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Ore Geology Reviews 33 (2008) 187 – 210

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The “calamine” nonsulfide Zn–Pb deposits of Belgium:

Petrographical, mineralogical and geochemical characterization
Vito Coppola a , Maria Boni a,d,⁎, H. Albert Gilg b ,
Giuseppina Balassone a , Léon Dejonghe c
a
Dipartimento di Scienze della Terra, Università di Napoli Federico II, Via Mezzocannone 8, 80134 Napoli, Italy
b
Lehrstuhl für Ingenieurgeologie, Technische Universität München, Arcisstr. 21, 80333 München, Germany
c
Geological Survey of Belgium, 13 Rue Jenner, B-1000 Brussels, Belgium
d
Geologisch-Paläontologisches Institut der Universität, Im Neuenheimer Feld 234, 69120 Heidelberg, Germany

Received 30 October 2005; accepted 7 March 2006

Available online 7 August 2007

Abstract

The Belgian nonsulfide Zn deposits represent the historical basis for the zinc mining and smelting industry in Europe. The zinc
ores were called “calamines” and consist of a mixture of Zn carbonates (smithsonite, hydrozincite) and Zn silicates (hemimorphite,
willemite and Zn clays), with a variable content of Pb minerals. The “calamines” are considered to be oxidation products of primary
sulfide ores.
The most important was the La Calamine orebody (more than 600,000 tons of Zn metal) that was continuously exploited for several
centuries. Nonsulfide ores were also exploited at Schmalgraf, Engis, Dickenbusch, Fossey, Rocheux-Oneux, Welkenraedt and in other
smaller deposits (all no longer accessible for study), where the “calamines” extended from the surface to an average depth of 40 to 50 m.
The primary Zn–Pb sulfide mineralization consists of post-Variscan hydrothermal veins and replacement bodies, mostly occurring in
the Dinantian (Visean) limestones. The sulfides intersect the Paleozoic rocks and are truncated and unconformably covered by Late
Cretaceous sediments (Santonian Aachen Fm.). The same setting has been observed for the nonsulfide ores, suggesting an Early to
Mid-Cretaceous weathering, consistent with other geological and geochronological data on paleoweathering in Europe.
The extensive occurrence of willemite, that appears to be the first deposited nonsulfide mineral, is a striking particularity of the
Belgian “calamines”. Most fluid inclusions in willemite (80%) and all inclusions in smithsonite are monophase (aqueous). Ice
melting temperatures suggest salinities between 0 and 5 wt.% NaCl equiv. Homogenization temperatures of rare two-phase
inclusions (liquid + vapor) in willemite display a large variation between 80 and 190°, an interval matching the temperature ranges
of other willemite ores throughout the world, so far considered of hydrothermal origin.
The stable isotope variation of Belgian smithsonites and cerussites is very similar to the range measured in other supergene
nonsulfide deposits similar to those of SW Sardinia. Belgian smithsonites exhibit a limited range of δ18O values from 27.1 to
30.6‰, averaging 28.4‰ ± 0.8‰ V-SMOW. This limited range points to a relatively uniform isotope composition of the oxidizing
waters and constant temperatures of smithsonite crystallization. Carbon isotope values, even from the same mine, show a
considerable range from −11.6 to −1.6‰. This extensive range indicates at least two carbon sources: 13C-depleted carbon derived
from the organic matter in the soils and 13C-enriched carbon originating from marine carbonate host rocks. Cerussites have oxygen
isotope values ranging from 16.8 to 19.3‰, averaging 17.8 ± 1.0‰ and carbon isotope values of −18.4 to − 14.7‰.
The metallic deposits of Eastern Belgium have undergone a polyphase history, which started with a possibly Jurassic sulfide
mineralization, followed by oxidation under high silica activities and consequently by supergene weathering. Owing to structure

⁎ Corresponding author.
E-mail address: boni@unina.it (M. Boni).

0169-1368/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.oregeorev.2006.03.005
188 V. Coppola et al. / Ore Geology Reviews 33 (2008) 187–210

and mineralogical association, we do not consider the high homogenization temperatures as reliable minimum temperature
estimates of willemite formation. However, it is possible that the willemite concentrations could have been derived from low-
temperature, localized hydrothermal processes caused by deeply reaching oxidizing fluids. Smithsonite and hemimorphite, often
developed at the expenses of willemite, have all the characteristics of supergene oxidation products.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Belgium; Zinc; Nonsulfide; Calamine; Mineralogy; Geochemistry; Paleoweathering

1. Introduction Eastern Belgium, together with Lower Silesia in Poland

Within the last decade, with the development of
solvent-extraction and electro-winning processes for the
treatment of nonsulfide zinc ores, there has been a
renewed commercial interest for this style of mineral-
ization throughout the world (Large, 2001; Boni, 2003;
Hitzman et al., 2003). The commercial exploitation of
nonsulfide deposits, commonly defined as “Zinc
Oxides” or “Calamine” (nonsulfide Zn ore in carbonate
rocks), is rapidly becoming an important source of
metallic zinc and it is foreseeable that in the near future
the annual production of zinc from these ores could
exceed 10% of the global zinc metal production.
Scientific research is now focused not only on several
economic “Zinc Oxide” deposits throughout the world
(Borg et al., 2003; Hitzman et al., 2003; Gilg et al.,
2003a; Monteiro et al., 2006, but also on older (mostly
European) mining districts containing smaller and
historically exploited deposits (Boni et al., 2003; Boni
and Large, 2003; Balassone et al., 2005). The aims of
these studies are both to understand the geological
constraints on the distribution of the nonsulfide
orebodies and on their timing of formation, and also to
improve our knowledge of mineralogy and geochemis-
try of the nonsulfide mineral phases. A thorough
understanding of the relationships of mineralogy to
each deposit type, will significantly aid in exploration
targeting and metal recovery.
Brass production from nonsulfide Zn ore began in
many parts of Europe, including Belgium, during the
Roman period and continued through the Middle Age at
a constant pace up to the start of the Industrial
Revolution, when the high demand for metals dictated
a more intensive exploitation. After the first half of the
20th Century, owing to the exhaustion of high grade
nonsulfide Zn resources in Europe, and to the
difficulties encountered during the treatment of their
complex mineralogy, Zn sulfide ores were preferred,
despite their lower grades. Over 1.5 Mt of zinc metal
have been produced from the zinc deposits (sulfides and
nonsulfides) in Belgium over the last two centuries.
and the Iglesias area in SW Sardinia, were the three most
important mining districts in Europe for the production
of “calamine” ores. The largest deposit, La Calamine
(“Kelmis” in German), also named Moresnet, Alten-
berg, Grande Montagne and Vieille Montagne (Tim-
merhans, 1905), situated ca. 30 km ENE of Liège, was
one of the first resources of nonsulfide zinc to be
developed. Production at La Calamine exceeded
600,000 tons of zinc metal and reached perhaps
760,000 tons; this uncertainty is due to the lack of
production statistics before 1825. When the mine was
still in operation, the concentrates were essentially made
up of only Zn nonsulfide ore at grades of 33 to 47%.
Other relatively important nonsulfide Zn resources
in Belgium were exploited up until the first half of the
20th Century in the oxidation zones of the Fossey,
Schmalgraf, Engis, Rocheux-Oneux, Theux, Welken-
raedt and other smaller sulfide deposits, all concentrated
in the NE of the country. At Fossey, a mine which was
active until 1918, the total production of nonsulfides
ranged around 485,000 tons with an ore grade between
35 and 60% Zn. The smaller mines of Dickenbusch,
Pandour, Heggelsbruck and Saint-Paul were included
in the Welkenraedt mining property. The Belgian depo-
sits, as well as most of the other European nonsulfide
zinc deposits, were hosted mainly in carbonate rocks
and consisted largely of smithsonite–hemimorphite–
hydrozincite. They have been considered so far to be
supergene in the sense of Hitzman et al. (2003)
(Dejonghe and Boni, 2005). However, the ore exploited
in the historically important La Calamine deposit in
Belgium, hosted in Upper Paleozoic carbonates,
contained up to 40% of the silicate willemite (Dejonghe
and Jans, 1983). This zinc silicate mineral was
discovered here by M. Levy and named after Willem I
of Orange-Nassau, King of Holland (Levy, 1843). With
few exceptions, the occurrence of willemite-rich ores
has been recently considered (Brugger et al., 2003;
Hitzman et al., 2003) as a proof of hydrothermal origin:
this thus poses a genetic problem for the Belgian
“calamines”.
 V. Coppola et al. / Ore Geology Reviews 33 (2008) 187–210
The main goal of the present contribution is to provide
a petrographical, mineralogical and geochemical char-
acterization of the Belgian nonsulfide Zn–Pb ores that
could help in clarifying the genetical interpretation of the
mineralization process and its timing. However, due to
the fact that the mines are now shut, and are inaccessible,
and owing to the virtual absence of good mineralized
outcrops, a major problem encountered during this study
was not being able to sample precisely from all those
areas that could reflect the depositional conditions of the
Zn-oxide ores. This study relies instead on specimens,
sampled by one of us (M.B.) at the Royal Belgian
Institute of Natural Sciences of Brussels and at the
Geological Survey of Belgium. Additional samples were
also taken from the Museo di Mineralogia dell'Univer-
sità di Napoli.
2. Geological setting
In Belgium, three main geological units can be
distinguished (Fig. 1). (1) A basement, made up of
Cambrian, Ordovician and Silurian rocks. The basement
crops out in the Stavelot, Rocroi, Givonne, Serpont,
Brabant and Condroz Massifs. (2) An older cover, made
up of Devonian and Carboniferous rocks. This sequence
crops out in the Namur, Verviers and Neufchâteau-Eifel
Synclinoria as well as in the Dinant and Ardenne
Anticlinoria. (3) A post-Variscan cover, consisting of
rocks whose ages range from Permian to Recent. This
younger cover is found in the northern part of the
country (approximately to the north of the line joining
Fig. 1. Geological sketch map of the Vallonie region in Belgium. The square shows the location of the mineralized district depicted in
Fig. 2.
189
Mons, Namur and Liège) and in the extreme south
(Belgian Lorraine).
The basement underwent a first deformation during
the Caledonian and was deformed again during the
Variscan orogeny, together with the post-Caledonian
Paleozoic cover. The main Variscan phase (Asturian
phase) started at the end of the Westphalian. A large
nappe, called Dinant Synclinorium (or, more generally,
Ardenne Nappe), overthrust the Namur Synclinorium
northward along a set of east trending faults (Fig. 1).
These faults have different names: Midi, Eifel and
Aachen (from West to East).
The geological history of Belgium after the Variscan
orogeny is difficult to reconstruct, due to the scarcity of
preserved sections comprising the time span from
Permian to Late Cretaceous. However it is generally
regarded that sub-horizontal Permian sediments were
deposited and then removed by erosion during later
uplifts. Vercautere and van den Haute (1993) considered
that approximately 3 km of Permo-Carboniferous
sediments, which covered the Brabant Massif, were
removed after the Middle Jurassic. Possible relicts are
preserved in the Malmédy Graben (Fig. 1) (Bultynck
et al., 2001). Triassic and Jurassic sediments were either
never deposited, or they were deposited only on the
eastern side of the Brabant Massif, where they were
completely eroded after the uplift related to the
Cimmerian phase of the Alpine orogeny.
The structurally complex Verviers Synclinorium
(Graulich et al., 1984) is located between Liège and
Aachen. This has been considered as a Variscan fold-
190 V. Coppola et al. / Ore Geology Reviews 33 (2008) 187–210
and-thrust unit (Hance et al., 1999), dominated by two
systems of faults: (1) NE–SW longitudinal faults, linked
to the Variscan overthrusting; and (2) NNW–SSE trans-
verse faults, linked to the tectonic pulses responsible for
the first initiation of the Rhine Graben. These faults, in
which most of the primary Zn–Pb vein-type sulfide
deposits occur, were reactivated on several occasions
during the Mesozoic and Tertiary.
Cretaceous sediments unconformably overlie the
folded Paleozoic rocks (Fig. 1). The Cretaceous
succession starts with the deposition of the Aachen
Formation (Breddin, 1932) of Santonian age (Late
Cretaceous). At the base of this formation the Mospert
Sands occur, followed by the Hergenrath Clays Member
(Breddin et al., 1963), which consists of alternating
layers of silty clays and argillaceous sands and silts, with
abundant plants debris. These are overlain by the
Aachen and Hauset Sands Members (Albers, 1978),
both consisting of shallow-water to continental sand-
stones. The Aachen Formation is then overlain by the
transgressive Vaals Formation (Felder, 1975) of Cam-
panian age, consisting of sandstone, siltstone and clay
layers with glauconite. The Gulpen Formation (Upper
Campanian to Maastrichtian chalk and calcarenites with
chert nodules) overlies the Vaals Formation. Tertiary
sediments, consisting mainly of alternating sandy and
clayey units, eventually overlie the Gulpen Formation.
The uplift of the Ardenne Massif, due either to
lithospheric buckling induced along the front of the
developing Alpine orogeny, or driven to plume activity
related to the Eifel volcanism (Demoulin, 2003), started
in the Upper Oligocene and continues up to the Present.
Since Oligocene time, a maximum of 500 m of uplift has
occurred throughout Belgium (Demoulin, 1995). In the
Ardenne region, the uplift has locally resulted in
complete erosion of nearly all the Cretaceous and
Tertiary cover.
If the Belgian “calamines” are, at least partly, of
supergene origin (as stated by Dejonghe and Boni,
2005), it becomes important, to consider the different
paleoweathering phases (that in carbonate terrains might
be associated with deep karsting) recorded in this part of
Europe from the end of Variscan orogeny throughout
Mesozoic and Tertiary until Recent (Boni and Large,
2003, 2005). In fact, some of these phases could have
caused the oxidation of primary sulfides in the Verviers
Synclinorium and the precipitation of secondary Zn–
Fe–Pb minerals in the “calamine” deposits.
Dupuis (1992), Alexandre and Thorez (1995),
Demoulin (2003) and Quesnel (2003) pointed out that
the Paleozoic rocks in Belgium were affected during the
Permian and Mesozoic (before the Cretaceous trans-
gression) by deep weathering with development of
paleosurfaces, as well as by multiple weathering phases
during the Tertiary. Among the many paleosurfaces,
three could be associated with especially strong
oxidation phenomena: the post-Variscan, the pre-
Triassic and the pre-Santonian paleosurface. As men-
tioned by Laloux et al. (2000), the top of the Paleozoic
rocks is deeply weathered (thickness reduced to between
5 and 30 m) to an alterite consisting of varicolored clays
in the Verviers Synclinorium. This is overlain by
Santonian sediments that mainly correspond to the
Aachen Formation. Several studies have been per-
formed throughout Belgium (Legrand, 1968; Dupuis,
1992; Dupuis et al., 1996) on the kaolinized post-
Variscan regoliths, developed on Paleozoic rocks of
various ages and composition and covered by Late
Cretaceous sediments. In the Transinne quarry
(Ardennes), where a supergene kaolinite deposit is
presently exploited, this regolith on the Paleozoic
surface can reach a maximum thickness of 70 m (Dupuis
et al., 1996). The formation of the regolith has been
dated by Yans (2003) and two distinct weathering
periods have been identified: an Early Cretaceous period
(126 ± 10 Ma and 135 ± 15 Ma, from Berriasian to
Barremian) from K–Ar data on two hollandites (ideally
BaMn8O16), and an Early Miocene (21.1 ± 0.4 Ma)
period from Ar–Ar and K–Ar data on cryptomelane
(ideally KMn8O16). Further evidence of Early Creta-
ceous paleoweathering (120 to 130 Ma) in this part of
Europe comes from paleomagnetic dating of a wide-
spread ferricrete occurrence denominated “Borne de fer”
in Lorraine (Théveniaut et al., 2002).
After the pre-Santonian paleoweathering phases,
Tertiary weathering episodes combined with karstic
dissolution are recorded in several areas of Belgium,
including the Verviers Synclinorium. A classic example
is given by halloysite accumulations occurring in the
Entre-Sambre-et-Meuse and Condroz areas at the
bottom of large cryptokarsts (100 to 150 m deep),
infilled by Oligocene marine sands and Neogene
continental deposits (Dupuis, 1992; Dupuis et al.,
2003). During part of the continental periods in the
Neogene (mostly Miocene), the percolation of moder-
ately acid fluids induced karstic dissolution of the
topmost limestone below the permeable sands. As a
result, deep sinkholes developed under the Tertiary
cover (cryptokarst or cryptolapiaz). Solutions were
buffered at the limestone contact, precipitating alumina
gel from which massive halloysite and associated
kaolinite crystallized (Ertus et al., 1989). Pleistocene
karst is recognized in Paleozoic limestones, in the region
of Liege (Quinif and Vandycke, 2001).
 V. Coppola et al. / Ore Geology Reviews 33 (2008) 187–210 191

3. Primary sulfides where four of the six largest zinc–lead deposits in

With the exception of La Calamine, the nonsulfide
deposits in Belgium were overlying primary Zn–Pb
sulfide orebodies (Dejonghe and Boni, 2005). The most
productive district for sulfide and nonsulfide Zn–Pb
ores in Belgium was mainly concentrated within an area
of about 400 km2 in the eastern part of the country
(Verviers-Namur Synclinoria; Dejonghe et al., 1993),
easternmost Belgium occur (Schmalgraf, Bleiberg,
Fossey and Eschroich; Fig. 2). Most of these deposits
follow a post-Variscan extensional fault network,
parallel to the northern sector of the Rhine Graben
(Bartholomé and Gérard, 1976; Dejonghe, 1998). The
tonnages of the deposits, each exceeding 50,000 tons
(Zn + Pb), and the intensity of displacement due to the
block-faulting tectonics increased along a SW/NE

Fig. 2. The northeast Belgium mining district of the Verviers Synclinorium, with the location of sulfide and nonsulfide ore deposits (modified from
Dejonghe, 1998).
192 V. Coppola et al. / Ore Geology Reviews 33 (2008) 187–210

Fig. 3. (a) Generalized plan of the La Calamine deposit below recent cover (Dejonghe et al., 1993); schematic cross-sections of the small (b)
Dickenbusch (Dejonghe et al., 1993) and (c) Mützhagen (Lespineux, 1905) orebodies: both sulfide and nonsulfide ores (in black) are truncated and
covered by Cretaceous sandstones (Aachen Formation).
 V. Coppola et al. / Ore Geology Reviews 33 (2008) 187–210 193

trending gradient. Similar Pb–Zn orebodies occur in the as well as pockets of cerussite were also irregularly
adjacent Aachen area of Germany (Gussone, 1964). To enclosed in the primary sulfide bodies down to 120 m in
constrain the weathering phase responsible for the depth (maximum reported depth of oxidation is 211 m at
majority of the nonsulfide ores, the setting of the the Schmalgraf mine).
primary deposits that were in turn subject to oxidation, The nonsulfide Zn products were called “calamine”
as well as their timing of deposition is of crucial by the miners. This term describes a mixture of minerals
importance (Muchez et al., 1994; Dejonghe, 1998; such as Zn carbonate (smithsonite, ZnCO3) and Zn
Heijlen et al., 2001). silicate [hemimorphite, Zn4(Si2O7)(OH)2·H2O], or the
The sulfide orebodies consist of hydrothermal veins,
cutting deformed carbonate rocks of Devonian and
Carboniferous age and often connected to stratabound
“flats” or “mantos” (Balcon, 1981). An exception to the Table 1
XRD analyses of the samples from the Belgian “calamine”; mineral
general carbonate host rock setting is represented by symbols are in order of abundance
the Bleiberg lode, which is hosted in Visean limestones
Sample Mineral(s)
as well as in Namurian siliciclastic rocks. Sulfide
mineralogy is quite simple, including sphalerite, La Calamine -Moresnet
RN1996 sm, cc, qz
galena, and pyrite/marcasite with collomorph struc-
RN2005 sm, wi, he, cc,
tures, often brecciated (Fig. 4a). Low amounts of Ni RN2008 he, sm, cc, wi
and Co are contained in the iron sulfides (Duchesne RN2017 sm
et al., 1983). Dejonghe (1990) also found gersdorffite RN2044 sm, he, cc
(NiAsS) and nickeline (NiAs) in the Bleiberg mine. RN2051 sm, he, cc
RN2101 sm, he
The mineralized lodes do not extend into the Upper
RN2172 sm, cc, qz
Cretaceous rocks (Aachen Formation) (Fig. 3a, b). RN2487 he, sm, cc, qz
Therefore, the emplacement age of the sulfide ores is RN3403 qz
constrained between the end of the Variscan orogeny RN3834 wi, sm
(ca. 295 Ma) and the beginning of the Late Cretaceous RN4106 sm, qz
RN5011 wi
(ca. 100 Ma). After de Magnée (1967), Dejonghe
RA4999 sm, cc
(1998) and Heijlen et al. (2001) the main hydrothermal RA5004 wi, sph, ga, py
mineralizing event in the Verviers district should date RA5012 wi
back to the end of the Jurassic (≈ 150 Ma). In fact, the RA5013 wi, sa
sulfide ores of the Verviers syncline are structurally RA5014 sm, cc, qz
RA6555 he, sm, cc, wi, sa
comparable to the Zn–Pb deposits of Maubach-
RA6661 wi
Mechernich in Germany, hosted in Triassic sandstones, R2B33 qz, sm, cc
some tens of kilometres to the southeast, and have R2B34/2624 sm, wi, cc
possibly been formed at the same time. Direct R2B35/3925 sm
sphalerite Rb–Sr dating of the Maubach deposit Museo Mineralogia (Na) wi
Fossey
yielded a Middle Jurassic age of 170 ± 4 Ma (Schneider
RN2208 sm, cc, qz, mo, cl
et al., 1999). RN2298 he, sm, do, mo
RN2300 sm, wi, sa
4. Nonsulfides RN2301 sm, he
Welkenraedt
RN2220 sm
Supergene weathering of the sulfide ores could have
RN2224 he, wi, sm
taken place at several intervals between the Late RN2236 sm, cc
Mesozoic and the present day. Gossans representing RN2242 sm, cc
the oxidation products of Zn, Fe and Pb sulfides RA4986 sm, cc, qz
exploited in the Belgian mineralized districts (Fig. 2), Theux
RN2270 sm, cc
occurred not only on top of the primary ores, but they
also represent the infill of deeper karstic cavities in Distinct parts of few samples (characterized by letters a, b and c) have
Paleozoic carbonates (Lespineux, 1905; Timmerhans, been analysed separately.
Abbreviations: cc = calcite, cl = clay minerals, do = dolomite, ga =
1905; Dejonghe et al., 1993). Oxidation of sulfides galena, go = goethite, he = hemimorphite, mo = monheimite, sm =
generally extends from the surface to an average of 40 to smithsonite, wi = willemite, py = pyrite, sa = sauconite, sph =
50 m in depth. However, in several mines, Zn carbonates sphalerite.
194 V. Coppola et al. / Ore Geology Reviews 33 (2008) 187–210
assemblage of hemimorphite, smithsonite, hydrozincite
[Zn5(CO3)2(OH)6] and willemite (Zn2SiO4), locally
associated with Fe-oxyhydroxides and clays. Pb and
Fe secondary minerals were always associated to the Zn
ores. Belgian “calamine” was grey, yellow or even black
in color and occurred as dense rock masses or with
concretionary, foliated or stalactitic shapes (Dejonghe
and Boni, 2005). Their aggregates were microcrystalline
(“amorphous” in the old literature) or coarse-grained,
but also displayed brecciated or vuggy textures. The
shape of the nonsulfide concentrations ranged from bulk
replacement bodies of entire blocks of the host
carbonates and/or sulfides, to the concretionary infilling
of isolated druses and cavities with idiomorphic
smithsonite and hemimorphite crystals at different levels
in the upper part of the oxidation zone.
The large La Calamine orebody was located in a
narrow syncline, dipping about 15° to the SW, made up
of Famennian sandstones and shales overlain by
Tournaisian dolomites and dolomitic shales (Dejonghe
and Jans, 1983). It formed a large lenticular pocket,
located in the core of the syncline (Fig. 3a). The
 V. Coppola et al. / Ore Geology Reviews 33 (2008) 187–210 195

economic nonsulfide concentrations overlaid the
Famennian siliciclastic sediments, as well as the layer
of silicified dolomite at the bottom. The deposit had the
shape of a sinkhole infill, extending for a length of 450
to 500 m and a width of 65 to 100 m, reaching 110 m in
its deepest part. The orebody is located on a SW–NE
thrust fault (the Schmalgraf Fault, at the front of the
Donnerkaul tectonic unit) (Laloux et al., 2000; Ghysel
et al., 2000), which could have facilitated the karstifica-
tion process and later also channelled meteoric and/or
hydrothermal fluids (Boni et al., 2005). Detailed
sections of La Calamine, redrawn from the old mining
documents have been published in Dejonghe (1998) and
Boni and Large (2003). Only traces of sulfides (galena,
sphalerite, pyrite, marcasite, greenockite) occurred along
the walls of the La Calamine pit (Dejonghe and Jans,
1983). Most of these sulfides were possibly supergene
in origin. The zinciferous nonsulfides, associated with
abundant Fe-(hydr)oxides, were concentrated as irre-
gular bodies hosted in mottled Zn clays. The ore as-
semblage at La Calamine ranged from dominantly
Zn carbonates at the near surface, to a mixture of Zn
carbonates and Zn silicates with increasing depth, and a
silicate assemblage (willemite and Zn clays) below −80/
85 m in depth (Dejonghe and Boni, 2005). In the old
literature (de Launay, 1913), huge willemite blocks have
been often described to occur in the lowermost parts of
the deposit, surrounded by iron hydroxides, smithsonite
and hemimorphite. The latter minerals were also
cementing collapse breccias containing broken willemite
clasts of variable size. In the open pit a few cavities have
been encountered, filled with siliciclastic sediments
comparable to sandstones of the Aachen Formation
(Dejonghe et al., 1993).
The mineralogy of the other, less important non-
sulfides Zn resources at the oxidation zone of Fossey,
Schmalgraf, Engis, Dickenbusch, Mützhagen, Rocheux-
Oneux and Welkenraedt mines in the NE of the country,
was variable. They contained a combination of Zn
carbonates and silicates, with willemite as a common,
albeit minor, component. In addition, variable amounts
of Pb and Fe minerals were always present. At Fossey, a
mine that was active until 1918, both sulfides and non-
sulfide ores were exploited. In the Welkenraedt mining
property the mineralization (also comprising both
sulfides and calamine) was controlled by the NW–SE
oriented Welkenraedt fault and other parallel lineaments
cutting NE–SW trending Variscan structures. The
calamines, including a significant amount of Pb carbo-
nates, could be traced to a depth of about 50 m below the
surface. The oxidation products and host rocks, locally
comprising pockets of unweathered sulfides, are covered
throughout the entire district by at least 10 m of
horizontal sediments of the Aachen Formation (Fig. 3b,
c). In the small permit of Theux, exploited until 1925, the
main ore consisted of Zn and Pb carbonates, with
abundant Fe- and Mn-oxyhydroxides (Mélon et al.,
1976). Abundant hemimorphite was recorded in Theux,
whereas willemite occurred only episodically.
5. Sampling and analytical methods
Presently, both sulfide and nonsulfide deposits in
Belgium are completely inaccessible, due to closure of
all the mines. Therefore, the characterization of the
Belgian “calamines” carried out in this study is based on
available old literature data, as well as on analyses of
selected samples (in total 45) from the collections of the
Royal Belgian Institute of Natural Sciences; the
Geological Survey of Belgium, and from the Museo di
Mineralogia dell'Università di Napoli.
While sampling from these collections, we selected
several ore types covering the wide spectrum of
nonsulfide minerals (most of them from La Calamine),

Fig. 4. Typical ore samples from the Verviers Synclinorium mining district. Smithsonite types are classified as in Sardinia nonsulfide ores (see text for
details): a) Primary sulfide breccia ore: zoned collomorph sphalerite fragments with minor galena are cemented by a microcrystalline sulfide
assemblage (Mineralogical Museum, La Calamine); b) Moresnet1: sphalerite bands (dark) partly replaced by microcrystalline willemite (red-brown)
(RN3861 Coll. Buttgenbach 1916); c) La Calamine: willemite as reddish microglobules (RN3856, Coll. Buttgenbach 1916); d) La Calamine:
dissolution breccia, with clasts consisting of hemimorphite (replacing sphalerite?) cemented by reddish microcrystalline willemite (RN2140);
e) Moresnet: crust made of honey-colored rhombohedral (Type I) smithsonite crystals (RN3834, Coll. Buttgenbach 1916); f) La Calamine: network of
rhombohedral smithsonite (Type I) crystals encrusting the (d) willemite breccia (RN2140); g) Welkenraedt: mammillary microcrystalline smithsonite
(Type V) concretions (RN4988, Coll. Buttgenbach 1916); h) La Calamine: globular smithsonite (Type V) concretions (RN2280, Coll. De Groote);
i) La Calamine: crusts of scalenohedral smithsonite (Type VI) crystals growing on globular willemite (RA5014, Coll. Buttgenbach 1916); k) La
Calamine: mottled sample with hemimorphite I (pale) microclasts cemented by brownish smithsonite (RN2051); l) Moresnet: hemimorphite II laths
in cavity (RA4790); m) Viola Calaminaria, a typical flower growing on “calamine” dumps (good for exploration!).

1
In the figures and tables we have used the names of La Calamine and Moresnet, as written on the samples at the Museum of the Royal Belgian
Institute of Natural Sciences in Brussels, even if both are probably related to the same old mining site of La Calamine. The numbers of the samples
are also referred to the catalogue of the Museum.
196 V. Coppola et al. / Ore Geology Reviews 33 (2008) 187–210
in their different morphological shapes. From the same
collections, we also sampled a number of Ca carbonate
crystals and concretions that were paragenetically asso-
ciated with the nonsulfide ores in several mines, in order
to establish their mineralogy and compare their stable
isotopic geochemistry with those of the Zn/Pb carbonates.
Finally, a small number of Ca/Mg carbonate samples,
corresponding to the local host rock, were collected from
a small outcrop near the old La Calamine open pit.
Before analysis, each pure mineral phase was obtained
by a combination of hand picking under a stereomicro-
scope and gravimetric separation techniques; then cleaned
in a sonic bath for 10 min, to eliminate impurities
deposited on crystal surfaces. X-ray powder diffraction
analyses (XRPD) were carried out at the Dipartimento di
Scienze della Terra, Università di Napoli, Italy, with a
SEIFERT MZVI automated diffractometer, CuKα radi-
ation. Synthetic CaCO3 (Mallinckrodt analytical reagent)
was used as internal standard (position of the 1014
reflection for CaCO3 taken as 3.035 Å, JCPDS-ICDD 5-
586). Clay minerals analyses (fraction b2 μm) have been
performed in oriented aggregates after glycolation (EG)
with several heating steps (250, 350 and 500 °C). SEM
observation and semi-quantitative major element analyses
were undertaken using a JEOL-JSM 5310 scanning
electron microscope with a Link EDS operating at 15 kV
and a Link AN10000-ZAF4/FLS. Silicates, sulfates,
sulfides, carbonates, oxides and pure elements were
used as standards. The water content was evaluated by
means of thermal analyses and/or stoichiometry. Chem-
ical analyses of willemite, smithsonite and hemimorphite
were performed by WDS on a Cameca SX50 electron
microprobe (IGAG at the CNR, Rome) operating at
15 kV, 15 nA and 10 μm spot size. Data were corrected
using the PAP program (Pouchou and Pichoir, 1991).
Minerals and pure elements were used as standards. Major
and minor elements in smithsonites and willemites have
been measured at ACME laboratories in Vancouver,
Canada. From each pulverized sample, 2 g were digested
with Aqua Regia (HCl–HNO3) at 95 °C. The measure-
ments have been carried out with a Perkin Elmer Elan
6000 ICP-MS in the 1-DX Group (36 elements).
Smithsonites and willemites, in polished thin section
(∼30 μm thick), were examined by conventional and
cold cathodoluminescence (CL) petrography utilizing a
CITL 8200 Mk3 Cold Cathodoluminescence instrument
at the Geologisch-Paläontologisches Institut, Universität
Heidelberg (Germany), with the following operating
conditions: 23–25 kV voltage and 500–550 μA beam
current. Microthermometric analytical measurements on
fluid inclusions of willemite were carried out at the
Dipartimento di Geofisica e Vulcanologia, Università di
Napoli, Italy, using a Linkam THMSG 600 heating/
freezing stage. The stage was calibrated using synthetic
fluid inclusion (Bodnar and Sterner, 1987). The
precision of the measurement is better than ± 1 °C in
the range of interest for this work. Stable oxygen and
carbon isotope ratios of carbonates were determined
using an automated on-line device (Finnigan Gasbench
II) operated in the continuous flow mode attached to a
Finnigan Deltaplus mass spectrometer at the Bayerische
Staatssammlung für Paläontologie, Munich, Germany
(Gilg et al., 2003b), or a Finningan DeltaS mass
spectrometer at the Ruhr Universität, Bochum, Ger-
many. The purity of handpicked samples was checked
by XRD. Ancillary calcite in smithsonite-dominated
samples was removed using a mild dilute hydrochloric
acid treatment before isotopic analysis. All carbonate
samples were reacted with anhydrous phosphoric acid at
72 °C for 1.5 h. Oxygen isotope analyses were corrected
using the phosphoric acid fractionation factors for
calcite (1.00864, Swart et al., 1991), dolomite
(1.00986, Rosenbaum and Sheppard, 1986), cerussite
(1.00919, Gilg et al., 2003b) and smithsonite (1.00962,
Gilg et al., 2003b). The precision of analyses based on
repeated measurements of laboratory and international
standards is about 0.1‰ (1σ). The isotopic composi-
tions are reported as δ-values in per mil relative to V-
SMOW for oxygen and V-PDB for carbon.
6. Mineralogy and geochemistry of nonsulfide ores
6.1. Mineralogy
The common mineralogical phases of the nonsulfide
ores in the NE Belgian mining district are smithsonite,
willemite, hemimorphite and sauconite (Table 1; Figs. 4,
5 and 6). Minor hydrozincite is present, as well as
remnants of primary sulfides. Calcite was often
observed, both as gangue mineral, which precipitated
with the primary sulfides, and as a newly formed phase
associated with smithsonite. Idiomorphic quartz crys-
tals, as well as spherules of chalcedony occur as one of
the last generations to form, together with transparent
hemimorphite laths (Fig. 5f). Fe- and Mn-oxyhydr-
oxides and small kaolinite agglomerates are also very
common. Nonsulfide minerals from Belgium have been
investigated previously by several authors (Levy, 1843;
Cesàro, 1886, 1887, 1898, 1908; Servigne, 1943; Mélon
et al., 1976), and particular attention was devoted to
willemite. However, with the exception of de Launay
(1913) almost no paragenetic studies of the nonsulfide
associations that could be applied to a genetic interpre-
tation have been carried out.
 V. Coppola et al. / Ore Geology Reviews 33 (2008) 187–210 197

Fig. 5. SEM micrographs of Zn silicates from Belgian nonsulfide deposits. Smithsonite Types are classified as in Sardinia nonsulfide ores (see text): a)
La Calamine: willemite (will) replaces sphalerite (sph) crystals (RA5004); b) La Calamine: hexagonal crystals of willemite in a cavity (Museo
Mineralogia Univ. Napoli); c) La Calamine: microcrystalline terminations of willemite spheroids in botryoidal aggregates (A5013a); d) La Calamine:
internal structure of the willemite aggregate 3c; e) La Calamine: smithsonite Type I filling a vein in willemite (R2B35/3925); f) Fossey: aggregate of
tabular hemimorphite crystals (type II), covered by opal microspheres (RN2298).

6.1.1. Willemite forms of willemite agglomerates: a) masses of clear,

Willemite has been detected in all nonsulfide deposits
in Belgium, but it was especially common at La
Calamine. de Launay (1913) noted the preponderance
of microcrystalline willemite over smithsonite in the
lower levels of the mine. Locally, traces of incompletely
replaced sulfides are intergrown with willemite (Figs. 4b
and 5a). Our observations, both at the stereoscopic
microscope and on SEM, have shown at least two distinct
idiomorphic hexagonal, mm-sized crystals with prismatic
terminations (Figs. 5b and 7a) (Cesàro, 1886, 1887); and
b) brownish massive concretions with minute botryoidal
terminations (rhombohedral) in druses and radial con-
cretions (Figs. 4c and 5c, d). Microcrystalline, massive
willemite also cements a reddish-brown mottled breccia,
showing evidence of mechanical reworking and chemical
dissolution of a possible paleokarst infill (Fig. 4d).
198 V. Coppola et al. / Ore Geology Reviews 33 (2008) 187–210

Fig. 6. SEM micrographs of smithsonite from Belgian nonsulfide deposits. Smithsonite Types are classified as in Sardinia nonsulfide ores (see text):
a) Fossey: cluster of rombohedral smithsonite (Type I) in a cavity (RN2300a, Coll. Buttgenbach 1916); b) Moresnet: rombohedral smithsonite (Type
I) in a cavity (RN4106); c) Fossey: scalenohedral smithsonite crystals ((Type VI)) in aggregates (RN2301a, Coll. Buttgenbach 1916); d) Welkenraedt:
scalenohedral terminations of pseudocolloidal “turkey fat” smithsonite (Type V) (RN2236a); e) Fossey: Fe-smithsonite (“monheimite") Type among
hemimorphite laths (RN2298): f) enlargment of Fe-smithsonite crystals from (e).

The prismatic idiomorphic hexagonal crystals can
reach up to 1 mm in length (Fig. 5b) and their habits are
well observed in open cavities. This morphology has
been recorded in the specimens of La Calamine and
Welkenraedt, where the crystals are often fragmented,
partly dissolved on the external side and cemented by
later carbonate phases (Fig. 5e). The brownish rounded
concretions, consisting of masses of elongated hexag-
onal crystals emanating from the centers of numerous
minute spheres, have a diameter of about 800 μm.
Remnants of hexagonal willemite crystals form the
nucleus of the spheres (Fig. 7c). These concretions have
only been observed in specimens from La Calamine.
From the results of X-ray analyses, the cell
parameters of the Belgian willemites are in agreement
with the literature data (Simonov and Belov, 1970;
Marumo and Syono, 1971; McMurdie et al., 1986).
They are: a from 13.912(3) to 13.969(1) Å and c from
9.321(2) to 9.369(7) Å with a ratio a:c constrained from
0.6703 to 0.6720. No systematic variations were
 V. Coppola et al. / Ore Geology Reviews 33 (2008) 187–210
observed between the cell parameters and willemite
morphologies.
6.1.2. Smithsonite
Smithsonite has been detected in most samples
(Table 1). Macroscopically, this mineral occurs in several
habits. An extensive SEM study, carried out on a large
number of smithsonite-bearing specimens, revealed also
several types of micromorphologies. These will be
compared with micromorphologies recorded in Sardin-
ian (Boni et al., 2003) and Irish (Balassone et al., 2007-
this volume) smithsonites. Type I smithsonite corre-
sponds to rhombohedral, distinctly idiomorphic, and
often zoned types, with the best crystals growing on
external surfaces or in cavities (Fig. 4e, f, i). Type 1
crystals have been observed in specimens sampled from
several Belgian mines (RN2003a, RN4106, RN3834).
The sizes of single rhombohedra (Fig. 6a, b) range from
50 to 600 μm. Locally, there is evidence of superficial
corrosion on the faces of the rhombohedra, and Fe-
oxyhydroxide globular iron concretions occur on these
surfaces.
Another, less widespread morphological type of
smithsonite consists of scalenohedral crystals of various
colors from white to yellow, red and grey, that can reach
centimetric sizes and are coated by Fe–Mn-hydroxides.
Locally these grow on a microcrystalline smithsonite
substrate or as infilling of vugs and fractures (Fig. 6c).
This morphology has been observed mainly in the
samples from the Fossey mine (RN2301a, RN2208a),
but also at La Calamine (RA5014). This type does not
occur in Sardinia: it has been classified as Type VI.
Concretionary, collomorphous structures (Fig. 4g, h),
possibly deposited in open cavities of the vadose zone,
or completely replaced internal sediments, are other
types of smithsonite morphologies. In the colloform
structures, a polycrystalline aggregate of scalenohedral
crystals with sizes smaller than 50 μm, oriented along
the crystallographic c axis, has been called smithsonite
Type V. Locally, this type evolves in globular or
mammillary forms, observed hanging in the karstic
cavities of the vadose zone (similar to that found in
Sardinia; Boni et al., 2003). This morphology has been
observed in several samples from the Welkenraedt
mining area (RN4988, RN2236a, RA4986a) and from
La Calamine (RN2101, RN2280).
Fe-rich smithsonite has been identified by SEM–
EDS analyses in two samples from the Fossey mine
(RN2298, RN2208). It occurs as tabular aggregates with
a fibrous appearance (maximum size ca. 400 to 500 μm),
growing between corroded hemimorphite crystals
(Fig. 6e, f). This mineral could correspond to former
199
“monheimite”, an intermediate member of the smith-
sonite–siderite series (Palache et al., 1951; Sitzia, 1965;
Bak and Niec, 1978; Bak and Zabinski, 1981). The cell
parameters of the measured smithsonites vary from a
4.647(1) to 4.678(6) Å and c between 15.024(8) and
15.061(6) Å, and are in quite good agreement with
literature data (Effenberger et al., 1981; Chang et al.,
1996). There is no observed direct relationship, however,
between the measured cell parameters and the crystal
chemistry or morphologies of the Zn carbonates. The
Belgian “monheimite” is quite different from the
Sardinian one, but also from similar Fe-rich smithsonites
occurring in the Irish nonsulfides (Balassone et al.,
2007-this volume).
6.1.3. Hemimorphite
Hemimorphite, though less important than willemite
or smithsonite in the Belgian nonsulfide ores, has been
identified by X-ray analysis in several specimens from
all the sampled mine sites. It appears to have formed in
several phases: hemimorphite I occurs in the matrix of
supergene breccias (Fig. 4k) or replaces completely the
clasts cemented by a willemite matrix (Fig. 4d); hemi-
morphite II forms crystals growing freely in late cavities
(Fig. 4l). Observed in the SEM, hemimorphite occurs
with a typical tabular habit along the b axis. Hemi-
morphite occurrences in the late phase of nonsulfide
deposits suggest a strong mobility of SiO2 (Moore, 1972)
and a lower buffering capacity of the host carbonates
(Hitzman et al., 2003). The occurrence of minute spheres
of chalcedony on the hemimorphite laths (Fig. 5f) also
indicates high SiO2 activity.
The X-ray diffraction data for hemimorphite reveals
a slight variation of the cell parameters for the different
samples. Parameter a is constrained from 8.345(0) to
8.400(0) Å, b from 10.712(6) to 10.768(7) Å and c from
5.081(6) to 5.136(1) Å. The values of the parameters
reported in literature (McDonald and Cruickshank,
1967; Cooper et al., 1981; Libowitzky et al., 1997;
Boni et al., 2003) are in good agreement with the range
values for the hemimorphites analyzed here.
6.1.4. Sauconite
Sauconite belongs to the group of trioctahedral
smectites with monoclinic symmetry [(Na0.3Zn3(Si,
Al)4O10(OH)2·4(H2O)]. Sauconite is associated with
clayey bodies in most zinciferous ore deposits of
Belgium. Together with hemimorphite it has been
recognized as one of the components of a mixture of
Zn-minerals known as “vaneuxemite” (Frondel, 1972).
This Zn clay was identified as “moresnetite” by the local
miners in the Zn deposit of Moresnet-Altenberg (La
200 V. Coppola et al. / Ore Geology Reviews 33 (2008) 187–210

Calamine) and described by Esquevin (1957) as an oriented samples, showing the main peak at 14.8 Å [the
association of sauconite and fraipontite. In this study, (001) reflection]. After glycolation of oriented samples,
sauconite was analyzed by X-ray powder diffraction on the main peak shifted to 17.0 Å. Successive heating runs
 V. Coppola et al. / Ore Geology Reviews 33 (2008) 187–210 201

Table 2
Microprobe analyses of selected willemites, smithsonites and hemimorphites from Belgian “calamines”, pointing to compositional variations
Willemite
Sample # RN3834 RN5011 RA5012 RA5013 RA6661 RA6661a RN2300
SiO2 26.45 26.15 27.20 27.05 26.61 25.70 27.03 26.68 26.21 26.09 26.69 26.31 26.77 26.55
ZnO 73.24 73.79 71.71 71.72 72.01 72.68 70.65 71.78 74.03 72.98 71.78 72.28 71.53 72.27
FeO 0.05 0.03 0.09 0.48 0.18 1.18 0.04 0.23 0.03
MnO 0.03 0.03 0.02 0.02 0.03 0.03 0.09 0.02
CaO 0.05 0.03 0.03 0.02 0.08 0.06 0.05
MgO 0.08 0.05 0.03 0.05 0.04
Total 99.74 99.97 98.94 98.92 98.77 98.41 98.25 98.66 100.30 100.42 98.63 98.61 98.58 98.89

Smithsonite Hemimorphite
Sample # RN2008 RN3834 RN4106 RA4999 R2B34/2624 RN2051
ZnO 61.70 39.21 57.62 51.99 62.20 39.48 62.80 39.60 65.29 57.21 SiO2 26.44 25.92 25.99
FeO 0.13 13.96 0.71 6.38 0.48 14.76 0.62 14.02 0.85 ZnO 67.51 67.42 67.40
MnO 0.03 2.93 1.54 0.41 0.03 2.42 0.25 3.79 1.51 FeO 0.02
CaO 1.22 0.29 0.23 0.93 0.13 0.38 0.05 0.32 0.03 0.23 CaO 0.02
MgO 0.18 4.40 4.09 3.29 0.25 3.90 4.19 0.28 4.65 H2 O a 6.04 6.65 6.61
CO2 a 35.19 37.40 36.73 36.20 35.16 37.21 34.72 37.30 34.42 37.12
Total 98.45 98.19 100.91 99.19 98.25 98.15 98.44 99.22 100.02 101.56 Total 100.01 100.01 100.00
Trace amounts of Cd, Co, Cu and Ni were sporadically detected in smithsonite, whereas hemimorphite and willemite showed traces of Co, Cu and Ni.
a
Calculated from stoichiometry.

at 250, 350 and 550 °C, showed a constant decrease of
this peak to 11 Å, confirming the smectitic nature of this
clay phase (Fig. 7). Also SEM images show clearly the
typical lamellar structures of this class of phyllosilicates.
6.1.5. Other minerals
Other minerals in the mining district include
cerussite, anglesite, allophane, aragonite, barite, dolo-
mite, gypsum, pyromorphite, hopeite, fraipontite, kol-
beckite, siderite and kaolinite. The minerals hopeite
{Zn3(PO4)2·4H2O} (Brewster, 1822, 1824; Levy, 1843)
and fraipontite {(Zn,Al)3(Si,Al)2O5(OH)4} (Cesàro,
1886, 1887; Fransolet and Bourguignon, 1975) were
described for the first time in samples from La
Calamine. Additionally, several types of oxyhydroxides
are present: goethite, hetaerolite, braunite, manganite,
hematite and pyrolusite.
6.2. Geochemistry
The nonsulfide ores in Belgium were characterized
by a variably high Zn grade (N30 wt.%), contained
mainly in smithsonite and in the Zn silicates will-
emite N hemimorphite. The Pb grade (from residual and
neoformed galena and from cerussite) was generally low
(b5 wt.%), this also due to the lower Pb content in the
primary sulfide ore.
WDS microprobe analyses of smithsonite, willemite
and hemimorphite, from an average of 6 to 8 measured
points, are reported in Table 2. Zn content in smithsonite
ranges from 65.29 to 39.21 wt.% ZnO, the latter
encountered in exceedingly iron-rich varieties. In the
latter, FeO can reach 13.96 wt.% (in sample RN2008) and
14.76% and 14.02% (in samples RN4106 and RA4999
respectively). Fe-rich smithsonites (the so-called “mon-
heimite”), coexist in the same sample with Fe-poor
smithsonites and are generally the final phases to be
precipitated. MgO values range from 0.28 and 4.65 wt.%.;
CaO up to 1.22 wt.%, and trace amounts of Cd, Co, Cu
and Ni were also detected. Both willemite and hemi-
morphite are nearly stoichiometric, and show only minor
amounts of Fe, Mn, Ca, Co, Cu and Ni. Microprobe
analyses of several Belgian hemimorphite samples
(Table 2), reveal that they are very homogeneous (almost

Fig. 7. a) Moresnet: hexagonal crystals of willemite; fluid inclusions are visible as black dots (thin section, NII) RN5004; b) La Calamine: the same
area in CL shows a blue color and a zoned structure; c) La Calamine: botryoidal roundish aggregates of willemite. Remnant of a hexagonal crystal in
the nucleus of the aggregate (thin section, N+) RA6661, Coll. Buttgenbach 1916; d) La Calamine: the same area in CL shows a blue color and a zoned
structure. e) Welkenraedt: Fe-rich zoned smithsonite replaces idiomorph willemite (thin section, N+), RN2224; f) Welkenraedt: the same area in CL
shows almost no luminescence for willemite and a zoned texture (from dark red to blue for smithsonite; g) La Calamine: microcrystalline smithsonite
vein cutting willemite (thin section, N+) RN2051; h) La Calamine: the same area in CL shows the dark colors of willemite and the zoned structure
(from blue to red-orange) of the smithsonite vein.
202 V. Coppola et al. / Ore Geology Reviews 33 (2008) 187–210

stoichiometric) in their composition. The only excep-
tions have been encountered in few samples from La
Calamine, where Al3+ and Fe2+ can reach 0.025 a.p.f.u.
and 0.145 a.p.f.u., respectively.
On the basis of chemical analyses performed by
ICP-MS, the Zn content in smithsonite varies from
44.77 to 54.28 wt.% (Table 3). Among the other
elements, Ca, Mn and Mg are lower than 1 wt.%, and
Fe is variable between 0.05 and 6.78 wt.%. The average
trace element composition of 11 smithsonite samples
also reveals high Pb (88 to 9052 ppm), variable Cu (3 to
162 ppm) and Co (3 to 128 ppm) contents. Ag (average
1 ppm) and As (average 10 ppm) are comparably low.
Ni and Cd are particularly abundant, the former ranging
from 35 to 921 ppm, the latter from 100 to N2000 ppm.
In the Fe-smithsonites, Zn is close to 27 wt.%, while Fe
ranges from 11.98 to 18.49 wt.%. Among the
smithsonites, the Fe-rich phases (“monheimite”) could
be distinguished through their high Fe content (from 10
to 18 wt.%), and consequently relatively low Zn values
(from 27 to 32 wt.%).
Zn contents in the willemite-rich samples range from
58.87 and 63.40 wt.% (Table 3). Fe and Mn contents are
higher in the reddish microcrystalline willemite occur-
ring in the breccia matrix, and much lower in the
isolated crystals. This could be an evidence of Fe–Mn
oxyhydroxide impurities around the former, typical of a
supergene environment. The trace element composition
of 4 willemite samples reveals again variable Cu (0 to
290 ppm), Ag and Co below detection limit, lower Pb
than in smithsonite (150 to 1790 ppm) and higher As
(73 to 98 ppm). Ni has been detected (7 to 217 ppm) in
all the willemite specimens whereas, in contrast to
smithsonite, Cd is absent.
7. Petrography and paragenesis
Willemite, characterized by high-order interference
colors when observed under crossed nicols, was the first
mineral to be deposited within the nonsulfide assem-
blage. Often, it can clearly be seen that a patchwork of
willemite crystals has replaced directly the collomorphic
concretions of “Schalenblende” (Dejonghe and Boni,
2005; Fig. 4b), or crystals of sphalerite (Fig. 5a). As
already established from the SEM analysis, two types of
willemite exist: (i) idiomorphic–pseudoidiomorphic
crystals with hexagonal habit and (ii) botryoidal
aggregates composed of acicular radiated crystals. The
hexagonal crystals appear deep blue when observed
using the cold CL microscope (Fig. 7b), whereas the
botryoidal concretions, although still displaying shades
of blue, have a luminescence that varies in intensity
from the center to the margins of the concretion
(Fig. 7d). In a few cases, a time relationship between
these two willemite types could be deduced. Locally, the
center of the rounded willemite concretions appears to

Table 3
ICP-MS analyses of major and trace elements in selected willemites and smithsonites nonsulfide Zn–Pb deposits
Zn Fe Mn Ca Mg Cd S Pb Cu Ag As Ba Be Co La Li Ni
% % % % % % % ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm
Willemite
RA5012 63.40 0.37 n.d. 0.03 0.01 n.d. 0.10 1790 290 21 98 4 79 b1 0 51 7
RA6661a 61.28 0.79 0.01 0.08 0.04 n.d. b0.10 240 5 1 91 13 35 1 10 29 73
RA5013a 61.62 0.47 n.d. 0.04 0.04 n.d. 0.30 150 b0.1 b0.1 73 17 26 1 3 19 53
RA5013b 58.87 0.84 n.d. 0.03 0.07 n.d. b0.10 280 2 b0.1 77 12 36 3 6 31 217

Smithsonite (+ Fe-smithsonite)
RN2208a 54.28 0.11 0.01 0.01 0.03 0.01 b0.05 127 9 b0.1 b0.5 b1.0 n.d. 12 b1.0 n.d. 169.1
RN2008b 27.63 11.98 0.58 5.52 1.04 n.d. b0.05 192 14 1 9 54 n.d. 21 6 n.d. 120.8
RN2017 50.70 1.65 0.10 0.14 0.25 0.03 b0.05 105.4 7 2 6 4 n.d. 11 b1.0 n.d. 220.7
RN2044b 52.66 1.27 0.04 0.22 0.15 0.03 b0.05 106 6 b0.1 4 6 n.d. 3 b1.0 n.d. 224.4
RN4106 44.77 3.57 0.67 0.33 1.36 0.01 b0.05 88 3 b0.1 6 10 n.d. 59 14 n.d. 567.2
R2B35/3925 32.10 10.68 0.44 8.50 1.27 n.d. b0.10 210 b0.1 0 b1.0 54 14.0 16 16 15.4 297.6
RN2300b 50.63 6.78 0.08 0.15 0.13 b0.1 0.40 1410 40 2 106 16 45.0 5 25 73.7 921.2
RN2220a 48.42 1.76 0.84 0.09 0.11 0.11 0.08 9052.7 8 1 1 1 n.d. 129 1 n.d. 296.2
RN2220b 51.99 1.08 0.47 0.10 0.06 0.15 b0.05 1724.2 4 1 1 1 n.d. 71 1 n.d. 140.8
RN2236b 52.25 0.05 0.12 0.15 0.02 0.19 b0.05 422 25 0 b0.5 1 n.d. 13 2 n.d. 110.5
RN2242a 27.07 18.49 1.00 0.32 1.25 0.03 b0.05 2869.4 55 11 16 7 n.d. 120 2 n.d. 141.1
RN2270b 50.15 0.46 0.38 0.91 0.21 0.05 b0.05 3533.8 162 2 4 67 n.d. 14 48 n.d. 418.9
RA4986a 51.36 0.86 0.02 0.37 n.d. 0.50 b0.05 9792.7 9 1 52 1 n.d. 6 35 n.d. 36
 V. Coppola et al. / Ore Geology Reviews 33 (2008) 187–210 203

be a fragment of one of the idiomorphic hexagonal
crystals (e.g., RA6661 and RA6661a) (Fig. 7c), whose
form can be clearly recognized by CL. This relationship
indicates that the idiomorphic willemite crystals can be
considered to be the precursor of the roundish concre-
tions. In some samples from the Welkenraedt mine
(RN2224), euhedral willemite is cut and locally replaced
by idiomorphic rhombohedra of Fe-rich zoned smith-
sonite (Fig. 7e), while thin and/or platy hemimorphite
crystals and rare hydrozincites represent the last
generation of the nonsulfide assemblage.
As mentioned above, smithsonite occurs in different
generations and as aggregates with variable forms. Zn
carbonate can be present as microcrystalline sediment of
subidiomorphic crystals, but it occurs also as clear
rhombohedral (Type I) or scalenohedral (Type V)
crystals growing in geodes or in fractures. Only the
rhombohedral crystals show well developed cleavage
traces. Smithsonite can also replace earlier willemite
(Figs. 5e and 7g) and (locally) hemimorphite (i.e., at La
Calamine). When observed under cold CL microscope,
smithsonite displays a zoned luminescence, with colors
varying from deep blue to deep red (Fig. 7f) or orange
(Fig. 7h). It is generally regarded that red or orange
luminescence colors in carbonates, including smithson-
ite, are strongly influenced by the Mn content (as CL

Table 4
Carbon and oxygen isotope data of Zn, Pb, and Ca carbonates from Belgian “calamine”
Sample Mineral Description Location δ13C V-PDB δ18O V-SMOW Ave Std.
(‰) (‰) dev.
RN1996a sm a Clear rhombohedral crystals, outer part (Type I) Moresnet −9.8 28.8
RN1996b sm Yellowish crust, inner part (Type I) Moresnet − 11.6 28.2
RN2008b sm Yellow scalenohedral crystals on RN2008c (Type VI) Moresnet −8.6 28.1
RN2008c sm Brownish massive matrix of breccia Moresnet −8.8 28.1
RN2008b sm Yellow scalenohedral crystals on RN2008c (Type VI) Moresnet −8.6 28.1
RN2101c sm Late clear crystals Moresnet −10.9 28.1
RN4106 sm Reddish-brown banded sediment Moresnet −7.4 30.6
RN2017 sm White crystals on globular smithsonite La Calamine −10.7 28.3
RN2044c sm Yellowish crystals La Calamine −1.5 28.1
RN2051a sm a Brownish matrix of mottled breccia and veins La Calamine −9.8 28.7
RA4999a sm a Greyish central part of concretion (Type V) La Calamine −6.2 28.0
RA4999b sm a Yellowish porous outer part of concretion (Type V) La Calamine −6.6 27.4
R2B35/ sm Brownish massive or veins La Calamine −9.2 28.4
3925
RN2208a sm a Yellowish clear crystals, outer part Fossey − 11.6 28.3
RN2208c mo Brownish massive matrix (Fe-rich) Fossey −7.6 30.2
RN2300d sm Clear rhombohedral crystals (Type I) Fossey −10.2 28.6
RN2220a sm Black sulfide-bearing crystals, inner part Welkenraedt −10.1 28.9
RN2220b sm Yellowish clear crystals, outer part Welkenraedt −10.2 28.2
RN2224b sm Zoned Fe-rich brown rhombohedral crystals (Type I) Welkenraedt −8.4 29.5
RN2236a sm Globular greyish concretion, outer part (Iype V) Welkenraedt −7.1 27.2
RN2236b sm Brownish massive inner part (Type V) Welkenraedt −3.2 27.1
RA4986a sm White botryoidal concretion (Type V) Welkenraedt −8.9 28.2
RN2270a sm a White concretion, outer part (Type V) Theux −2.2 27.7
RN2270b sm Brownish, massive inner part (Type V) Theux −1.6 28.1 28.4 0.8
RN2487b cc Green botryoidal crust on will. Moresnet −10.4 24.7
Be4a cc White vitreous crystals in the oxidation zone La Calamine −7.4 25.7
Be5b cc Red vitreous crystals associated to smithsonite La Calamine −6.5 25.5
Be8c cc Red vitreous crystals associated to smithsonite La Calamine −6.5 25.7
Be9b cc Red vitreous crystals associated to smithsonite La Calamine −6.1 25.5 25.4 0.4
Be1a dol Black massive dolomite (wall rock) La Calamine 2.8 16.4
Be2b dol Black massive dolomite (wall rock) La Calamine 2.8 19.5
RA 7898 ce Fibrous crystals Theux −14.7 17.6
RA 8497 ce Clear crystals Theux −15.0 17.2
RN 2330 ce White fibrous crystals Theux −14.8 16.8
RA 8494 ce Fibrous crystals Angleur −15.1 18.4
RN 2339 ce Greyish massive aggregate Welkenraedt −18.4 19.3 17.8 1.0
Abbreviations: sm = smithsonite; mo = Fe-rich smithsonite (“monheimite”); ce = cerussite; cc = calcite; do = dolomite.
a
Mild acid treatment to remove calcite.
204 V. Coppola et al. / Ore Geology Reviews 33 (2008) 187–210

activator) in the carbonate lattice (Götte and Richter,
2004). From chemical analyses, both in WDS and ICP-
MS, all the smithsonites are enriched in Mn.
Hemimorphite I, consisting of very small, radiated
crystals with lower-order interference colors, can replace
the macrocrystals of willemite starting from their
margins (Fig. 4d, k). Hemimorphite in radial aggregates
occurs also as vein-fillings, cutting both limestone and
nonsulfide masses. It is often associated with Fe–Mn-
(oxy)hydroxides, but its relationship with smithsonite is
not yet clear. Although the prismatic smithsonite crystals
in concretions can often be considered as the last
generation occurring in the nonsulfide deposits, there is a
second apparently even younger generation of platy
hemimorphite crystals (hemimorphite II) growing on
them (Fig. 4l). Sauconite and other clay minerals are
interspersed with the other nonsulfide minerals, mostly
with hemimorphite I. A late generation of quartz mi-
crocrystals occurs mainly as inclusions in carbonates,
or crystallizes as subidiomorphic individual crystals in
veins (RN3403).
8. Fluid inclusions
A fluid inclusion study has been carried out on
smithsonite, quartz and willemite of the nonsulfide ores,
in order to obtain information on the temperature and
salinity of the fluids involved in the formation of the
secondary ore deposits. Due to the brittle nature of
willemite, samples needed to be handled very carefully
during section preparation, avoiding rough or prolonged
(unnecessary) polishing steps and avoiding the use of
heating in resin-mounting the sections. In order to
minimize the risk of induced stretching and/or leakage,
inclusions were also heated very slowly during analysis,
to avoid the risk of overheating.
Only monophase (liquid) inclusions, both primary
and secondary, have been observed in smithsonite and in
few, very late quartz crystals. In these inclusions, after
several freezing and subsequent melting cycles, no
bubble could be generated. The predominant occurrence
of monophase inclusions points to a formation of these
minerals at temperatures below about 70 °C (Roedder,
1984, p. 292). More interesting – though problematic –
data were obtained from fluid inclusion measurements of
willemite samples, representative of a small number of
mine localities (Boni et al., 2005). The dimensions of the
inclusions observed in willemite, range between 2 and
30 μm. 80% of them are monophase (L) and 20% liquid-
rich two-phase (L + V). Secondary monophase inclu-
sions are very common: they are lined along a network of
small fractures crossing the contacts between crystals,

Fig. 8. Plot of δ13C vs. δ18O for various Pb, Zn and Ca carbonates (smithsonite, cerussite and calcite cogenetic with the former minerals) from Belgian
calamine ores. The open circles represent early diagenetic Tournasian dolomite hosting La Calamine deposit. Field 1 depicts the isotope compositions
of Dinantian limestones and Variscan veins throughout the mining district (Muchez et al., 1994). The isotope values of the hydrothermal calcite
gangue of the Bleiberg primary sulfides are concentrated in field 2, while field 3 comprises all the published values for several generations of
Dinantian dolomites (Nielsen et al., 1994).
 V. Coppola et al. / Ore Geology Reviews 33 (2008) 187–210
but some secondary two-phase have been also encoun-
tered. More than 60 of the two-phase inclusions, both
primary and secondary in origin, have been measured.
Widespread necking-down and leakage phenomena
were detected, and those inclusions were avoided,
using as the main criteria, the shape and excessive
dispersion of the vapor/liquid ratio (cf. Roedder, 1984).
Homogenization temperatures (Th) ranging between 80
and 190 °C were subsequently obtained from a set of
reliable willemite inclusions (Boni et al., 2005). No
apparent correlation could be detected between size and
temperature of the measured fluid inclusions.
The ice melting temperatures (Tm) suggest salinities
between 0 and 5 wt.% NaCl equiv. (Bodnar, 1993;
Goldstein and Reynolds, 1994), and the few first
melting temperatures (Te) (− 18 to − 23 °C) indicate
that the aqueous fluids were dominated by NaCl in
solution (Roedder, 1984).
9. Stable isotope geochemistry
The results of oxygen and carbon isotope measure-
ments on smithsonite, cerussite, calcite and two wall-
rock dolomite samples from La Calamine (Moresnet),
Welkenraedt, Fossey, Theux and Angleur mines are
presented in Table 4 and depicted in Fig. 8.
9.1. Zn and Pb carbonates
Smithsonite exhibits a limited range of δ18O values
from 27.1 to 30.6‰, with an average value of 28.4‰ ±
0.8‰ (1σ, n = 23) with most analyses ranging between 27
and 29‰. There is no systematic difference in δ18O
values from different deposits or between petrographic
types. This indicates a relatively uniform isotope
composition of the oxidizing water, and constant
temperatures of smithsonite crystallization (Boni et al.,
2003; Gilg and Boni, 2004). The oxygen isotope value of
iron-rich smithsonite (“monheimite”) RN2208c is higher
than that of the Fe-poor smithsonites. Similarly, sample
RN4106, a neoformed internal(?) sediment replaced by
smithsonite, has an oxygen isotope value that is about 2‰
higher than the average of all other smithsonites. In
contrast to oxygen, carbon isotope values of smithsonites,
even from the same mine site, show a considerable range
from −11.6 to −1.6‰. There is, however, no relationship
between the stable carbon isotope composition and crystal
morphology as was observed for smithsonites from the
Iglesiente district, Sardinia (Boni et al., 2003). Cerussites
have oxygen isotope values ranging from 16.8 to 19.3‰
with an average value of 17.8 ± 1.0‰ and carbon isotope
values of −18.4 to −14.7‰. The isotope compositions of
205
smithsonite and cerussite from Belgium (Fig. 8) are very
similar to those from the Iglesiente district, Sardinia,
which are considered as typical for supergene carbonate-
hosted nonsulfide Zn–Pb deposits (Boni et al., 2003; Gilg
and Boni, 2004).
9.2. Ca and Ca–Mg carbonates
Some calcite samples associated with the calamine
ores were also investigated (Fig. 8). Sample RN2487b
from La Calamine consists of a yellow-orange concre-
tion growing on late smithsonite crystals. The other
calcites are reddish crystals occurring in veinlets
together with nonsulfide ore minerals at the margin of
the former La Calamine deposit. The δ13C values of the
calcites show a small range from − 10.4 to − 6.1‰,
while the δ18O values cluster around 25.5 ± 0.5‰, about
3‰ lower than those of smithsonite. The isotope values
of calcite from calamine ores are again identical to those
from the Iglesiente district. The δ13C values of two
diagenetic dolomites, considered as the host rock of the
La Calamine deposit, are clearly positive (2.81 and
2.75‰), while their δ18O values are 16.4‰ and 19.5‰,
respectively. These results are broadly comparable to
published data (Fig. 8) on Dinantian dolomites from
Eastern Belgium (Nielsen et al., 1994).
10. Discussion and conclusions
Most characteristics of the nonsulfide Zn–Pb ores in
Eastern Belgium point to supergene weathering pro-
cesses of primary sulfides, and reprecipitation of metal
silicates and carbonates from oxidized solutions in
karstic cavities and host rock discontinuities. These
processes included deep karstification and development
of oxidation–cementation profiles in the mineralized
sections, with deposition of Zn(NPb) secondary non-
sulfides. As in most supergene deposits, a moderate
tectonic uplift and brittle fracturing occurred, and this
paired with favourable climatic conditions (hot and
humid), were the key factors for the development of
extensive weathering profiles. In this context, it should
be mentioned that the European geological record
reveals a series of Mesozoic and Tertiary time intervals,
during which deep weathering profiles were established,
many of which have been widely preserved (Migoñ and
Lidmar-Bergström, 2001). These weathering profiles
have been recognized in several areas of Europe
including Scandinavia, the British Isles, France, Ger-
many, Austria, Poland and of course Belgium (Boni and
Large, 2005). In the Verviers Synclinorium, both the
primary sulfides deposits and some “calamines” have
206 V. Coppola et al. / Ore Geology Reviews 33 (2008) 187–210
been truncated by erosion and are unconformably
covered by the sediments of the Late Cretaceous
Aachen Formation (Fig. 3a, b). It is highly probable
therefore, that at least part of the nonsulfide deposits
were formed by the same pre-Late Cretaceous paleo-
weathering processes that produced the kaolinized
regoliths on siliciclastic lithotypes well known else-
where in the region (Dejonghe and Boni, 2005). Further
evidence for the genesis of the nonsulfide deposits
during paleoweathering phases is the fact that the depth
of oxidation in most primary sulfide veins and
associated flats reached substantially below the pres-
ent-day water table (more than 100 m in depth from
surface outcrops at La Calamine).
The predominance of willemite, often pervasively
replacing earlier sphalerite, in the lower levels of the
giant La Calamine deposit, as well as in other smaller
mines throughout Eastern Belgium, contrasts with the
typical mineral assemblage of smithsonite and/or
hemimorphite found in most European supergene
nonsulfide ores. Willemite does not appear to replace
the host carbonates or siliciclastic rocks, but only the
sulfide assemblages. Thus, a distinct event of sulfide
oxidation, followed by willemite precipitation in condi-
tions of high silica activity, has to be postulated for the
Belgian deposits. This early willemite was later partially
replaced by the typical assemblage of smithsonite and
hemimorphite. No willemite was deposited after
smithsonite or hemimorphite. The physico-chemical
conditions and geological scenario of willemite forma-
tion in the Verviers district of Eastern Belgium,
however, remain unclear. Thermodynamic considera-
tions (e.g., Markham, 1960; Takahashi, 1960; Brugger
et al., 2003) imply that willemite is a more stable phase
than hemimorphite at lower water activities and/or
higher temperatures (Ingwersen, 1990), although the
thermodynamic properties of hemimorphite and of the
Zn clay minerals, are still not very well constrained
(e.g., Ingwersen, 1990; McPhail et al., 2004). Willemite
should prevail over smithsonite under conditions of
higher silica activity, lower CO2 fugacity, and higher
temperature. At La Calamine, high silica activity in the
alteration fluid may have been buffered by the dolomitic
wall rocks that are slightly siliceous.
Recent studies (e.g., Sweeney et al., 1991; Monteiro
et al., 2000; Brugger et al., 2003; Hitzman et al., 2003)
have suggested that willemite formed in some non-
sulfide Zn deposits of the southern hemisphere (e.g.,
Vazante, Beltana, Star Zinc, Berg Aukas) under
hydrothermal conditions at temperatures in excess of
100 °C. The mineralizing fluids were interpreted as
oxidized, acidic sulfur-poor brines with salinities of 4 to
22 wt.% NaCl equiv. (Hitzman et al., 2003). The
hypogene willemite mineralization is often accompa-
nied by a pervasive hematitization and carbonatization
(ferroan dolomite). At La Calamine however, willemite
mineralization does not have the structural and para-
genetic characteristics of hypogene nonsulfide Zn de-
posits described by Hitzman et al. (2003). Salinities of
willemite-hosted fluid inclusions are also much lower
than those reported in hypogene deposits (Hitzman
et al., 2003) and the majority of fluid inclusions
suggest formation temperatures below 70 °C. The
presence of few two-phase inclusions with homogeni-
zation temperatures of 80 to 190 °C may be caused
either by post-entrapment modifications of the fluid
inclusion density related to heating or to tectonically
induced deformation (Boni et al., 2005), or by
heterogeneous entrapment of air and water within the
vadose zone. Therefore, we do not consider these high
homogenization temperatures as reliable minimum
temperature estimates of primary willemite formation.
Thus, the willemite bodies occurring in the deeper
zones of most Belgian deposits were deposited either
during weathering processes which took place under
conditions of peculiar aridity and silica activity, or
because of a very low-temperature hydrothermal event.
A rather special weathering phase, paired with arid
conditions (e.g., Pough, 1941) to account for the high
silica content, moderately low salinity, and thus low
water activity of the oxidizing fluids cannot be ex-
cluded at present. We are not able to envisage a pos-
sible timing of such hypothetical arid climatic phase in
this part of Europe after the deposition of the primary
sulfides. Alternatively, a low-temperature hydrother-
mal overprint must be considered.
We note here that a variety of active, low-
temperature (b 70 °C) hot springs occur within the
area of the Pb–Zn mineralization, e.g., Chaudfontaine
(Graulich, 1983) or the Aachen district (Beyer, 1995;
Herch, 2000), all located along the SE dipping
Variscan thrust zones. Their waters are mixtures of
deep (N 3500 m), highly mineralized thermal fluids
and cool meteoric waters from a shallow reservoir
(Herch, 2000). The salinity of the Aachen hot spring
fluids is moderately low (about 4000 ppm TDS), but
their silica content is high (about 30 ppm Si), and the
fluids are oxidized (sulfate-dominated). Thus, similar
low-temperature hot spring fluids would have been
potentially capable of forming the willemite-rich
deposits from their sulfide precursors. Such a scenario
could also explain the mineralogical composition, the
apparently localized process, and the fluid inclusion
data.
 V. Coppola et al. / Ore Geology Reviews 33 (2008) 187–210
The range of isotope compositions of Zn, Pb and Ca
carbonates from the calamine ores in Belgium overlap
considerably with those found in the supergene Zn–Pb
ores of the Iglesiente district, Sardinia (Boni et al., 2003;
Gilg and Boni, 2004). We only note a slightly smaller
range of carbon isotope values from the Belgian
cerussites that is probably related to a limited set of
samples (n = 5) as compared to those from Sardinia
(n = 10). The broad range of carbon isotope values of Zn,
Pb and Ca carbonates points to at least two sources of
carbon: a 13C-depleted carbon (derived from the organic
matter of C3 plants in the overlying soils) and a 13C-
enriched carbon, originated from dissolution of the
carbonate host rocks. The relatively small variability of
oxygen isotope values for the carbonate minerals (b1%,
1σ) suggests that both temperatures and oxygen isotope
composition of the waters did not change much during
oxidation. Also the isotope data of Ca carbonates from
SW Sardinia suggest that local meteoric waters did not
change significantly during the Mesozoic to the present
(Boni et al., 2003). Present-day meteoric waters in NE
Belgium have δ18O values of − 6.8 to − 8.1‰ (Rozanski
et al., 1993; Beyer, 1995), slightly heavier than the
values of meteoric waters in the Iglesiente district
(− 6.5‰). Gilg (2000) showed that paleometeoric waters
responsible for deep kaolinization in Central Europe
from Cretaceous to Neogene, were heavier than present-
day meteoric waters. Thus, our isotope data of Zn, Pb
and Ca carbonates of the Belgian calamine are
consistent with an old age of weathering.
In conclusion, we know that the metallic ore deposits
in Eastern Belgium have undergone a polyphase history
which started possibly in the Jurassic with a hydrother-
mal sulfide mineralization (Heijlen et al., 2001),
followed by sulfide oxidation under high silica activity
(hydrothermal? supergene?), and then by unambiguous
supergene weathering. At least the processes causing
willemite deposition could have had a pre-Santonian
timing, in common with other paleoweathering evi-
dence in Western Europe. We cannot exclude however,
that the deposition of the abundant willemite concentra-
tions, occurring at the base of the Belgian nonsulfide
deposits, could have been derived from low-tempera-
ture, localized hydrothermal processes operated by
deeply reaching oxidizing fluids, that might have
followed only shortly the emplacement of primary sul-
fide mineralization.
Smithsonite and hemimorphite, often developed at
the expenses of willemite, occur in the upper parts of the
nonsulfide orebodies. They have all the characteristics
of pure supergene oxidation products, whose emplace-
ment age is still highly speculative.
207
Acknowledgments
This is the third contribution to an EC-funded project
(M. Boni and L. Dejonghe) on “The nonsulfide Zn ores
in Belgium: A new perspective” that used the facilities
of the Royal Belgian Institute of Natural Sciences
(RBINS) and Geological Survey of Belgium (GSB).
The help of O. Retout and I. Van de Velde (international
co-operation RBINS, management of the Access to
Belgian Collections Programme) and M. Deliens
(curator of the mineralogical collection at RBINS)
is warmly acknowledged. We also want to thank Prof.
M.R. Ghiara of the Museo di Mineralogia dell'Univer-
sità di Napoli for allowing us to sample some willemite
specimens, and Uli Struck of University of Munich for
his help with the isotope measurements. Thanks are also
due to T. De Putter and to an anonymous referee, who
improved a first version of this manuscript and to Dr.
Terry Williams of NHM for checking the English text.
The first author is also indebted to Gaia for support.
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