1. Sample site and data sets
Mineralogical description of 82 representative vein-
type samples (dkbT, deqT, and debT ore-type) from the
Freiberg district is included in Table 3. The samples
were taken in the last two mining periods at the end of
the 19th, and the middle of the 20th Century by mine
geologists; localities of all samples are unambiguous.
Excluding the samples from the dWilhelm veinT (Table3) which were collected during mapping by the
authors, the samples are from the ore deposit collection
of the TU Bergakademie Freiberg and the ore vein
collection of the VEB Bergbau-und Huttenkombinat
dAlbert FunkT Freiberg. Typical base metal veins
were analyzed from the North (Obergruna, Kleinvoigts-
berg, Mohorn), Central (Halsbrucke, Freiberg, Mulden-
hutten), and South sub-districts (Zug, Brand; Fig. 3).
The samples BED 1-4 (debT ore-type with Fe-rich
sphalerite) from the dHimmelsfurstT mine in the
Brand ore field, Zinnw 1-5 (cassiterite–sulphide ore)
from the Sn–Li deposit Zinnwald/Cınovec in the east-
ern Erzgebirge, and Pecht 2-1 (wolframite–sulphide
ore) from the W vein-type deposit Pechtelsgrun in the
western Erzgebirge are included for purposes of com-
parison (Fig. 2). Published and unpublished data from
the Freiberg district, and from Sn-polymetallic vein-
and greisen-type ores from the Marienberg–Wolken-
stein, Annaberg, Ehrenfriedersdorf–Geyer, and Muhl-
leithen districts, and Sn deposits in the southern part of
the eastern Erzgebirge (e.g., Altenberg, Zinnwald) are
also included to cover deposits from the Erzgebirge
metallogenetic province.
4.2. Geochemical bulk analyses
Representative slabs of bulk ore samples from typ-
ical Ag-base metal veins of the study area (Table 3;
Fig. 3) were carried out commercially, at Actlabs Ltd.
(Ontario, Canada) by instrumental neutron activation
analyses (INAA), inductively coupled plasma-optical
emission spectroscopy (ICP-OES), inductively coupled
plasma-mass spectrometry (ICP-MS), and cold vapor
flow-injection mercury system (FIMS). The major
(Zn, Pb, Cu, As), and trace element contents (Au,
Hg, Tl, Se, Te, Ag, Sb, Bi, Sn, Sc, In, Cd, Ge, Ga)
are listed in Table 4. The bulk In contents were
measured by the ICP-MS method. This method greatly
improved the accuracy of In determinations including
low detection limits (V50 ppb) and good precisions
(e.g., Hannington et al., 1999a; Schwarz-Schampera
and Herzig, 2002). The used standards, measurement
conditions, and detection limits are described in the
certificated analytical reports 17843 and 20668 pro-
duced by Actlabs Ltd.
The studied samples are typically ores from dkbT,debT, and deqT veins (Table 3). The weight of the sam-
ples ranges between about 0.2 and 2 kg. From each ore
sample two representative slabs were cut by a saw to
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T. Seifert, D. Sandmann / Ore Geology Reviews 28 (2006) 1–31 17
prepare polished sections and bulk ore sub-samples.
The slabs for the geochemical analyses (10 to 40 g in
weight) were crushed and milled at Actlabs Ltd.
4.3. Electron probe microanalyses
Mineral identification and relative age relationships
were obtained from the examination of polished thick
and thin sections in reflected and/or transmitted light.
Based on bulk geochemistry, In-rich samples were
selected for detailed mineralogical and electron-micro-
probe analyses. Electron-microprobe analyses were
carried out on a JEOL JXA 8900 electron microprobe
at the TU Bergakademie Freiberg under conditions of
20 kV and 25 nA, and a beam diameter of 2 to 4 Am.
Reproducibility of the results is better than 2%. Nat-
ural minerals, and synthetic mineral equivalents were
used as standards (e.g., the dIn2Se3_CanMetT standardfor In, and the dCdS_MACT standard for Cd). The
detection limit of the electron-microprobe was about
0.07 wt.% In.
5. Bulk ore geochemistry
The first modern geochemical bulk ore analyses of
the Freiberg district are presented in this paper (Table
4). Average base metal concentrations of the polyme-
tallic sulphide samples (n =82) are 13.2 wt.% Zn, 7.2
wt.% Pb, 0.8 wt.% Cu, and 3.4 wt.% As, with maxi-
mum values reaching 46.2 wt.% Zn, 7.2 wt.% Pb, 7.1
wt.% Cu, and 34.1 wt.% As (Table 5). The highest
concentration of silver occurs in the deqT (mean 3880
ppm Ag, n =14), and debT ore-type samples (mean 5634
ppm, n =7). The dkbT ore-type suite shows moderate Ag
contents (mean 768 ppm Ag, n =61) and a significant
correlation of Pb–Ag ratios (r =0.51; Fig. 6A). In the
deqT and debT veins, Ag concentrations correlate strong-
ly with Sb (r =0.69; Fig. 6B). Silver occurs mainly in
galena, which contains microscopic inclusions of miar-
gyrite and pyrargyrite (Ag3SbS3), and in sphalerite with
inclusions of argentite. Silver concentration is also
associated with stephanite, polybasite, freibergite, and
native silver (Fig. 4I, K). The highest Bi contents (up to
8200 ppm Bi) are typically associated with high Ag-
concentrations in dkbT veins of the Muldenhutten ore
field (r =0.98, n =10), and partly of the Freiberg ore
field (Table 5; Fig. 6C). The strong positive correlation
of Ag–Bi values is related to matildite/schapbachite-
inclusions (AgBiS2) in galena of the dkbT ore-type
samples (Fig. 4G). Additionally this correlation is
almost certainly due to partial solid solution between
PbS and AgBiS2 with a coupled substitution Ag++
Bi3+f2Pb2+ (cf. Boyle, 1968). Bismuth occurs also
in microscopic grains of aikinite (CuPbBiS3) (Fig. 7)
which can indicate high-temperature conditions (see
Section 7). For comparison, aikinite was also detected
by microprobe-analyses in a cassiterite-sulphide sample
of the Sn–Li deposit Zinnwald/Cınovec (sample Zinnw
1-5). Low Bi concentrations are typical for the low-In
deqT and debT veins (range from 2 to 41 ppm Bi, n =21;
Table 5). The Cu-rich dkbT ore-type veins of the Mul-
denhutten ore field show a strong positive Ag–Se
(r =0.96) and Ag–Te (r =0.87) correlation. The dkbTores are also characterized by a significant positive
correlation of Bi–Se (r =0.87), Bi–Te (r=0.91), and
Se–Te (r =0.72).
The highest In concentration occurs in the dkbT ore-type veins of the Freiberg (up to 1560 ppm In, mean
253 ppm; n=36), Muldenhutten (up to 785 ppm In,
mean 284 ppm; n =10), and Brand ore fields (up to 638
ppm In, mean 156 ppm; n =15). The In concentrations
of the dkbT ore-type samples (n =61) correlate strongly
positively with Zn (r =0.58) and Cd (r =0.69), and only
moderately with Cu (r =0.26) (Fig. 6F–H). This is in
agreement with the microprobe analyses of sphalerites
(Table 6). Low In contents were measured from deqT(up to 30 ppm In, mean 5 ppm; n =14), and debT ore-type samples (up to 40 ppm In, mean 9 ppm; n =7).
These samples (n =21) show no correlation of In con-
tents with Zn (r =0.06), Cd (r =0.11), and Cu
(r =�0.17).
On average, sphalerite-bearing polymetallic ores
from the Freiberg district are enriched in Cd (Fig.
6D). High Cd concentrations are associated with Fe-
rich (11 to 13 wt.% Fe) sphalerite of the deqT (up to
1492 ppm Cd, mean 648 ppm; n =14) and dkbT veins(up to 4919 ppm Cd, mean 1542 ppm; n =61). Con-
centrations of Ga (up to 25.5 ppm Ga, mean 6.8 ppm;
n =82) correlate positive with Zn-values (Fig. 6E). In
contrast, Ge values show no distinct geochemical
affiliation to Zn ores (r =�0.24, n =82) or sphalerite
(e.g., debT sample 50105 with 44.9 ppm Ge; Table 4).
The high Sn concentration of dkbT veins in the Frei-
berg (up to 1.3 wt.% Sn, mean 0.15 wt.%; n =36),
Muldenhutten (up to 0.62 wt.% Sn, mean 0.12 wt.%;
n =10), and Brand ore fields (up to 0.59 wt.% Sn,
mean 0.18 wt.%; n =15) is related to hydrothermal
cassiterite and stannite. Moderate Sn contents (up to
0.18 wt.% Sn) were determined from debT ore-type
samples (Table 5). The dkbT veins, especially samples
from the Muldenhutten ore field, show slight enrich-
ments in Mo (up to 113 ppm) and W (up to 5210
ppm) which indicate molybdenite and wolframite
mineralization.
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Table 5
Summary of bulk geochemistry analyses of polymetallic sulfide vein-type ores from the Freiberg district
Locality (ore-type) Sample no. Zn Pb Cu As Au* Hg Tl Se* Te* Ag Sb Bi Sn* Mo* W* Sc In Cd Ge Ga Mn
wt.% wt.% wt.% wt.% ppb ppb ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm
North subdistrict Average 9.7 2.5 0.2 2.6 1882 2144 1.30 13 0.2 3880 2903 5 779 1 11 1.8 5 648 2.0 6.1 2498
(deqT) Minimum 1.9 0.1 0.1 0.1 15 46 0.25 3 0.1 218 145 2 100 1 1 0.4 0.1 155 0.6 0.7 117
n =14 Maximum 21.6 5.3 1.4 11.7 9040 16436 5.21 115 0.4 19000 21400 12 3400 7 128 4.0 30 1492 7.2 11.5 14920
Freiberg ore field Average 15.7 3.0 0.3 4.8 168 611 1.57 13 0.7 449 380 213 1519 4 4 1.0 253 1595 2.1 8.1 2497
(dkbT) Minimum 0.1 0.1 0.1 0.1 2 24 0.12 1 0.1 5 6 1 41 1 1 0.1 0.2 5 0.1 0.9 60
n =36 Maximum 46.2 7.2 1.7 34.1 2300 3000 7.78 58 6.8 3070 2530 3310 13000 56 40 5.6 1560 4919 12.4 22.0 20175
Muldenhutten Average 10.1 3.5 3.4 3.8 1015 897 2.22 42 7.8 1385 248 2003 1160 15 618 1.1 284 1335 2.3 4.1 1099
Ore field Minimum 0.3 0.3 0.3 0.1 2 280 0.23 3 0.1 43 27 2 200 1 1 0.2 0.5 110 0.3 0.5 216
n =10 Maximum 26.2 5.7 7.1 10.4 2370 2000 4.75 153 36.5 4670 750 8201 6200 113 5210 2.5 785 4004 5.6 7.1 2232
Brand ore field Average 16.7 3.6 0.8 1.3 185 270 1.98 4 0.2 1120 829 126 1763 9 2 0.4 156 1552 0.9 7.9 2002
(dkbT) Minimum 0.6 0.4 0.1 0.1 5 51 0.52 1 0.1 63 1 2 300 1 1 0.1 0.1 186 0.1 3.2 523
n =15 Maximum 36.6 5.9 6.1 6.3 893 1000 5.89 15 1.2 3060 2060 699 5900 122 5 1.3 638 3682 4.3 25.5 4625
Freiberg ore field Minimum 0.1 0.4 0.1 0.1 88 645 0.19 3 0.1 5 9 2 200 1 1 0.1 8.3 10 1.6 0.1 8505
(debT) n =2 Maximum 8.6 2.2 0.2 2.5 258 1139 1.33 9960 0.1 3750 121 41 200 9 1 1.7 40 792 44.9 5.0 9447
Brand ore field Average 3.5 3.2 0.2 1.7 420 396 1.91 9 0.3 7136 2144 4 920 1 2 1.3 3 246 0.7 3.8 23141
(debT) Minimum 1.4 0.3 0.1 0.1 2 39 0.51 2 0.1 1550 1300 2 400 1 1 0.3 0.1 101 0.2 1.5 670
n =5 Maximum 6.3 4.4 0.7 4.9 1700 1000 3.09 34 0.6 16900 3930 9 1800 1 4 3.6 8 633 0.8 6.4 53180
Average 13.2 3.1 0.8 3.4 582 839 1.68 136 1.3 1714 977 363 1325 5 79 1.1 176 1282 2.3 6.8 3653
Total Minimum 0.1 0.1 0.1 0.1 2 24 0.12 1 0.1 5 1 1 41 1 1 0.1 0.1 5 0.1 0.1 60
n =82 Maximum 46.2 7.2 7.1 34.1 9040 16436 7.78 9960 36.5 19000 21400 8201 13000 122 5210 5.6 1560 4919 44.9 25.5 53180
Note: * Detection limit is used as minimum value.
n =number of analyses.
T.Seifert,
D.Sandmann/Ore
GeologyReview
s28(2006)1–31
18
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Fig. 6. (A–H) Selected binary variation bulk geochemistry diagrams for polymetallic sulphide ores (n =82) of the Freiberg district. Sample
descriptions and locations see Table 3.
T. Seifert, D. Sandmann / Ore Geology Reviews 28 (2006) 1–31 19
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Fig. 7. Aikinite-(CuPbBiS3) inclusion (aik) in galena (gn) revealed by BSE imaging. Galena intergrowth with chalcopyrite (cp); py = pyrite. Sample
50473 (see Fig. 4G).
T. Seifert, D. Sandmann / Ore Geology Reviews 28 (2006) 1–3120
The highest average Au contents were analyzed
from samples of the deqT ore-type (up to 9 ppm Au,
mean 1.9 ppm; n =14). The dkbT ore-type veins show
also significant Au concentrations (up to 2.37 ppm Au,
mean 0.31 ppm; n =61). The highest average Au values
of the dkbT ore-type samples (1 ppm Au, n =10) are
Table 6
Electron microprobe analyses of sphalerites from the Freiberg district
Sample 222 50437-1
Sphalerite type High-Fe Low-Fe High-Fe
n= 202 5 25
wt.%
Zn 51.14 62.55 53.92
Fe 12.89 1.59 11.34
Cu 0.19 0.42 0.17
In 0.16 n.d. 0.09
Cd 0.50 1.03 0.38
Ga 0.07 0.09 0.10*
Mn 0.20 0.06 0.17
S 33.03 33.07 34.19
Total 98.26 99.46 100.41
For comparison samples from the Sn–Li-deposit Zinnwald, eastern Erzgeb
analyzed.
Notes: * n =16.
n.a. — not analyzed, n.d. — not detected.
n =number of analyses.
dkbT ore-type samples 222 and 50437-1 from the Freiberg district, see Tabl
Sample BED 1-4 from dHimmelsfurstT mine, Brand–Erbisdorf.
Sample Zinnw 1-5 (cassiterite–sulphide ore from the Sn–Li-deposit Zinnwa
Sample Pecht 2-1 (wolframite–sulphide ore from the W-deposit Pechtelsgru
For locations see Figs. 2 and 3.
related to the Cu-rich dkbT veins in the Muldenhutten
ore field (Table 5). Elevated Au concentrations were
also determined from the debT samples (up to 1.70 ppm,
mean 0.35 ppm; n =7). The deqT ores from the North
district are characterized by notable Hg (up to 16 ppm,
mean 2.1 ppm; n =14) and Sb concentration (up to 2.14
BED 1-4 Zinnw 1-5 Pecht 2-1
Low-Fe High-Fe Low-Fe High-Fe
1 27 19 4
62.18 52.03 61.51 50.34
2.27 12.32 3.29 11.20
0.62 0.32 0.22 0.37
n.d. 0.10 0.07 0.05
1.11 0.68 0.48 0.48
n.a. n.a. n.a. n.a.
n.d. 0.23 0.21 1.64
34.01 34.06 33.62 34.16
100.67 99.92 99.51 98.34
irge and from the W-deposit Pechtelsgrun, western Erzgebirge were
e 3.
ld, eastern Erzgebirge).
n, western Erzgebirge).
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Fig. 8. Frequency diagram of indium contents in Fe-rich sphalerite in sample 222 (see Fig. 4C). Electron microprobe measurements n =202 (see
Table 6).
T. Seifert, D. Sandmann / Ore Geology Reviews 28 (2006) 1–31 21
wt.%, mean 2900 ppm; n=14). Elevated Hg contents
are associated with the fahlore-bearing samples (52827
with 10.2 ppm Hg; 53089 with 16.4 ppm Hg). The
polymetallic veins in the Central and South sub-districts
show moderate to low Hg contents (dkbT ore-type: up to
3 ppm Hg, mean 0.6 ppm, n =61; debT ore-type: up to
1.1 ppm Hg, mean 0.5 ppm, n =7).
Fig. 9. Binary diagrams of Zn+Fe–Cd, Zn+Fe–In, Cu–In, and Cd–In com
measurements n =202 (see Table 6).
6. Electron microprobe analyses
Two types of In concentration can be distinguished,
based on microanalytical study. The first type is char-
acterized by microprobe analyses of representative
sphalerites (222, 50437-1) which show an In average
of 0.16 wt.% (Table 6). For comparison, sphalerites
positions of Fe-rich sphalerite in sample 222. Electron microprobe
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Fig. 10. A. Representative quartz(qtz)-bearing chalcopyrite(cp)–sphalerite(sl)–arsenopyrite(asp)–pyrite–stannite–galena(gn) sample (Cu-rich dkbTore-type). Sample 50437, bulk analyses show 197 ppm In. dSchieferleiteT mine, dWeisser LoweT vein, level 0, Muldenhutten ore field. B. Polished
section 50437-1 with pyrite (py), marcasite (mr), galena (gn), chalcopyrite (cp), and quartz relicts (qtz); scale bar=300 Am. Location of quantitative
electron microprobe study is highlighted. C. Quantitative electron microprobe images of microscopic Zn–Cu–Sn–In–S grains in pyrite surrounded
by a galena rim (see Fig. 10B) showing high levels of In (1.3 to 2.9 wt.%), Zn (5.6 to 52.8 wt.%), Cu (4.1 to 19.6 wt.%), Sn (0.3 to 17.2 wt.%), Pb
(up to 7.15 wt.%), and Fe (4.6 to 26.6 wt.%). Representative colour photographs of quantitative electron microprobe images showing zonal
enrichments of high In, Cu, Sn, Pb, and Zn levels (red and yellow colour) of grain #9 (see Table 7).
T. Seifert, D. Sandmann / Ore Geology Reviews 28 (2006) 1–3122
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Fig. 11. Ternary Cu+Ag–Sn+In–Zn+Fe plot of indium-rich grains
hosted by pyrite of sample 50437 (see Fig. 10 and Table 7), in
comparison with literature data compiled by Schwarz-Schampera
and Herzig (1999).
T. Seifert, D. Sandmann / Ore Geology Reviews 28 (2006) 1–31 23
from a cassiterite-sulphide greisen of the Sn–Li deposit
Zinnwald (mean 0.07 wt.% In, n =19), and a wolfram-
ite–sulphide ore from the W deposit Pechtelsgrun
(mean 0.05 wt.% In, n =4) were analyzed. The studied
sphalerites show Cd contents of up to 1.11 wt.%, and
significant Ga contents in the range between 0.03 and
0.17 wt.% (Table 6). Iron-rich sphalerites (mean 12.89
wt.% Fe, n =202) from a representative dkbT vein in the
Freiberg ore field (sample 222) are characterized by In
contents between 0.03 and 0.38 wt.% (mean 0.16 wt.%
In, n =202; Fig. 8). A negative correlation exists be-
tween Zn+Fe and Cd (r =�0.28), and Zn+Fe with In
(r =�0.49; Fig. 9A, B), reflecting the structural substi-
tution of Zn, In, and Cd in sphalerite. The In concen-
tration of sphalerite in sample 222 correlate positively
with Cu (r=0.36) and Cd (r=0.51) (Fig. 9C, D).
The second type of In concentration is related to
microscopic Zn–Cu–Sn–In–S grains in pyrite of a dkbTore-type sample (Fig. 10A) from a Cu- and Sn-rich base
metal vein in the Muldenhutten ore field. Quantitative
electron microprobe image of twenty Zn–Cu–Sn–In–S
grains (up to 6 Am) which are located in the highlighted
area of sample 50437 (Fig. 10B) show high levels of In
(1.3 to 2.8 wt.%), Cu (4.1 to 19.6 wt.%), Sn (0.3 to 17.2
wt.%), and Zn (5.6 to 52.8 wt.%) (Table 7). The highest
In content correlates with the highest Sn content. Rep-
resentative colour photographs of electron microprobe
images indicate the spatial distribution of elevated In,
Cu, Sn, and Zn concentrations of grain #9 (Fig. 10C).
The geochemical composition of these grains (Table 7)
suggests a complex solid solution in the system sphal-
Table 7
Selected data of quantitative electron microprobe images of submi-
croscopic Zn–Cu–Sn–In–S grains. Polished section 50437-1 from Cu-
rich dkbT ore-type sample 50437
Grain #8 #9 #12 #14 #15 #16 #17 #18
wt.%
Zn 39.29 37.85 52.84 5.62 25.87 46.31 12.46 24.25
Fe 4.63 5.39 6.42 19.19 16.80 9.20 26.64 17.85
Cu 14.35 14.18 4.08 19.61 10.47 6.10 9.63 11.16
Sn 2.54 5.80 0.30 17.21 6.59 2.08 7.12 6.83
Pb 7.15 2.33 0.29 n.d. 0.80 0.23 n.d. n.d.
Ag 0.46 0.28 n.d. 0.21 n.d. n.d. n.d. n.d.
In 1.27 1.72 1.29 2.85 1.51 1.44 1.75 1.58
Cd 0.28 0.24 0.37 0.07 0.17 0.27 0.05 0.11
Ga 0.06 0.08 0.09 n.d. 0.08 0.12 n.d. 0.04
Mn 0.02 n.d. n.d. n.d. n.d. n.d. n.d. 0.01
S 31.17 30.28 34.31 34.48 37.97 35.08 41.74 37.37
Total 101.44 98.33 100.13 99.35 100.41 101.00 99.54 99.26
Grain # = analysis point.
n.d. — not detected.
For the location of quantitative electron microprobe analyses see
Fig. 10.
erite–petrukite/sakuraiite (Fig. 11). No microscopic in-
tergrowth of sphalerite, chalcopyrite, and cassiterite
was found around the spot analyses. We cannot exclude
that Zn–Cu–Sn–In–S grains occur in ore minerals of the
Zn–Sn–Cu sequence (e.g., sphalerite, chalcopyrite).
However, pyrite and arsenopyrite represent the early
mineralization stage of the dkbT ore-type, which is over-
printed by the In-bearing Zn–Sn–Cu sequence (Fig. 5).
7. Discussion
Indium concentrations in the polymetallic veins in
the Freiberg district show a wide range (0.1 to 1560
ppm In, mean 176 ppm, n=82; Table 4). Based on
correlation coefficients of bulk ore geochemistry, sig-
nificant In (up to 1560 ppm) and Cd concentrations
(up to 4920 ppm) are associated with the Zn–Cu–Sn
mineralization sequence (dindium stageT; Fig. 5), repre-sented by the dkbT ore-type of the Freiberg, Mulden-
hutten, and Brand ore fields (Fig. 6G). This is in
accordance with literature data (Table 1), which show
an average of about 0.1 wt.% In. The highest average In
values occur in samples from the Cu-rich dkbT ore-typein the former Sn ore field Muldenhutten, which show
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T. Seifert, D. Sandmann / Ore Geology Reviews 28 (2006) 1–3124
close similarities with samples from the Freiberg ore
field (Table 5). Samples of the dkbT ore-type from the
Brand ore field show a slightly lower enrichment of In
concentration. Much lower In contents are reported
from the deqT, debT, and barite–fluorite–sulphide
(dfbaT) ore-types (Tables 1, 4, 5). Significant Cd con-
centrations are closely associated with Fe-rich sphaler-
ite (Fig. 6D) which confirmed literature data of
sphalerites from different late-Variscan ore-types of
the Erzgebirge (cf. Jung and Seifert, 1996).
Statistical evaluations of In concentrations in poly-
metallic Sn-base metal deposits have shown that chal-
copyrite-rich sphalerite ores generally contain the
highest In concentrations (cf. Schwarz-Schampera and
Herzig, 2002). This can be explained by solid solution of
CuInS2 in ZnS which is forming Zn2�2xCuxInxS2, sim-
ilar to that of Cu2FeSnS4 (stannite) in ZnS (cf. Schwarz-
Schampera and Herzig, 2002). There is evidence that
secondary replacement processes, such as those associ-
ated with the formation of dchalcopyrite diseaseT (Bartonand Bethke, 1987; Eldridge et al., 1988), are responsible
for the formation of roquesite (CuInS2) in solid solution.
The In concentrations of the dkbT ore-type samples
correlate moderately with Cu (Figs. 6H and 9C). Re-
placement processes like dchalcopyrite diseaseT are typ-ical for Fe-rich sphalerites of the dkbT ore-type (Fig. 4D).In contrast, the deqT and debT veins with relatively high
chalcopyrite contents show no correlation of In contents
with Cu (Fig. 6H). In this context it is important to note
that the In-rich dkbT veins in the Freiberg, Muldenhutten,
and Brand ore fields show significant high Sn concen-
trations (Table 5) which indicate a genetic link between
Sn- and In-bearing fluids. This is supported by notable
Mo and W contents in dkbT ore-type samples. In sum-
mary, the geochemical and mineralogical signature of
the dkbT veins show similarities to the Sn–W-base metal
mineralization stage.
Indium concentrations are also related to microscop-
ic Zn–Cu–Sn–In–S grains in sulphides (e.g., pyrite; Fig.
10). In the ternary (Cu+Ag)–(Sn+In)–(Zn+Fe) dia-
gram (Fig. 11), the compositions of the Zn–Cu–Sn–
In–S grains of sample 50437 fall along a linear com-
positional trend between a Fe–Cu–In-rich sphalerite
(analysis #12, Zn0.76Fe0.11Cu0.06In0.01S) and the ideal
fields of petrukite and sakuraiite (analysis #14,
Cu0.29Zn0.08Fe0.32In0.02Sn0.13S; see Table 7). The min-
eral sakuraiite was originally described by Kato (1965)
from one of the polymetallic Cu–Zn–Pb–Sn–W(–Au–
Ag) veins of the Ikuno mine, central Japan. The sakur-
aiite formula (Cu, Zn, Fe, In, Sn)S is approved by the
International Mineralogical Association (IMA). Petru-
kite was found in tin-polymetallic vein deposits which
are associated with granitic intrusions (e.g., Mount
Pleasant mine, New Brunswick; Petruk, 1973). The
general formula is (Cu, Fe, Zn)3(Sn, In)S4, where
CuNFeNZnNAg and SnN In. This composition is
somewhat variable and can be related to a coupled
substitution Cu+Sn =In+Zn (cf. Schwarz-Schampera
and Herzig, 2002). The complex mineralogical siting
of In attests to the In mineralogy of the Erzgebirge
metallogenetic province is dominated by variable re-
placement processes and/or solid solution in the system
sphalerite–chalcopyrite–stannite. In summary, both
types of In concentration support that the In minerali-
zation is associated with the Zn–Sn–Cu sequence
(dindium stageT) of the dkbT ore-type (Fig. 5).
Hydrothermal Ag-rich Sn-bearing base metal veins
and vein-like metasomatites of other districts in the
Erzgebirge (Marienberg, Wolkenstein, Jachymov) and
the Moldanubian terrane (Kutna Hora, Havlıcklv Brod)
are comparable to the dkbT ore-type of the Freiberg
district (Seifert et al., 2001). Iron-rich sphalerites from
these veins show significant In concentrations of up to
0.2 wt.% (Table 1). High In concentrations of Sn-bear-
ing base metal veins are also reported from the Massif
Central, France, and base metal vein-type deposits in
Japan (Table 1). In contrast, sphalerites from Ag-rich
base metal veins of the Keno Hill deposit (Yukon
Territory), and the Coeur d’Alene district (Idaho)
have significantly lower In concentrations between
b0.001 and 0.04 wt.% (Fryklund and Flechtner, 1956;
Boyle, 1965; Leach et al., 1998; Table 1). In contrast to
the dkbT veins and similar base metal deposits, the
paragenesis of the Keno Hill and Coeur d’Alene veins
show absent to minor cassiterite and stannite mineral-
ization. This facts support the genetic link between Sn-
and In-rich fluids in Ag-base metal vein-type mineral-
ization with a notable In potential.
Significant In mineralization is reported from Sn-
polymetallic vein- and greisen-type deposits worldwide
(France, Japan, Bolivia, Russia, Canada; cf. Table 1).
The granite-related Mount Pleasant deposit contains
approximately 25% of the known world In reserves
(Kooiman and Ruitenberg, 1992; Sinclair et al., 2005—
this volume). It is important to note that this economic In
enrichment is related to Sn-polymetallic ores which
show similarities to Sn deposits in the Erzgebirge (cf.
Seifert et al., 1996b). High In concentrations are
reported from Sn-polymetallic greisen and vein-type
deposits in the Erzgebirge (Table 1; Fig. 2). Sphalerite
from the Sn-polymetallic vein-like metasomatites of the
dBriccius mineT in the Annaberg district shows In con-
centrations up to 1 wt.% (Seifert, 1994). A representa-
tive sphalerite–chalcopyrite–stannite–chlorite bulk ore
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T. Seifert, D. Sandmann / Ore Geology Reviews 28 (2006) 1–31 25
sample from the dBriccius mineT has an In content of 0.3wt.%. Significant In concentrations are also reported
from the dRohrenbohrerT exploration mine in the
Geyer Sn district (Jung, 1992). Iron-rich sphalerites of
cassiterite–sphalerite greisen samples show In concen-
trations of up to 1.2 wt.% (mean 0.4 wt.% In, n =19).
Sphalerites from Sn-polymetallic greisen ores of the
Cınovec/Zinnwald deposit are characterized by In con-
centrations of up to 2.5 wt.% (Novak et al., 1991).
Significant In contents are also reported from sphalerites
in Sn-polymetallic skarn ores of the Oelsnitz deposit
(0.4 to 1.0 wt.% In; Doering et al., 1994), and the Plavno
shaft located in the Jachymov district (0.2 to 0.3 wt.%
In; Hak et al., 1979). Cassiterites from greisen- and vein-
type deposits in the Geyer–Ehrenfriedersdorf, Marien-
berg–Pobershau, and Altenberg–Zinnwald/Cınovec dis-
tricts show In averages from 5 to 600 ppm (cf. Table 1).
Tin-greisen bulk ore samples from the Altenberg district
(Altenberg, Zeidelweide, Lowenhain deposits) have In
concentrations between 10 and 70 ppm (W. Schilka,
unpublished data, 1989). Significant In contents (up to
250 ppm) are also reported from cassiterites of the F-rich
rare metal granite-hosted Sn deposits in the French
Massif Central (e.g., Echassieres; Raimbault et al.,
1999).
High In contents were measured from sphalerites
(up to 4.7 wt.% In) of the volcanic-hosted epithermal
Au–Ag-base metal vein-type deposit Prasolov, Kuril
Island Arc, Russia (Kovalenker et al., 1993). Base
metal-rich ores from the Cu(–Mo) porphyry deposits
Bingham and Central district include sphalerites with
In contents of up to 0.12 wt.%, and chalcopyrite with
up to 0.1 wt.% In (Rose, 1967). High In concentra-
tions are reported from the Kidd Creek (Canada) and
Neves Corvo (Portugal) volcanic-hosted massive sul-
phide deposits (cf. Table 1). Indium contents of up to
3.0 wt.% in stannite and 0.3 wt.% in sphalerite from
the Neves Corvo Cu–Zn–Sn deposit, and sphalerites
with up to 0.2 wt.% In from the Kidd Creek Cu–Zn–
Pb–Ag–Sn deposit show the high In potential of these
VMS deposits (cf. Schwarz-Schampera and Herzig,
2002). The Kidd Creek ores are enriched in Sn, Sb,
As, Ag (lower temperature Zn–Pb ore) and Bi, Se, and
In (higher temperature Cu-rich ore; Hannington et al.,
1999a).
High-temperature (up to 940 8C) gases (e.g., HCl,
HF) of active magmatic systems (e.g., Kudryavyi and
Merapi volcanoes) are transporting In and elements
such as Zn, As, B, Tl, Pb, Sn, Mo, W, Cd, Cu, Ag,
Te, Au, As, and Se (Kovalenker et al., 1993; Kavalieris,
1994; Wahrenberger et al., 2002; see Table 1). For
volatile In transport in high temperature gases from
Kudryavyi volcano gaseous species such as InCl,
InCl3, and InBr are important phases (Wahrenberger
et al., 2002). Recent sphalerite mineralization of the
Kudryavyi volcano (Kuril Island Arc, Russia) show In
concentrations of up to 14.9 wt.% (Kovalenker et al.,
1993). Magmatic In degassing may be related to its
high volatility and incompatible geochemical behavior
(cf. Schwarz-Schampera and Herzig, 2002). This is
confirmed by the present-day Cu, Zn, Pb, Mo, Sn,
As, Sb, Ag, and Au fluxes of degassing volcanoes
that have been estimated from aerosol and fumarole
data (cf. Hedenquist, 1995).
Obvious correlations with magma-affiliated Sn-poly-
metallic, hydrothermal Ag-rich base metal, epithermal
Au–Ag-base metal, Cu(–Mo) porphyry and VMS depos-
its, and the occurrence in fumaroles in active volcanic
systems may suggest the magmatic origin of In in these
ore deposit types (Table 1). The magmatic influence is
also indicated by d34SCDT-values from In-rich minerals
of Sn-polymetallic and base metal deposits in the range
from - 3x to + 3x (e.g., Akenobe and Fukoku, Japan;
Erzgebirge, Germany; cf. Schwarz-Schampera and Her-
zig, 2002; Jung and Seifert, 1996; Seifert, 1999).
Magmatic volatiles may be responsible for unusual
trace element compositions of ore deposits containing
In, Sn, Se, and Bi, perhaps also because of high con-
centrations of potential metal ligands (i.e., fluorine,
chlorine). In hydrothermal solutions, In(III)chloride
complexes such as InCl4� and hydrolyzed species
such as InClOH+ will be important in the transport of
In (Seward et al., 2000). According to these authors
increasing temperature leads to an increase in the num-
ber of chloride ligands bound to the In3+ ions. The
highest InCl4� concentrations were detected in hydro-
thermal solutions with temperatures between 300 and
350 8C. In this context, it is important to note that
lamprophyric melts show elevated concentrations of
Cl as well as F, S, CO2, H2O+, P, and extreme LILE
and HFSE enrichment which may indicate the metallo-
genetic potential of this magmatism (cf. Rock, 1991;
Seifert, 1999, 2004, in press). Strongly mineralized
central shear fault zones up to 15 km in length are a
prominent feature in polymetallic districts of the Erz-
gebirge. These mineralized central shear fault zones
largely control the polymetallic vein-type deposits,
and show a strong spatial and probably temporal affin-
ity to lamprophyres and F-rich post-collisional (anoro-
genic) rhyolitic/granitic magmatites (Seifert and
Baumann, 1994; Seifert, 2004, in press). Based on the
above data, the high In concentrations of base metal
veins in the Erzgebirge (e.g., Freiberg, Marienberg)
may indicate an influence of fluids expelled from mag-
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T. Seifert, D. Sandmann / Ore Geology Reviews 28 (2006) 1–3126
mas during the emplacement of post-collisional lam-
prophyric and rhyolitic dikes.
The following mineralogical, geochemical, isotopic,
fluid inclusion, age relationship, and structural features
indicate a genetic link to a magmatic-(mantle-) related
source of late-Variscan Ag-base metal mineralization
stages:
(a) Typically for dkbT ore-type veins are quartzes
with low-salinity (up to 9 wt.% NaCl equivalent)
primary fluid inclusions which show homogeni-
zation temperatures between 250 and 410 8C into
liquid and minor into vapor state (Thomas, 1979;
Seifert et al., 1992; Seifert, 1994; Drechsel et al.,
2003). Quartzes from debT ore-type veins have
lower homogenization temperatures between
120 and 300 8C into liquid state (M. Drechsel
and Th. Seifert, unpublished data, 2002). The
fluid inclusions in dkbT ore-type vein quartz can
be grouped into two types on the basis of their
phase relationships at room temperature (Drech-
sel et al., 2003). Type 1 inclusions contain an
aqueous phase of low salinity (up to 8.6 wt.%
NaCl equivalent) and vapor phase. In a few cases
in type 1 inclusions low concentrations of CO2
were detected by melting of clathrates between
+1 and +5 8C. Type 2 inclusions contain at room
temperature one gaseous phase of pure CO2
detected by the melting point at �56.6 8C.Above this temperature the solid CO2 changed
into the gaseous phase by sublimation. In sum-
mary, the high temperatures of ore-forming pro-
cesses and CO2-bearing fluids indicate a
magmatic source for the Ag-base metal hydro-
thermal systems. In confirmation to the d13C
values of debT ore-type carbonates, which indicate
a mantle source for carbon (see below), the CO2-
bearing fluid inclusions in quartzes of the dkbTore-type suggest a genetic link to CO2-rich lam-
prophyric magmas (Seifert, in press).
(b) High-temperature hydrothermal systems are also
indicated by the occurrence of dchalcopyrite dis-
easesT in Fe-rich sphalerites with significant In
concentrations (Bortnikov et al., 1991; Schwarz-
Schampera and Herzig, 1997, 2002), similar to
the In-rich sphalerites of the dkbT ore-type.(c) Another possible indication for high-temperature
fluids is the occurrence of Bi-minerals (e.g., aiki-
nite; see Fig. 7). Aikinite was proven in high-
temperature Sn–Li greisen-type (e.g., Zinnwald,
Fig. 2) and gold–quartz vein-type mineralization
(e.g., Ural Mts., Russia; Ramdohr, 1975).
(d) Using a temperature of 370 8C for dkbT ore-typequartzes, and 250 8C for debT ore-type carbo-
nates, the means of calculated d18O fluid com-
position are +4.6x and +9.5x, respectively
(Seifert, in press). These data indicate a magmat-
ic source for the hydrothermal fluids. The mag-
matic origin of Ag-base metal hydrothermal
fluids is also apparent from carbonates of the
debT ore-type which show the following d13Cmeans and ranges (Harzer, 1970; Seifert, 1999):
rhodochrosite (�9.0x,�7.9x to�11.0x;n =9),
siderite (�6.8x,�3.0x to�10.7x; n=30), and
calcite (�6.9x, �1.6x to �10.1x; n =37).
These d13C values are similar to the carbon isotope
composition of primary carbonates in lampro-
phyres of the Erzgebirge (Seifert, in press). In
summary, the d13C values of carbonates in debTore-type veins and lamprophyres partly overlap
the carbon isotope compositions of magmatic car-
bon from the mantle (d13C=�3x to �7x;
Ohmoto and Rye, 1979). However, fluid-mixing
with meteoric water and wall rock leaching con-
tamination of the original magmatic fluids is indi-
cated by low salinities of primary fluid inclusions
(Thomas, 1979; Seifert, 1994; Drechsel et al.,
2003), and wide-ranging d18OSMOW values of car-
bonates (+9.6x to +25.2x) and quartzes (+6.1xto +15.6x) (Seifert, in press).
(e) At the Freiberg district all Ag-base metal sulphide
d34S values cluster at 0x, indicating a single
dominant, magmatic sulphur source for this
stage of hydrothermal activity. This signature is
similar to the S isotopic composition of high-
temperature sulphides of post-magmatic W and
Sn mineralization in the Erzgebirge (cf. Seifert,
1994; Jung and Seifert, 1996).
(f) The major group of Pb isotope ratios of galena-
bearing ores and galena-separates from Ag-base
metal and Sn–W–Mo–Bi–Cu–Li–F mineralization
stages in the Erzgebirge form a distinct cluster
(206Pb / 204Pb=17.890 to 18.586, n =112; 207Pb /204Pb=15.490 to 15.590, n =97; 208Pb / 204Pb=
37.890 to 38.750, n =114; Seifert, in press). This
Pb isotope composition is interpreted as the
dprimary Pb isotope signatureT of late-Variscan
Ag-base metal and Sn mineralization (Seifert et
al., 2001) which is overlapped by low-radiogenic,
primary Pb isotope ratios of lamprophyre dikes
(Seifert, in press). The close similarity in Pb iso-
tope compositions between lamprophyric rocks,
and galena-bearing Sn- and Ag-base metal ore-
types, especially from dkbT veins, implies a genetic
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T. Seifert, D. Sandmann / Ore Geology Reviews 28 (2006) 1–31 27
relationship between mineralized veins and the
intrusion of lamprophyric dikes.
(g) Relatively and absolutely age and spatial relation-
ships suggest a genetic link between Ag-base
metal veins and lamprophyric magmatism in the
Erzgebirge (Seifert, 1999, 2004).
(h) The similar paragenetic, geochemical, isotopic,
and fluid inclusion characteristics of the dkbT min-
eralization stage in the Freiberg district and those
in the Kutna Hora and Havlıcklv Brod districts
(Moldanubian Terrane/central Bohemian Massif)
attest to limited wall rock control on the mineral-
izing processes (Seifert et al., 2001). Therefore, it
is likely that the formation of the In-rich base
metal veins was not significantly influenced by
wall rock leaching. In this context, the close spa-
tial–time relationship of Ag-rich, Sn-bearing base
metal veins in the Erzgebirge and In-enriched Zn–
Cu–As–Sn–Pb–Ag veins in the Moldanubian Ter-
rane to post-collisional lamprophyric and granitic
magmatic activity is interpreted as an argument in
favour for a deep-seated source of base metal-rich
hydrothermal fluids (Seifert, 1999, in press). In-
dium-enriched Sn-polymetallic ore which is asso-
ciated with A-type granite intrusions in the Mount
Pleasant district (Taylor et al., 1985; Murao et al.,
1995) could be interpreted as an additional argu-
ment for a deep-seated source of In-enriched Sn-
polymetallic mineralization.
(i) Based on temporal, mineralogical, geochemical,
fluid inclusion, as well as S and Pb isotope data, a
genetic link between Sn-polymetallic and Ag-base
metal ore deposits in the Erzgebirge is postulated
(Seifert, in press). The significant In concentration
of Cd–Fe-rich sphalerites of both deposit types
(Tables 1 and 4) is an additional argument for the
genetic relationship between these late-Variscan
postmagmatic mineralization stages.
The deqT veins in the North sub-district show min-
eralogical (e.g., pyrite, chalcopyrite, galena, arsenopy-
rite, electrum?) and geochemical (Ag, Au, Zn, Pb, Cu,
Sb, As, Hg) similarities to low-sulphidation epithermal-
style Ag–Au mineralization (cf. Simmons and Albin-
son, 1995; Hedenquist and Arribas, 1999). Low-In deqTore-type samples are characterized by significant high
concentrations of Au (up to 9 ppm), Hg (up to 16 ppm),
and Sb (up to 2.1 wt.%). In this context, the comparison
with Mexican Ag–Au and Ag–Pb–Zn epithermal
deposits is of special interest (cf. Simmons and Albin-
son, 1995). In particular, the Fresnillo district shows
base metal-rich ore bodies in the centre. Fluid inclu-
sions indicate that this mineralization formed at 270 to
355 8C. In contrast, Ag-rich ore veins occur towards the
periphery of the district, and contain sulphosalts and
sulphides with quartz and calcite, similar to the deqT anddebT ore-type in the Freiberg district. Isotope data (S, H,
He) strongly suggest that hydrothermal fluids of Ag-
rich base metal mineralization in the Fresnillo district
derived from a magmatic source (cf. Simmons and
Albinson, 1995).
8. Conclusions
(1) The Freiberg base metal vein district and other
late-Variscan base metal and Sn-polymetallic grei-
sen-, vein- and skarn-type deposits (e.g., Zinn-
wald/Cınovec, Ehrenfriedersdorf–Geyer, Pohla)
show that the Erzgebirge is among the largest
In-enriched provinces worldwide.
(2) The economic In potential is indicated by bulk
ore concentrations of up to 3000 ppm In in the
Freiberg, Marienberg and Annaberg districts.
(3) Sphalerite from the Zn–Sn–Cu sequence of the
dkbT ore-type is the most important host mineral
for In in the Freiberg district. Indium concentra-
tions are also related to microscopic Zn–Cu–Sn–
In–S grains in sulphides of the Cu- and Sn-rich
dkbT ore-type.(4) The significant In concentrations in sphalerite
from Ag-rich base metal (vein-type) and Sn-poly-
metallic (vein-, greisen, and skarn-type) deposits
in the Erzgebirge indicates a genetic relationship
between these late-Variscan mineralization stages.
Both deposit types are potential In hosts in the
Erzgebirge, and may account for several hundred
tonnes of In metal.
(5) Indium-rich base metal veins in the Erzgebirge
(e.g., Freiberg, Marienberg) and the Moldanubian
Terrane (e.g., Kutna Hora), and In-rich Sn-poly-
metallic mineralization in the Erzgebirge show
spatial-time relationships to lamprophyric and
A-type granitic intrusions. This close relationship
may be interpreted in the way of mantle-derived
magmatic origin of In-rich fluids.
(6) The Erzgebirge may represent a key district for the
identification of mantle-derived In mineralizing
processes in the geological past. Lamprophyric
and/or anorogenic granitic intrusions could be
significant for the exploration of high-temperature
In-enriched polymetallic sulphide ore deposits.
(7) Highest concentrations of Au (up to 9 ppm), Sb
(up to 2.14 wt.%), and Hg (up to 16.4 ppm) occur
in the low-indium deqT ore-type samples which
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T. Seifert, D. Sandmann / Ore Geology Reviews 28 (2006) 1–3128
show mineralogical and geochemical similarities
to epithermal-style Ag–Au mineralization.
Acknowledgements
We express our gratitude to U. Schwarz-Schampera
for fruitful discussions and constructive comments to
the manuscript. We gratefully acknowledge K. Rank for
providing sample material from the ore deposit collec-
tion of the TU Bergakademie Freiberg, M. Drechsel for
technical support and friendly comments, and P.M.
Herzig for organizational support. We are very grateful
to M. Stemprok and Ch. Gauert for their detailed
reviews and valuable constructive comments that im-
proved the manuscript. The authors thank the editor
N.J. Cook for his helpful and friendly comments. This
work has been financially supported by the Bergbau-
Berufsgenossenschaft Bochum and Gera through a
grant to TS and the Leibniz program by the DFG
through a grant to P.M. Herzig and his working group.
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