©2005 Society of Economic Geologists, Inc.

Economic Geology, v. 100, pp. 63–86

Ore-Forming Processes in Irish-Type Carbonate-hosted Zn-Pb Deposits: Evidence from

Mineralogy, Chemistry, and Isotopic Composition of Sulfides at the Lisheen Mine
J. J. WILKINSON,† S. L. EYRE,*
Department of Earth Science and Engineering, Royal School of Mines, Imperial College London,
Exhibition Road, London SW7 2AZ, United Kingdom

AND A. J. BOYCE
Scottish Universities Environmental Research Centre, East Kilbride, Glasgow G75 0QF, Scotland

Abstract
Lisheen is a strata-bound zinc-lead deposit formed during the Mississippian by replacement of hydrother-
mally dolomitized, grossly stratiform breccia bodies located near the base of the Carboniferous Waulsortian
Limestone. It represents one of a number of carbonate-hosted massive sulfide ore deposits in the Irish ore field
that, due to several unique features, have been classified as Irish type.
Disseminated pyrite occurs in preore dolomite and around the margins of preore dolomite clasts within
dolomite breccias. Early fine-grained sphalerite-pyrite mineralization occurs as infill of intergranular dolomite
porosity. Locally, massive to semimassive iron sulfide is observed, mainly comprising pyrite with lesser marca-
site. A complex polymetallic sulfide assemblage typifies the main ore stage, dominated by fine-grained dis-
seminated, massive or colloform sphalerite and galena, with minor pyrite, chalcopyrite, arsenopyrite, tennan-
tite, nickel- and cobalt-bearing minerals. Silver occurs in solid solution in tennantite, galena, and sphalerite.
Dolomite and barite dominate the gangue, with lesser calcite. Main-stage mineralization involved the progres-
sive replacement of preexisting iron sulfides and the dolomite breccias, initially by replacement of the breccia
matrix and ultimately by replacement of clasts. Coarse crystalline sphalerite and euhedral galena crystals are
generally restricted to fracture-fill mineralization or vugs within main ore-stage assemblages where they occur
with euhedral dolomite and calcite.
Barite intergrown with main ore-stage sulfides has δ34S values of 14.3 to 18.1 per mil, consistent with the de-
rivation of sulfate from coeval Carboniferous seawater. The δ34S values for sulfides range from –44.1 to +11.8
per mil, with a mean value of –13.7 per mil, typical of the Irish ore deposits. The dominant low δ34S signature
is considered to be the result of bacterial reduction of coeval seawater sulfate. Extremely low δ34S values, in
the range of –38 to –44 per mil, are only observed in preore disseminated pyrite; such extreme fractionations
are thought to be due to low bacterial sulfate reduction rates coupled with oxidative cycles in near-sea floor
pore waters. Main ore-stage sulfides have δ34S values in the range of –4 to –18 per mil, with a mode of –10 per
mil, consistent with a typical bacterial fractionation from coeval seawater sulfate. Isotopic equilibrium between
cogenetic sulfides is not observed. The bacteriogenic sulfur component was probably transported from bacte-
rial colonies fringing the ore system by low-temperature brines.
The δ34S values of late ore-stage sulfides mainly range from –20.2 to +12.0 per mil, with the majority having
relatively high values (mean = –3.0 ± 8.5‰, 1σ) interpreted as being due to the presence of a hydrothermal
sulfur component, leached from the lower Paleozoic basement. For galena and sphalerite there is a general in-
crease in δ34S values with depth in the system, with time, and with proximity to east-west– and northwest-
trending faults. These relationships suggest that input of hydrothermal sulfur from depth via fractures became
increasingly important. Hydrothermal sulfur appears to be more important at Lisheen than the other major
Irish deposits.
Galena lead isotope analyses gave average 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb values of 18.183, 15.594,
and 38.080, respectively. These data do not correlate with ore-stage, galena texture or δ34S. The results are
comparable to previous data from Lisheen and from Silvermines, 35 km to the west, implying a common lead
source in the lower Paleozoic basement.
The textural, mineral, chemical, and isotopic evidence suggests that main-stage ore was precipitated as a con-
sequence of rapid supersaturation, caused by fluid mixing within the permeable dolomite breccias. This
process involved relatively high temperature (ca. 240°C), metal-bearing solutions derived from a basement-
equilibrated fluid reservoir (carrying Zn, Pb, Fe, Cd) and shallow, saline (ca. 25 wt % NaCl equiv) formation
waters rich in bacteriogenic H2S. Minor metals (Cu, As, Ni, Co) are thought to have been stripped from the
footwall Old Red Sandstone during hydrothermal alteration around fault conduits. The availability of abundant
seawater sulfate, operation of open-system bacterial sulfate reduction, and episodic availability of free oxygen
imply that ore formation cannot have occurred at significant depth below the paleosea floor. Cessation of min-
eralization was due to a cut-off of the sulfur-rich brine supply, possibly by deposition of impermeable hanging-
wall sediments. This process of ore formation is consistent with evidence from the other economic Irish-type
deposits in the ore field.

† Corresponding author: e-mail, j.wilkinson@imperial.ac.uk

*Present address: TLC Ventures Corporation, Suite 285–200 Granville Street, Vancouver, British Columbia, Canada V6C 1S4.

0361-0128/01/3486/63-24 $6.00 63
64
Introduction
THE LISHEEN DEPOSIT, situated in County Tipperary, Ireland
(Fig. 1), is the most recent of six carbonate-hosted Zn-Pb de-
posits to have been discovered in the Irish ore field in the last
35 yr. Found in 1990 by a Chevron Mineral Corporation-Iver-
nia West joint venture, the deposit began production in late
1999. It contained a total premining resource (undiluted) of
16.7 million metric tons (Mt) of ore, grading 14.1 percent Zn
and 2.4 percent Pb (weighted average calculated from Fus-
ciardi et al., 2003), together with approximately 16 percent Fe
and 26 g/t Ag (Elmes et al., 2000). The ore is hosted princi-
pally by carbonate breccias near the base of the Mississippian
(Courceyan) Waulsortian Limestone. The deposit is the most
significant of a number of mineralized occurrences in the
Rathdowney trend of the southern Midlands (Fig. 1) that in-
clude the Galmoy deposit (Doyle et al., 1992), 10 km to the
northeast. Lisheen, together with the deposits of Galmoy,
Navan, Tynagh, and Silvermines, represents the deposit class
known as “Irish-type” as redefined by Wilkinson (2003).
Early studies at Lisheen (Hitzman et al., 1992; Earls, 1994;
Shearley et al., 1995, 1996) provided the initial geologic
framework for the deposit. This work showed that Lisheen
has geologic affinities with the other Waulsortian-hosted de-
posits of Galmoy and Silvermines (B and G zones). Mineral-
ization in all three deposits is hosted primarily by dolomite
breccias, the so-called “black matrix” or “rock matrix” brec-
cias. Recently, Hitzman et al. (2002) and Fusciardi et al.
(2003) presented geologic descriptions of the deposit and
preliminary genetic models. Here we report the results of a
detailed petrological and geochemical study of the deposit,
carried out as part of a Ph.D. research project between 1994
and 1998 (Eyre, 1998). This study builds on previous work
and provides new insights into ore-forming processes at
Lisheen. In this paper, we concentrate on the mineralogy and
chemistry of the sulfide ore, together with sulfur and lead
isotope evidence for the sources of metals and sulfur in the
deposit. The nature and causes of spatial and temporal
LEGEND
Namurian-Westphalian
Dinantian Navan
Old Red Sandstone
Caledonian Granite
Silurian
Ordovician
Precambrian
Tynagh
Leinster
Lough nd
Derg Tr
e Massif
y faults (Hitzman et al., 2002; Carboni et al., 2003; Fusciardi et
ne
Silvermines w
h do
at Galmoy
R
Lisheen
0 km 30
FIG. 1. Simplified geologic map of the Irish Midlands, showing location of
major deposits.
0361-0128/98/000/000-00 $6.00
WILKINSON ET AL.
variations in mineral chemistry and isotopic systematics are
considered and compared with data from other deposits in
the ore field. The geochemical, fluid inclusion, and isotopic
studies of carbonate alteration and fluid evolution in the de-
posit will be presented elsewhere.
Geologic Setting
The Irish deposits are hosted by a Lower Carboniferous
marine transgressive sequence that conformably overlies a
terrigenous clastic red-bed succession (Old Red Sandstone)
of Devonian-Carboniferous age. This lies unconformably on a
peneplained basement of Silurian graywackes, siltstones,
shales, and volcanic rocks that were deformed and weakly
metamorphosed in the Caledonian orogeny. Mineralization is
hosted by a variety of carbonate facies, primarily shallow ma-
rine deposits of the Navan Group and the deeper water mud
mounds of the Waulsortian Limestone (Hitzman and Large,
1986; Phillips and Sevastopulo, 1986; Andrew, 1993; Hitz-
man, 1995; Hitzman and Beaty, 1996).
At Lisheen, the lower part of the Carboniferous marine se-
quence includes carbonate-rich shales, siliciclastic sedimen-
tary rocks, and argillaceous bioclastic limestones (Lower
Limestone Shale and Ballysteen Limestone; Philcox, 1983).
The deposit is hosted by the Courceyan to early Chadian
Waulsortian Limestone, which comprises coalesced wacke-
stone or packstone mud mounds flanked by argillaceous bio-
clastic limestone (Philcox, 1983; Phillips and Sevastopulo,
1986). Growth fault control of sedimentation in the
Courceyan-Chadian (immediately prior to and during deposi-
tion of the Waulsortian Limestone) is indicated by thickness
variations across structures (Boyce et al., 1983; Hitzman et al.,
2002; Carboni et al., 2003; Fusciardi et al., 2003).
Geology of the Lisheen Deposit
Stratigraphy
The local stratigraphy in the Lisheen area is described by
Hitzman et al. (2002) and is summarized in Figure 2. The
main host to mineralization is the Waulsortian Limestone,
dominantly comprising massive, pale-gray biomicrite, to-
N gether with green-gray and gray argillites, wavy laminated
and stylonodular micrites. The Waulsortian is commonly
brecciated, particularly toward its base, and it is these brec-
cias that host the bulk of the ore. Although there is still de-
bate over the relative importance of sedimentary and hy-
drothermal controls on the genesis of Waulsortian breccias
Dublin (Hitzman and Beaty, 1996; Lee, 2002; Lee and Wilkinson,
2002; Reed and Wallace, 2003; Wilkinson and Lee, 2003),
their significance is clear as the primary host rocks to ore in
the south and west Midlands. At Lisheen, synsedimentary
breccias are present locally in the hanging wall of normal
Ireland
al., 2003), but it is not clear whether these are always precur-
sors for the hydrothermally overprinted and mineralized
dolomite breccias as has been documented at Silvermines
(Lee and Wilkinson, 2002).
Muunnssteter rBB
M asaisnin
100km Structure
The Lisheen deposit is localized by a left-stepping exten-
sional fault array (Hitzman et al., 1992, 2002; Shearley et al.,
64
 ORE-FORMING PROCESSES, LISHEEN CARBONATE-HOSTED Zn-Pb DEPOSITS, IRELAND 65

1995, 1996; Carboni et al., 2003; Fusciardi et al., 2003) with

three main east-northeast–trending strands: the Killoran,
Derryville, and Bog faults (Fig. 3). This fault zone continues
across the Tipperary-Kilkenny border to the northeast and is
an important control on mineralization at Galmoy (G fault).
A series of subordinate hanging-wall accommodation struc-
tures have also been described. Hitzman et al. (1992) stated
that west-northwest–trending structures may have played a
role in controlling mineralization in the Main zone, although
these faults are not shown in maps produced subsequent to
more extensive drilling (e.g., Hitzman and Beaty, 1996). Un-
derground observations have not identified the north-south
structures shown in Hitzman et al. (2002) but the presence of
numerous early east-northeast– and northwest-trending nor-
mal faults and late northwest-trending structures, important
in controlling present-day ground-water flow and also be-
lieved to control mineralization, has been confirmed (Carboni
et al., 2003; Fusciardi et al., 2003; see Fig. 3). Facies varia-
tions across these structures indicate that fault activity began
during deposition of the Ballysteen Limestone in the
Courceyan (J. Güven, pers. commun., 2004).
Regional dolomitization
Several phases of dolomitization occur in the Lisheen area,
the origin of which are still debated (e.g., Wilkinson, 2003).
The earliest is a fine- to medium-grained, subhedral to euhe-
dral gray dolomite that preferentially replaces micritic com-
ponents of the precursor Waulsortian Limestone (D1a). This
is partially recrystallized to and/or postdated by a coarse white
planar to weakly nonplanar dolomite (D1b) that preferentially
replaces coarser crystalline components of the Waulsortian,
such as early marine calcite cements in stromatactis cavities
and bioclasts. Together, these phases form what has been de-
scribed as the “regional dolomite” that occurs throughout
much of the Waulsortian in southeast Ireland (Hitzman et al.,
1998).
In the Lisheen area, the entire Waulsortian Complex, as
well as relatively nonargillaceous beds within the lowermost
part of the overlying Crosspatrick Formation, are dolomitized
(Shearley et al., 1996). Regional dolomite occurs on both the
hanging-wall and footwall sides of the main Killoran and
Derryville faults (Hitzman and Shearley, 1991, unpub. tech-
nical report for Chevron Mineral Corporation of Ireland,
Intercompany Technical Group on Carbonates Seminar
LN91000514). In the northern part of the Rathdowney trend
and along the margin of the Leinster massif, dolomitization of
this type has been observed locally to extend higher in the
stratigraphy, into the Aghmacart Formation. However,
dolomite has not been observed in the Arundian-age upper
portion of the Aghmacart Formation (Sheridan, 1977). The
Rathdowney trend essentially marks the northwest limit of
pervasively dolomitized Waulsortian, with the Lisheen and
Galmoy deposits located just to the southeast of the dolomite
front (Hitzman and Beaty, 1996).
The most recent studies conclude that D1a formed during
early seawater diagenesis but later underwent neomorphic re-
crystallization (Wright et al., 1999, 2000; Gregg et al., 2001).
D1b is thought to have developed in response to the onset of
FIG. 2. Summary stratigraphy of the Lisheen area (modified after Eyre, extensive fault-controlled hydrothermal circulation in the late
1998). Courceyan-Chadian (Wilkinson, 2003). The regional dolomite

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66 WILKINSON ET AL.

2195

2200

2205

2210

2215

2220
Barnali
sheen
Fault
N
1675
DERRYVILLEZONE
DERRYVILLE ZONE BOG ZONE
ZONE LK-529
LK-361
NORTH ZONE
NORTH ZONE
LK-400 LK-451
LK-395
F2
ult LK-449
LK-416
g Fa
1670
LK-517
LK-402
Bo
LK-420
F35 LK-095 LK-275
LK-171 LK-262
LK-463
MAIN ZONE
MAIN ZONE LK-475 LK-394LK-264
LK-359

LK-045 LK-325
LK-137

Derryville Fault
LK-457

1665 LK-471 F4
LK-121
LK-431
LK-514 Killora
LK-515 LK-429 nF F1
LK-105 ault
LK-235
LK-179
F7
0 metres
meters 500
1660

FIG. 3. Simplified structural map of the Lisheen deposit, showing main ore zones and locations of drill holes sampled in
the present study (Lisheen mine, 1998).

plays a pivotal role in arguments concerning deposit genesis
because it is considered to predate ore formation at Lisheen
and Galmoy (Doyle et al., 1992; Shearley et al., 1995; Eyre,
1998; Hitzman et al., 2002; Wilkinson et al., 2003), thereby
providing a maximum limit for the age of mineralization.
Hydrothermal dolomitization
A weakly developed, dark-gray dolomite of uncertain gene-
sis forms the first localized alteration phase at Lisheen (Hitz-
man et al., 1992). The first well-developed dolomite of in-
ferred hydrothermal origin (D2) forms the matrix of the
grossly stratiform, wedge-shaped breccia bodies (“black ma-
trix breccias”) that occur near the base of the Waulsortian
Limestone (Fig. 4). The term “matrix” is used here in a gen-
eral sense to mean the material surrounding breccia clasts,
rather than implying a specific origin for this material since its
origin is uncertain. At Lisheen, it is not clear whether the ma-
trix dolomite is (1) merely a replacement of the precursor
dolomitized limestone, (2) a true cement to breccia clasts, or
(3) predominantly a replacement of an earlier (synsedimen-
tary) breccia matrix, as has been shown to be the case in the
Silvermines district (Lee and Wilkinson, 2002). It could have
formed from a combination of these processes (Hitzman et
al., 2002). Fluid inclusion data from the Tynagh basin have
shown that the black dolomite commonly observed associated
with mineralization in the Irish ore field is likely to be a char-
acteristic product of fluid mixing (Wilkinson and Earls, 2000),
probably forming ahead of sulfides in a prograding reaction
front (Hitzman et al., 2002; Lee and Wilkinson, 2002; Wilkin-
son et al., 2003).
The matrix dolomite is extremely fine grained, with planar
subhedral to euhedral morphology. Under the microscope,
unmineralized and weakly mineralized examples display high
intergranular porosity (>5 vol %) and clast margins are dif-
fuse, showing clear evidence of recrystallization. The clasts
are angular to subrounded and range from tens of centime-
ters (though this may be an underestimate due to the limita-
tion imposed by core observations) down to microscopic size.
In the latter case, it becomes difficult to distinguish precursor
regional dolomite clast material from the later hydrothermal
matrix dolomite. Although polymictic breccia intervals occur
from the lower half of the Waulsortian to the lower Cross-
patrick Formation at Lisheen (Hitzman et al., 2002; Carboni
et al., 2003; see Fig. 2), the breccias are normally dominated
by regionally dolomitized Waulsortian micrite. Preore sul-
fides either occupy intergranular porosity or replace the ma-
trix dolomite (Hitzman et al., 1992, 2002; Eyre, 1998). Ore-
stage sulfides replace both the matrix and, ultimately, also the
clasts in the breccias (Shearley et al., 1996; Eyre, 1998). The
matrix dolomite at Lisheen is nonstoichiometric (being
markedly enriched in Ca over Mg; Eyre, 1998), making it
much more susceptible to recrystallization and replacement
(Tucker and Wright, 1990).
Crackle breccias and stockworks cemented by medium- to
coarse-grained white, planar or weakly nonplanar variably fer-
roan dolomite (D3), commonly referred to as “white matrix
breccias,” form a broad halo to the D2 dolomite breccias and
are developed through much of the thickness of the Waulsort-
ian. These are comparable to the “crystalline dolomite brec-
cias” at Galmoy (Doyle et al., 1992). The relative timing of

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 ORE-FORMING PROCESSES, LISHEEN CARBONATE-HOSTED Zn-Pb DEPOSITS, IRELAND
FIG. 4. North-south cross section through the Derryville zone, showing major lithological units and location of main ore
lens (Lisheen mine, 1998).
these breccias is uncertain as they tend to occur above and/or
lateral to D2 dolomite breccias (Hitzman et al., 2002), such
that crosscutting relationships are rarely observed. Shearley
et al. (1996) inferred a post-D2 timing, but the local presence
of both crystalline white dolomite in D2 breccia clasts and
black dolomite in D3 dolomite breccias (also observed at Sil-
vermines; Lee et al., 2001; Lee and Wilkinson, 2002) implies
a broadly contemporaneous origin (also see Fusciardi et al.,
2003). The textural differences are believed to result from the
mode of formation; black dolomite precipitated rapidly dur-
ing fluid mixing, whereas white dolomite crystallized from a
single hydrothermal fluid (Earls and Wilkinson, 2000; Wilkin-
son, 2003).
The dolomite breccias are crosscut by generally steeply dip-
ping veins of ferroan dolomite, dolomite (D4), and calcite
(C4). These phases also fill residual vuggy porosity within ear-
lier dolomite generations. The veins typically display sym-
metrical drusy crystal growth and may be composite. They
also commonly contain sulfides.
A late-stage, distinctive pink dolomite (D5) crosscuts and
aggressively dissolves all previous dolomite and/or sulfide
generations and is often coprecipitated with minor pyrite
and/or chalcopyrite (Eyre, 1998; Hitzman et al., 2002;
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67
Fusciardi et al., 2003). This is similar to late pink dolomite ob-
served elsewhere in the Midlands (e.g., Boast et al., 1981;
Wilkinson, 2003). Sometimes, residual porosity in this
dolomite is filled by a white, blocky calcite (C6).
Mineralization
Mineralization at Lisheen occurs within 30 m of the base of
the Waulsortian, forming single and locally multiple, gener-
ally stratiform, sulfide lenses separated by D2 dolomite brec-
cias (Fig. 4). The orebodies comprise texturally complex,
polymetallic massive sulfide, displaying both gradational and
sharp, planar or undulating contacts with the enclosing brec-
cias. Sometimes, postore stylolites are developed along these
contacts. Sulfides are also present in the Lisduff Oolite Mem-
ber (Fig. 2), predominantly in the footwall but also in the
hanging wall of the Killoran and Derryville faults (Eyre, 1998;
Hitzman et al., 2002; Fusciardi et al., 2003). The Lisduff Oo-
lite is much less extensively mineralized than the basal
Waulsortian and only comprises a minor proportion of the
total resource.
Four main ore zones have been defined: Main, North, Der-
ryville, and Bog (Fig. 3). The Main zone forms the largest ore-
body, followed by Derryville, North, and the Bog zone. Detail
67
68 WILKINSON ET AL.

on metal zoning patterns in the four zones is available in Hitz-
man et al. (2002) and Fusciardi et al. (2003).
Methodology
Textural and petrographic relationships of sulfides were de-
termined by the detailed study of more than 200 polished
blocks and thin sections in reflected light and under the scan-
ning electron microscope (SEM). This work was based only
on drill core samples collected between 1994 and 1997, prior
to underground exposures becoming available for study. Rep-
resentative drill core samples covering the spectrum of ore
stages, mineralization styles, and a range of lateral and verti-
cal positions within the four main ore zones (Fig. 3) were col-
lected in order to evaluate temporal and spatial variations in
sulfide mineralogy and sulfur isotope composition. Quantita-
tive analysis of sulfides using the microprobe was carried out
mainly on the ore-stage mineralization to determine the tem-
poral and spatial distribution of trace elements, particularly in
relation to putative hydrothermal feeder structures. Analyses
were performed using a Cameca SX50 wavelength dispersive
electron microprobe at the Natural History Museum, Lon-
don. A summary of results is presented in Table 1 and full re-
sults are available from the author on request.
Sulfur isotope analysis
Standard techniques were employed for determining sulfur
isotope compositions of both sulfides and barite. Samples of
individual mineral grains (5–10 mg) representing different
stages of the paragenesis were drilled from split core using a
fine diamond-tipped drill. Separation of individual (submil-
limeter) growth zones within sulfides was not possible so the
data record the average sulfur isotope composition of specific
sulfide generations.
Sulfur was extracted as SO2 from sulfides by fusing samples
under vacuum at 1,076°C in a Cu2O (200-mg) matrix (Robin-
son and Kusakabe, 1975). Sulfur was extracted as SO2 from
sulfates following the method of Coleman and Moore (1978)
and analyzed on a VG SIRA II mass spectrometer to obtain
values of δ66SO2, which were converted to δ34S. Standard cor-
rection factors were then applied (e.g., Craig, 1957). Results
are given in conventional δ34S notation relative to the Vienna
Cañon Diablo troilite standard (V-CDT) and are summarized
in Table 2 and given in full in the Appendix. Reproducibility
based on full replicate analyses of internal laboratory stan-
dards was ±0.2 per mil (1σ). Repeat analyses on duplicate
splits were carried out for some samples (see Appendix), with
all but three replicates being within 1 per mil.

TABLE 1. Summary of Sulfide Compositions (wt %) from the Lisheen Deposit Determined by Microprobe Analysis

Zn S Fe Cd Cu Mn Ga Ge In As Ag Tl

Sphalerite N 368 368 368 323 50 2 35 12 68 99 36 39

Max 33.53 68.63 4.96 2.48 1.09 0.05 0.16 0.09 0.09 1.11 0.24 0.61
Min 27.31 61.54 0.00 0.09 0.05 0.05 0.03 0.04 0.04 0.06 0.10 0.05
Mean 32.29 66.37 0.64 0.38 0.15 0.05 0.06 0.05 0.05 0.13 0.13 0.22
Std. Dev. 0.57 1.31 0.99 0.37 0.24 0.00 0.04 0.02 0.01 0.16 0.04 0.14

Pb S Zn Cd Cu Mn Ga Ge Te As Ag Tl

Galena N 192 192 14 5 24 49 21 85 80 20 3 18

Max 88.10 13.85 2.26 0.20 0.39 0.27 0.07 0.13 0.27 0.20 0.19 0.23
Min 82.12 12.76 0.37 0.13 0.16 0.05 0.04 0.02 0.05 0.05 0.13 0.06
Mean 85.84 13.31 0.84 0.16 0.23 0.10 0.05 0.05 0.11 0.07 0.17 0.12
Std. Dev. 0.94 0.22 0.65 0.03 0.05 0.05 0.01 0.03 0.05 0.03 0.04 0.05

Fe S Mn Cd Cu Co Ni As

Pyrite N 75 75 6 5 18 38 35 73
Max 48.36 53.59 0.07 0.08 0.22 0.44 1.92 5.21
Min 44.13 50.22 0.03 0.06 0.04 0.05 0.03 0.06
Mean 47.31 52.46 0.04 0.07 0.07 0.08 0.14 0.67
Std. Dev. 0.79 0.65 0.02 0.01 0.05 0.07 0.32 0.97

Cu Fe S Mn Co Ni As

Chalcopyrite N 18 18 18 3 4 5 11
Max 36.24 30.85 35.08 0.04 0.11 0.05 0.73
Min 34.16 29.40 34.00 0.03 0.05 0.03 0.06
Mean 35.03 30.35 34.52 0.03 0.07 0.04 0.16
Std. Dev. 0.87 0.36 0.30 0.01 0.03 0.01 0.19

Cu As S Fe Zn Cd Ga Ge In Sb Ag Tl

Tennantite N 39 39 39 39 39 26 12 5 8 7 38 22
Max 42.82 21.50 28.25 5.63 8.55 0.19 0.17 0.10 0.12 0.13 0.32 0.45
Min 40.90 20.58 27.41 1.55 3.57 0.06 0.04 0.02 0.04 0.06 0.05 0.05
Mean 41.80 21.06 27.79 2.37 6.07 0.10 0.09 0.05 0.07 0.08 0.15 0.21
Std. Dev. 0.40 0.22 0.22 1.31 1.53 0.04 0.04 0.03 0.03 0.02 0.06 0.12

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 ORE-FORMING PROCESSES, LISHEEN CARBONATE-HOSTED Zn-Pb DEPOSITS, IRELAND 69

TABLE 2. Summary of Sulfur Isotope Data by Mineral Preore stage

from the Lisheen Deposit1
Minor disseminated pyrite occurs in preore D1a dolomite
N Min Max Mean Std. Dev. and around the margins of preore D1a/D1b dolomite clasts
within the D2 dolomite breccias (Fig. 6a). This pyrite contains
Sphalerite 41 –31.5 +8.6 –7.9 8.4
Galena 34 –26.8 +3.2 –11.7 7.5
up to 0.79 wt percent As. There is intergranular porosity in-
Pyrite 37 –44.1 +11.8 –22.4 13.3 filling in D2 dolomite by early, fine-grained sphalerite and
Chalcopyrite 3 –8.3 –6.6 –7.4 0.9 pyrite, with pyrite occurring interstitial to sphalerite. The
All sulfides 115 –44.1 +11.8 –13.7 11.7 pyrite is granular in appearance and is composed of polycrys-
Barite 4 +14.3 +18.1 +16.0 1.9 talline aggregates of anhedral to euhedral crystals a few mi-
1 All
crons in size. This is overgrown by large, euhedral, equant
data are as per mil variations relative to the V-CDT standard
pyrite grains with approximately 120° interfacial angles, often
enclosing aggregates of early, fine-grained, noncolloform
sphalerite. The first significant zinc mineralization comprises
Lead isotope analysis a very fine crystalline, locally colloform, pale pink-brown
Galena samples for lead isotope analysis were drilled from sphalerite (Fig. 6b). This sphalerite occurs mainly in the D2
core specimens. Approximately 2 to 5µg of galena was dis- dolomite matrix, primarily within intergranular porosity but
solved in an excess of 6M HCl. These solutions were pipetted also as a replacement of matrix crystals where it is better de-
directly onto a single rhenium filament using a standard lead veloped.
loading technique with phosphoric acid and silica gel. The The most extensive iron sulfide mineralization postdates
206
Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios were measured the earliest noncolloform and weakly colloform pink-brown
on a VG 54E mass spectrometer. The results were normalized sphalerite but predates the main sphalerite-galena ore stage.
to the NBS 981 international standard and corrected for in- Pyrite is the earliest and dominant iron sulfide and is over-
strumental mass fractionation (see Table 3). grown by pyrite-marcasite growth bands, with marcasite be-
coming more abundant through time (also observed by Hitz-
Ore Mineralogy and Paragenesis man et al., 2002; Fig. 6c). Small pyrite spheroids (1–10 µm
Sphalerite and galena are the principal ore minerals in a diam) probably acted as nuclei for pyrite growth, leading to
relatively simple mineral assemblage that also contains abun- the development of colloform banded pyrite, a significant tex-
dant iron sulfides, including both marcasite and pyrite. Chal- tural component of the massive iron sulfide. Pyrite framboids
copyrite, arsenopyrite, bornite, and tetrahedrite-tennantite, are observed locally and tend to occur in isolation or in small
Pb-Sb sulfosalts, such as boulangerite (Pb5Sb4S11), and Pb-As clusters, particularly in samples close to the major east-
sulfosalts including jordanite (Pb14As6S23) are present in west–trending faults. They are commonly overgrown by mas-
minor amounts. Hitzman et al. (2002) also reported the pres- sive pyrite. Good examples of pyrite replacement textures
ence of gratonite, seligmannite, and gersdorffite, and Fuscia- exist, such as the pseudomorphous replacement of elongate
rdi et al. (2003) noted the local presence of cobaltite, niccol- laths of barite by fine-grained granular pyrite and subhedral
ite, pararammelsbergite, bournonite, and ullmannite. pyrite-marcasite intergrowths (Fig. 6d). Pyrite also locally re-
Based on the broad textural and mineralogical associations places ooids in the Lisduff Oolite Member, with the preser-
observed within the deposit, mineralization has been classi- vation of relict ooid textures.
fied into four stages: (1) preore stage, (2) main ore stage, (3) Marcasite occurs in colloform masses, elongate radiating
late ore stage, and (4) postore stage (Fig. 5). laths intergrown with pyrite, and as coarse subhedral grains.

TABLE 3. New Lead Isotope Data from Lisheen and Comparison with Previous Work

Sample Zone Texture Stage 206

Pb/204Pb 207
Pb/204Pb 208
Pb/204Pb δ34S

This study
416/195.5 Derryville Anhedral Main 18.182 ± 10 15.602 ± 11 38.076 ± 24 –10.2
262/162.1 Derryville Euhedral, vein hosted Late 18.197 ± 10 15.585 ± 8 38.078 ± 16 –26.1
179/176.25 Main Massive, fine grained Main 18.160 ± 22 15.563 ± 28 38.010 ± 38 –6.4
431/205.70 Main Massive, banded Main 18.193 ± 12 15.624 ± 11 38.158 ± 28 –11.2
Mean (1σ) 18.183(0.017) 15.594(0.026) 38.080(0.061)
NBS981 standard 16.945 ± 7 15.494 ± 6 36.728 ± 16

Previous work
3262-11 Lisheen 18.150 15.584 38.017
90-LK-51 Lisheen 18.194 15.592 38.070
3263-21 Tonduff 18.236 15.594 38.098
Silvermines2 18.246-18.305 15.590-15.597 38.131-38.181

Notes: New Lisheen data corrected for mass fractionation, fractionation factors from Scottish Universities Environmental Research Centre over the pe-
riod November 1996 to March 1997; δ34S data given as per mil variations relative to the V-CDT standard
1
Hitzman et al. (1992)
2
O’Keeffe (1986)

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70
Time
Mineral Preore
D1 dolomite
D2 dolomite
Barite
Pyrite/Marcasite
Sphalerite
Galena
Chalcopyrite
Tennantite
D3 dolomite
D4 dolomite/calcite
D5 pink dolomite
C6 calcite
FIG. 5. Summary paragenesis for the Lisheen deposit (after Eyre, 1998). Width of bar corresponds to relative abundance;
bars for sulfides are shown hatched for clarity.
Sphalerite, galena, and dolomite locally occur as inclusions
within the banded iron sulfides, either in discrete layers or as
isolated crystals along particular iron sulfide growth bands
(Fig. 6e). Galena commonly occurs as small spheres within
massive iron sulfide. Sulfides displaying radial coxcomb tex-
tures are generally uncommon but are well developed in the
Lisduff Oolite Member adjacent to the main fault zone.
Cataclastic textures in pyrite and marcasite are common
near to major faults in the Main and Derryville zones. There
is infilling and partial replacement of pyrite along fractures by
sphalerite and dolomite (Fig. 6f) and also by ore-stage galena.
Main ore stage
A complex polymetallic sulfide assemblage characterizes
the main ore stage, dominated by sphalerite and galena, with
minor pyrite, chalcopyrite, arsenopyrite, tennantite,
dolomite, and barite. Coprecipitation of some phases is sug-
gested by the presence of mutual growth boundaries, al-
though replacement of one sulfide by another is also com-
mon. No consistent paragenetic sequence can be defined and
the assemblage appears to be the product of multiple over-
printing and recrystallization events. Sulfides of the main ore
stage often replace early iron sulfides (Fig. 7a) and overprint
the dolomite breccias, preferentially replacing the D2
dolomite matrix and ultimately also D1a clasts (Fig. 7b). This
sequence of progressive replacement can be clearly traced
laterally into the ore from essentially pristine, unmineralized
breccias. Apparently brecciated massive sulfide pseudo-
morphs may in fact represent preexisting dolomite breccia
textures (Fig. 7b), although rebrecciation in situ during in-
tense mineralization close to the main fault zones is also
likely.
Main ore-stage sphalerite (Fig. 7c) is dominated by collo-
form aggregates within mixed massive sulfides that display
pale-cream to dark-brown color banding. Galena and pyrite
are common in the form of interbands or as discrete crystals
distributed along colloform layers in the sphalerite. Rhombic
dolomite with inclusions of early pyrite and sphalerite in
growth zones also occurs in colloform sphalerite (Fig. 7d), to-
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WILKINSON ET AL.
Ore Stage Late to Post-Ore
gether with granular Zn-rich carbonate (Fig. 7c). Locally, the
colloform sphalerite is broken and rotated.
Colloform sphalerite displays marked compositional varia-
tion (Table 1). Individual samples may contain up to 40 dis-
tinct zones with significant variations in Cd, Fe, and As con-
centrations (Fig. 8a). Cu (up to 0.11 wt %) is also observed in
some zones. The color of colloform sphalerite generally cor-
relates with mineral chemistry. For example, in a sample from
the North zone, gray-yellow bands contain up to 0.12 wt per-
cent Fe (avg 0.06 wt % Fe), yellow sphalerite contains up to
1.95 wt percent Fe (avg 0.37 wt % Fe), and orange-brown lay-
ers contain up to 2.84 wt percent Fe (avg 0.63 wt % Fe).
Other elements may also be present such as Ag (up to 0.24 wt
%), Cd (up to 0.47 wt %), and As (up to 0.60 wt %). In two
samples analyzed for Tl, highly variable concentrations of up
to 0.54 wt percent were found. However, there are no statis-
tically significant correlations between major or trace ele-
ments within any of the colloform sphalerite analyzed.
Massive, fine-grained sphalerite is the second most com-
mon textural variety after colloform sphalerite. This spha-
lerite is unzoned and is commonly intergrown with pyrite and
galena. Fe and Cd concentrations in this type of sphalerite are
lower than in colloform sphalerite, generally less than 0.5 wt
percent. Fine-grained, pale-gray sphalerite is nearly pure,
with less than 0.5 wt percent impurities. Concentrations of up
to 1.09 wt percent Cu are observed in massive sphalerite in
samples containing chalcopyrite from the footwall of the Kil-
loran fault in the Main zone, and low concentrations of Cu in
crystalline and colloform sphalerite are found in samples
within 200 m of the main faults in the Main, Derryville, and
Bog zones. Elsewhere in Ireland, Cu-bearing sphalerite has
only been noted in the 3-1 lens at Navan (T. Thorpe, pers.
commun., 2001) and from the Lower G zone at Silvermines
(Rhoden, 1960). Backscattered electron imaging of Navan
samples showed that Cu was present in solid solution, varied
significantly between adjacent growth zones (up to 1.30 wt
%), and covaried with Sb.
Replacement textures are common, such as the replace-
ment of dolomite rhombs by sphalerite and/or galena. Selec-
70
 ORE-FORMING PROCESSES, LISHEEN CARBONATE-HOSTED Zn-Pb DEPOSITS, IRELAND 71

FIG. 6. Core photographs and reflected light photomicrographs of preore-stage samples. (a). Preore-stage pyrite prefer-
entially replacing the matrix of typical black dolomite matrix breccia. Sample LK262/153.6m, Derryville zone. (b). Pale-
brown early sphalerite preferentially replacing matrix of dolomite breccia. Sample LK121-189.3m, Main zone. (c). Preore-
stage colloform pyrite with minor carbonate and sphalerite inclusions overgrown by subhedral pyrite (py) and marcasite (ma).
Sample LK420/190.7m, Derryville zone. (d). Fine-grained granular pyrite (py) pseudomorphous after barite laths. Timing of
euhedral pyrite uncertain. Subhedral-anhedral sphalerite (sp) overgrows and replaces pyrite. Sample LK262/162.1m, Der-
ryville zone. (e). Massive sulfide sample showing colloform banding. Preore-stage fine-grained pyrite-marcasite (py-ma) with
sphalerite-rich outer zone is overgrown by pyrite-marcasite band, itself succeeded and partly replaced by ore-stage sphalerite
(sp), dolomite (dol), and euhedral galena (gn). Sample LK394/164.3m, Derryville zone (Derryville fault). (f). Preore-stage
massive pyrite (py) and marcasite (ma) that has undergone cataclasis and cementation by dolomite (dol) and sphalerite (sp).
Sample LK262/159.1m, Derryville zone.

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µ µ

µ µ

µ µ

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 ORE-FORMING PROCESSES, LISHEEN CARBONATE-HOSTED Zn-Pb DEPOSITS, IRELAND 73

tive replacement of microfossils by sphalerite and other sul-
fides is also observed locally (Fig. 7e), as has been reported at
Navan (Anderson et al., 1998). Sphalerite bow-tie textures in
pyrite and elongate laths of sphalerite in a mixed assemblage
of pyrite and galena are probably pseudomorphs after early
barite or gypsum (Fig. 7f). Sphalerite also occurs in small
veinlets crosscutting and replacing pyrite (Fig. 7a) and galena.
Galena locally forms skeletal and dendritic growths, similar
to those described from Navan (Anderson et al., 1998). How-
ever, ore-stage galena is predominantly coarsely crystalline or
massive and replacive, as indicated by caries textures, where
galena replaces D2 dolomite, and by the selective replace-
ment of microfossils, early marine cements, and ooids (Fig.
7g). Galena is particularly abundant in zones proximal to the
Killoran and Derryville faults where it commonly contains in-
clusions of tennantite, especially in the Main zone. Galena in-
clusions are also found within tennantite. Boulangerite is
commonly associated with galena.
Galena generally does not contain detectable concentra-
tions of trace elements (Table 1). Massive Waulsortian-hosted
ore-stage galena locally contains elevated Te (up to 0.27 wt
%). Ag concentrations are usually below detection with the
exception of a few samples located proximal to faults that con-
tain up to 0.19 wt percent Ag. The phase that contains the
highest concentrations of Ag in the deposit is tennantite (see
below).
Tennantite, chalcopyrite, arsenopyrite, and barite are most
abundant near the Killoran and Derryville faults, especially
within the footwall Lisduff Oolite Member. In this unit, ten-
nantite commonly occurs as irregular inclusions in galena,
chalcopyrite, and sphalerite and is characterized by up to 3.91
wt percent Zn, 5.63 wt percent Fe, and 0.32 wt percent Ag
(Table 1). This contrasts with tennantite in galena from the
Waulsortian, which contains up to 8.55 wt percent Zn, less Fe
(<1.72 wt %), and less Ag (<0.24 wt %).
Short intervals of massive chalcopyrite are observed in drill
core from the footwall Lisduff Oolite of the Main zone and
this contains up to 0.73 wt percent As (avg 0.16 wt %). Minor
chalcopyrite in the Bog zone Lisduff Oolite also contains As,
up to 0.11 wt percent (avg 0.07 wt %). Minor disseminated
arsenopyrite rhombs commonly occur in ore-stage galena,
proximal to faults in the Main and Derryville zones.
Main ore-stage pyrite generally comprises fine- to coarse-
grained euhedra intergrown with and locally interstitial to
sphalerite and galena (e.g., Fig. 7f). Trace element concen-
trations in ore-stage pyrite are quite variable (Table 1). Ar-
senic concentrations range up to 5.21 wt percent and are sig-
nificantly higher than in preore pyrite. In As-rich samples, As
correlates with Cu with both showing a strong antipathetic re-
lationship with Fe. Co and Ni are usually below detection,
with the notable exception of pyrite hosted by the Lisduff Oo-
lite Member in the footwall of the Killoran fault (up to 0.44
wt % Co and 1.92 wt % Ni). This pyrite also contains up to
3.34 wt percent As, which is strongly correlated with Ni con-
tent. Elevated levels of Co and Ni are also observed in the
Ballysteen Limestone close to a secondary fault (F-291) in the
hanging wall of the Derryville fault (Fig. 3).
Barite was probably deposited both prior to and during the
main period of sulfide mineralization. Early sulfides, in par-
ticular pyrite and sphalerite, and ore-stage sulfides (Fig. 7f)
both replace barite. Later barite, associated with complex
mixed sulfide assemblages, crosscuts early pyrite-sphalerite
assemblages.
Late ore stage
Coarse (1–7 mm) crystalline sphalerite and euhedral galena
crystals are restricted to fracture-fill mineralization that cross-
cuts the main ore-stage assemblages and to vugs within main-
stage ore. These phases commonly predate or were coprecip-
itated with D4 dolomite and C4 calcite veins and vug-filling
cements (Fig. 7h). Sphalerite was generally the last sulfide to
precipitate, commonly as rims on galena. Concentrically
zoned pyrite grains locally occur within these sphalerite
rims and late, euhedral, fracture-filling galena is sometimes
observed.
Although texturally late, there is no evidence to suggest that
these phases are unrelated to the main ore stage and are
therefore regarded as representing waning hydrothermal
activity, precipitated within residual porosity and tectonic
fractures.

FIG. 7. Core photographs and reflected light photomicrographs of main ore-stage samples. (a). Massive fine-grained
pyrite in gray Waulsortian micrite (m), crosscut and replaced by sphalerite (sp) and galena (gn) in white dolomite stockwork.
Sample LK121/190.2m, Main zone. (b). Complex massive sulfide with pyrite (py) intergrown with and replaced by galena
(gn) and pale-brown sphalerite (sp). Note apparent breccia texture (replaced dolomite breccia?). Sample LK262/159.85m,
Derryville zone. (c). Colloform sphalerite containing thin bands of fine-grained pyrite and occasional botryoidal pyrite in-
tergrown with dolomite and fine-grained, zinc-rich (?geopetal) carbonate. Sample LK262/159.85m, Derryville zone. (d).
Pyrite (py) and sphalerite (sp) incorporated in dolomite (dol) euhedra along growth surfaces and overgrown by apparently
homogeneous colloform sphalerite. Sample LK416/193.6m, Derryville zone. (e). Selective replacement of foraminifera (En-
dothyrid). Sphalerite (sp) preferentially replaces chamber walls with chambers filled by galena (gn) and carbonate gangue
(c), the whole surrounded by pyrite (py). An unidentified Fe-As sulfide (u) with minor Ni, Co, and In forms a thin layer in-
side the microfossil. Sample LK137/134.9m, Derryville zone (sub-Waulsortian, footwall of Derryville fault). (f). Mixed ore-
stage sulfide assemblage comprising intergrown euhedral pyrite (py) and galena (gn), together with sphalerite (sp), probably
pseudomorphous after barite laths. Sample LK325/146.2m, Derryville zone. (g). Selective replacement of ooid by galena
(gn), surrounded and partly replaced by sphalerite (sp) and minor pyrite (py). Galena replacement may postdate plastic de-
formation of ooid reflected by oval shape and curviplanar contacts that parallel distorted laminae (upper right). No replaced
stylolites truncating laminae, or fractured, or spalled laminae are observed indicating replacement preceded mechanical
compaction, or that mechanical compaction did not occur. Sample LK394/164.3m, Derryville zone (Derryville fault). (h).
Symmetrical vug-fill sulfides comprising sphalerite (sp) intergrown with laminated and/or colloform pyrite (py), with both
being replaced from the margins inward by subhedral galena (gn). Carbonate infilling in remaining space (c), with minor dis-
solution of sphalerite along contact. Sample LK420/196.0m, Derryville zone.

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74 WILKINSON ET AL.

2.5
Very dark brown crystalline
Dark brown crystalline
Bog zone Brown crystalline
2.0 oolite-hosted
Bog zone Red crystalline
Ballysteen-hosted Amber crystalline
Yellow crystalline

Cd (wt%)
1.5
Pale yellow crystalline
Buff to pink fine-grained
Pale gray fine-grained
1.0 Main zone Orange-brown colloform
post ore Derryville zone Yellow colloform
MAIN ORE oolite-hosted
ZONES
0.5 Derryvile Fault

Bog Fault

0.0
0.0 1.0 2.0 3.0 4.0 5.0
Fe (wt%)

FIG. 9. Variation of cadmium and iron concentrations in sphalerite as a

function of textural type and location. Note that the vast majority of samples
are enriched in either cadmium or sphalerite, but not both, suggesting sub-
stitution of one or other element into the same lattice site. Darker brown
sphalerite may be either Cd or Fe rich. The most Cd rich sphalerites are
hosted by the Lisduff Oolite; Fe-rich sphalerites are generally from within
the main fault zones. Most sphalerite in the main orebodies (within thick
hatched line) contains variable Fe and low Cd.

red sphalerite from the Main zone, Fe and Cd are positively

correlated (Fig. 8b). Silver concentrations in dark-brown
sphalerite are below detection but in the amber-yellow
Waulsortian-hosted sphalerite Ag concentrations up to 0.24
wt percent were recorded (avg 0.13 wt %). This sphalerite is
an important host for silver in the deposit.

FIG. 8. Examples of variations in chemical composition of sphalerite as de-

termined by microprobe analyses (supplementary information on detection
limits and full data available from author on request). (a). Traverse across
main ore-stage color-banded colloform sphalerite (sample 262/159.1m, Der-
ryville zone). Note lack of correlation between element concentrations in in-
dividual bands and occasional detectable Cu. (b). Traverse across late ore-
stage finely crystalline, red-amber color-zoned sphalerite (sample
471/210.4m, Main zone). This sample is unusual in that it shows elevated Cd
and Fe and shows a rare correlation between Cd and Fe concentrations.
The color of late-stage crystalline sphalerite is extremely
variable, ranging from pale yellow, through amber and red, to
dark brown. The darkest sphalerite is observed within the
main fault zones (Fig. 9) and is dominant in sub-Waulsortian
veins, whereas yellow-amber sphalerite is prevalent in the
Waulsortian Limestone. In general, the crystalline sphalerite
is richer in Fe and contains less As (usually <1.0 wt %) than
the main ore-stage colloform sphalerite. Dark-brown crys-
talline sphalerite is usually more Fe rich (up to 4.96 wt % Fe)
than yellow and amber sphalerite (generally <0.50 wt % Fe)
and is spatially associated with the main faults in the Der-
ryville and Bog zones. Cadmium concentrations are mainly
uniform (0.2–0.4 wt %) within individual crystalline spha-
lerite samples, in contrast to the colloform sphalerite. How-
ever, Lisduff Oolite-hosted brown sphalerite from the Bog
zone and pink dolomite-hosted amber sphalerite from the
west Main zone are anomalous with elevated and variable Cd
(0.65–2.48 and 0.26–1.14 wt %, respectively; Fig. 9). There is
an antipathetic relationship between Fe and Cd in brown
sphalerite, whereas pale sphalerite is characterized by low
concentrations of both elements (Fig. 9). In a rare example of
Postore stage
Sulfides that occur in veins that clearly crosscut all previous
stages are defined as postore stage. At Lisheen, these sulfides
are commonly associated with pink saddle dolomite (D5),
which is associated with extensive dissolution of earlier car-
bonates and sulfides. This often leaves extensive vuggy poros-
ity and abundant pink dolomite typically correlates with poor
ore grades. Chalcopyrite and pyrite are the dominant sulfides,
typically forming encrustations on saddle dolomite crystals to-
gether with minor sphalerite and galena. There is white
blocky calcite (C6) infilling of residual porosity in some sam-
ples.
Sulfur and Lead Isotopes
Sulfur Isotopes
A total of 119 analyses were carried out on 53 samples of
sulfides (mainly pyrite, sphalerite, and galena) and barite
from the four main ore zones and from all stages of the para-
genesis (Table 2, Appendix).
The δ34S values show a very wide range from –44.1 to +11.8
per mil, with a mean value of –13.7 per mil (Fig. 10a). Ex-
tremely low δ34S values in the range of –38 to –44 per mil are
only observed in preore-stage disseminated pyrite (Fig. 10b),
and pyrite in general has lower values than the other sulfides,
a feature typical of the Irish-type deposits (e.g., Boyce, 1990;
Anderson et al., 1998; Fallick et al., 2001; Blakeman et al.,
2002). Sphalerite and galena have similar ranges in isotopic
composition.
Main ore-stage sulfides always have negative δ34S values
and fall dominantly within the range of –4 to –18 per mil, with

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FIG. 10. Histograms of sulfur isotope compositions, subdivided according

to (a) sulfide phase and (b) ore stage. Sphalerite and galena have very similar
ranges and average values, whereas pyrite is much more variable and trends
to much lower δ34S values. Preore sulfides (mainly pyrite) are characterized
by very low δ34S values indicative of an extreme bacteriogenic fractionation.
Main ore-stage values are intermediate due to mixing between bacteriogenic
and hydrothermal sulfur sources coupled with less extreme bacteriogenic
fractionation during sulfate reduction. Late ore-stage sulfides are dominated
by hydrothermal sulfur with high δ34S. Postore-stage sulfides have low δ34S
values, probably indicative of sulfur remobilized from early main ore-stage
sulfides.

a mode of –10 per mil (Fig. 10b). Although the different ore
zones have broadly the same range in sulfur isotope composi-
tions, there appears to be a slight trend toward lower δ34S val-
ues in the Derryville zone compared to the Main zone (see
below). Late ore-stage, vein-hosted, and vug-filling sulfides
have δ34S values of –20.2 to +12 per mil (excluding three
anomalously low values in pyrite, sphalerite, and galena in
sample 451/139.1 m from the Bog zone; see Appendix) with
the majority having higher values (avg –3.0 ± 8.5‰, 1σ). Po-
store-stage sulfides have δ34S values mainly between –24 and
–27 per mil, with one very low value at –37.9 per mil.
Sphalerite: δ34S values of sphalerite (n = 41) fall within the
range of –31.5 to +8.6 per mil (avg –7.9 ± 8.5‰, 1σ; Fig. 10a).
Ore-stage sphalerite (n = 25) has a narrow range of δ34S with
a mean of –11.1 ± 3.8 per mil. There is a relationship between
sphalerite texture and δ34S, with main ore-stage colloform
sphalerite having values consistently around –11 per mil, fine
crystalline sphalerite having a markedly wider range, and late
ore-stage crystalline sphalerite being the most heterogeneous
of all (Fig. 11a).
FIG. 11. Variations in sulfur isotope composition of (a) sphalerite, (b)
galena, and (c) pyrite with depth and textural type. Outliers: BZ = Bog zone,
DZ = Derryville zone, MZ = Main zone, NZ = North zone. Samples from
sub-Waulsortian units are indicated. Sphalerite and galena show trends to-
ward higher δ34S values with depth in the main ore zones and in sub-
Waulsortian sulfides consistent with input of an 34S-enriched sulfur compo-
nent from depth. Pyrite does not show such a trend in the main ore zones,
suggesting that much of it formed relatively early when the flux of hy-
drothermal sulfur from depth was minor or absent.
Sphalerite shows a broad correlation between sulfur iso-
tope composition and sample depth. More negative δ34S val-
ues occur in shallower, Waulsortian-hosted sulfides, and
higher δ34S values occur lower in the stratigraphy at the base
of the Waulsortian and in the Ballysteen Limestone Forma-
tion, including the Lisduff Oolite Member (Fig. 11a). Varia-
tion in the sulfur isotope composition of sphalerite between

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76 WILKINSON ET AL.
the ore zones is also observed. Sphalerite in the Main zone is
relatively homogeneous in sulfur isotope composition (Fig.
11a). δ34S values for sphalerite from the Derryville zone are
slightly more negative and have a wider range, and sphalerite
from the Bog zone has the widest range of isotopic composi-
tions, albeit based on only four analyses (Fig. 11a).
Galena: δ34S values of galena (n = 34) fall within the range
of –26.8 to +3.2 per mil (avg –11.7 ± 7.5 per mil, 1σ; Fig. 10a).
Main ore-stage galena (n = 22), like sphalerite, has a narrow
range of δ34S values with an average of –11.2 ± 3.3 per mil.
Galena hosted by the Lisduff Oolite Member and intergrown
with fine-grained sphalerite has the highest δ34S value of +3.2
per mil. The lowest δ34S value, –26.8 per mil, was obtained
from late- to postore-stage, vein-hosted galena associated
with tennantite at the base of Waulsortian-hosted massive sul-
fide in the Derryville zone. Galena shows a clearly defined in-
crease in δ34S values with depth and increasing heterogeneity
from the Main to Derryville to Bog zones (Fig. 11b), similar
to sphalerite.
Pyrite: δ34S values in pyrite (n = 37) range from –44.1 to
+11.8 per mil (avg –22.4 ± 13.3 per mil, 1σ; Fig. 10a). Dis-
seminated preore-stage pyrite hosted by well-developed hy-
drothermal D2 dolomite has the lowest δ34S values of –44.1 to
–38.1 per mil. Main ore-stage pyrite (n = 24) has a restricted
range of sulfur isotope compositions but is still more variable
than sphalerite and galena and also has markedly lower values
than the other sulfides, with a mean of –20.1 ± 7.1 per mil. In
the Waulsortian, no correlation with depth is apparent (Fig.
11c). However, the highest δ34S value of +11.8 per mil is from
relatively deep in the system, from a vein within the upper
calcarenite member of the Ballysteen Limestone Formation.
Pyrite from the Main zone has a more uniform isotopic com-
position than in the Derryville zone, similar to the other main
sulfides. Only two data from one drill hole in the Bog zone
were analyzed, and these are rather similar.
Chalcopyrite: Chalcopyrite samples, all from the Main
zone and representing the main ore stage, have typical ore-
stage δ34S values ranging from –6.6 to –8.3 per mil (n = 3; Fig.
10a).
Barite: Barite intergrown with main ore-stage sulfides in
the Derryville zone (n = 2) has δ34S values of +18.1 and +17.2
per mil (repeat analyses on splits of a single sample, Fig. 10a).
Barite associated with main ore-stage sulfides in the Main
zone (n = 2) has lower values (although possibly sulfide cont-
aminated) of +14.3 and +14.5 per mil.
Lead isotopes
A preliminary study of four galena samples was carried out
to provide supplementary data on the lead isotope character
of the deposit and to compare the results with existing data
from the Irish ore field. The samples analyzed were from
massive ore-stage galena and from vein-hosted, late- to pos-
tore-stage galena (Table 3). The results are compared to data
from other deposits in the ore field in Figure 12.
Discussion
Timing of mineralization
Mineralization within the D2 dolomite breccias postdates
the regional dolomite, which provides a potential maximum
0361-0128/98/000/000-00 $6.00
15.7
S&K growth
0 Ma curve
15.6 500 Ma
Pb / 204Pb
750 Ma
Silvermines
15.5 1000 Ma average
Deposit array
207
15.4
15.3
17.0 17.5 18.0 18.5 19.0 19.5
206 204
Pb / Pb
FIG. 12. 207Pb/204Pb vs. 206Pb/204Pb plot, showing lead isotope composi-
tions of galena from Lisheen (this study) with error bars, compared to deposit
array (encompasses average values for all Irish deposits and prospects) and
average Silvermines value (see Table 3). Lisheen data fall close to the Silver-
mines average, implying a common lead source from local lower Paleozoic
rocks. Pb growth curve of Stacey and Kramers (1975) is marked in 250 Ma
increments for reference.
age limit for ore formation. Assuming that formation of the
regional dolomite is not diachronous and is not an early dia-
genetic product, ore formation occurred no earlier than the
late Chadian (Shearley et al., 1995, 1996; Sevastopulo and
Redmond, 1999; Hitzman et al., 2002). However, if models of
early seawater dolomitization are correct (Gregg et al., 2001)
then crosscutting relationships do not provide a useful con-
straint on the timing of mineralization (Wilkinson, 2003;
Wilkinson et al., 2003).
Since there is good evidence that mineralization is localized
by the Lisheen fault array, the timing of fault movement pro-
vides some constraints on the timing of mineralization. We
consider that it is highly unlikely for extensive fluid flow to ex-
ploit these potential fluid conduits except during periods of
active tectonism, since any fault-related permeability would
be rapidly sealed by hydrothermal precipitates in times of
quiescence. Sediment thickness variations imply that fault-
controlled sedimentation in the area initiated immediately
prior to Waulsortian deposition, significantly earlier than pre-
viously thought (Carboni et al., 2003; Fusciardi et al., 2003).
Thus, mineralization could have begun as early as the
Courceyan (cf. Lee and Wilkinson, 2002). The frequent ob-
servation of cataclastically deformed preore sulfides in the
Main and Derryville zones overprinted by main ore-stage
mineralization (e.g., Fig. 6f) indicates that ore formation did
not entirely postdate fault movements, as suggested by Sev-
astopulo and Redmond (1999), Hitzman et al. (2002), and
Carboni et al. (2003). Synsedimentary faulting continued dur-
ing deposition of the Crosspatrick Formation, suggesting that
mineralization could have persisted into, or initiated in, the
Chadian (Fusciardi et al., 2003).
The fact that ore-stage sulfides at Lisheen replace early
marine cements and regional dolomite indicates that the
main phase of mineralization must have occurred subsea-
floor during or subsequent to early diagenesis of the
Waulsortian Limestone. However, it is probable that ore for-
mation occurred close in time and space to the oxic and/or
suboxic transition in the connate porewaters (Wilkinson et al.,
76
 ORE-FORMING PROCESSES, LISHEEN CARBONATE-HOSTED Zn-Pb DEPOSITS, IRELAND
2003). Furthermore, the sulfur isotope data indicate that this
must have occurred at a depth where the ore-forming system
remained open to seawater sulfate. These features, coupled
with the evidence for near-sea floor and exhalative mineral-
ization in other Irish-type deposits (Wilkinson et al., 2003),
suggest that mineralization probably occurred within a few
tens of meters, and at most a few hundred meters below the
sea floor, much sooner during burial than suggested by Hitz-
man et al. (2002).
Source of lead
The limited new lead isotope data from Lisheen show no
obvious correlation between ore stage or galena texture and
lead isotope composition and there is no indication of a co-
variance between lead isotopes and δ34S values in galenas
(Table 3), as has been observed in some Mississippi Valley-
type deposits (Sverjensky, 1981). This lead isotope homo-
geneity is consistent with results from the other Irish deposits
and suggests a well-homogenized crustal reservoir. The data
are comparable with those reported for Lisheen by Hitzman
et al. (1992) and are similar to results from Silvermines, 35
km to the west (O’Keeffe, 1986; Fig. 12). The similarity be-
tween Lisheen and Silvermines implies a common lead
source; the match between deposit galenas and estimated
composition of the lower Paleozoic sequence in the southwest
Midlands at the time of mineralization (Dixon et al., 1990)
implicates Silurian graywackes, siltstones, and grits of the
Hollyford Formation. The lead isotope data therefore sup-
port fluid-flow models involving deep basement circulation
and are inconsistent with fluid flow through and derivation of
lead from the Old Red Sandstone, as summarized by Everett
et al. (2003).
Distribution and source of other metals
Petrographic and mineral chemical studies show that Cu-,
As-, Co-, and Ni-bearing phases are abundant close to the
major faults and in sub-Waulsortian mineralization, particu-
larly within the Lisduff Oolite (also see Fusciardi et al.,
2003). Similarly, these elements are enriched (and covary) in
other main ore-stage phases (sphalerite, pyrite, chalcopyrite)
in proximity to the major structures. The co-occurrence of
these elements in a range of phases, both as major and minor
constituents, suggests that they were enriched in the hy-
drothermal fluids active during the main ore stage. The clear
spatial association with major east-west faults implies that
these structures were important conduits for fluids trans-
porting these elements from depth. Intense bleaching of the
Old Red Sandstone is observed close to the main fault zones
at Lisheen (Mallon, 1997; Everett, 1999; Hitzman et al.,
2002; Everett et al., 2003), and results of acid leaching ex-
periments on unaltered Old Red Sandstone samples show
that Ni and Co are readily liberated (C. Everett, pers. com-
mun., 2000). Therefore, it is suggested that Cu, As, Co, and
Ni were stripped during early, localized alteration of the
sandstone footwall around fault conduits and redeposited in
ore-stage minerals at higher levels by buoyant hydrothermal
fluids.
Trace element substitutions in sphalerite appear to have
been controlled by different processes. Fe is generally en-
riched in vein sphalerite from close to faults, particularly in
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77
the Derryville and Bog zones and in the sub-Waulsortian
stratigraphy. There is no obvious correlation with fluid inclu-
sion homogenization temperatures (Eyre, 1998), suggesting
that temperature is not a primary control on Fe content.
Given the probability of high sulfur fugacity in the upper
parts of the system during ore formation (see below), it is sug-
gested that the Fe content of sphalerite is controlled by sul-
fur fugacity in an inverse relationship (cf. Czamanske, 1974).
Cd concentrations in sphalerite are generally decoupled
from Fe and show no obvious systematic pattern in space or
time. A weak correlation with sulfur isotope composition
(Fig. 13) suggests that Cd may be cotransported with iso-
topically heavy sulfur (derived from depth; see below) and is
favorably partitioned into the first sphalerite precipitated in
fluid conduits. There is no evidence for liberation of Cd dur-
ing alteration of the Old Red Sandstone, therefore it is sug-
gested that Cd is sourced, with Pb, from the lower Paleozoic
basement.
Sources of sulfur
Barite δ34S values are comparable to results reported by
Hitzman and Beaty (1996) and are identical to Lower Car-
boniferous seawater sulfate (Claypool et al., 1980). This sug-
gests that barite precipitation at Lisheen involved essentially
unmodified Carboniferous marine sulfate, as inferred for
barite in all the other Irish deposits (δ34S = 15–23‰; Graham,
1970; Greig et al., 1971; Coomer and Robinson, 1976; Boast
et al., 1981; Caulfield et al., 1986; Anderson et al., 1998). The
very low solubility of barium in seawater excludes this as a
source for Ba. Given that barium is not present as a significant
constituent of the host rocks, it can be concluded that, as in
modern submarine hydrothermal systems, Ba was introduced
(with the bulk of the ore metals) in a second, relatively re-
duced, fluid phase. Analyses of fluid inclusions in lower Pale-
ozoic-hosted vein systems interpreted as feeders for the over-
lying mineralization show that the relatively high temperature
(170°–240°C), moderate-salinity (10–18 wt % NaCl equiv)
fluid involved in mineralization (hereafter referred to as the
“principal ore fluid”) contained high concentrations of Ba
FIG. 13. Range of cadmium concentrations in sphalerite samples (deter-
mined by microprobe analysis) plotted against sulfur isotope composition. A
weak positive correlation exists, suggesting that cadmium is associated with
the hydrothermal sulfur component, both being derived from the lower Pa-
leozoic basement.
77
78 WILKINSON ET AL.
(C. E. Everett, unpub., in Wilkinson et al., 2003) and is there-
fore a viable source.
The very low δ34S values observed in the early pyrite rep-
resent an extreme isotope fractionation that can only be ex-
plained by the action of sulfate-reducing bacteria in a system
open to sulfate. The data represent a fractionation of around
60 per mil from contemporaneous seawater sulfate, the only
viable large sulfate reservoir. Similar low δ34S values in pyrite
have been noted at Silvermines (Boyce et al., 1983; Boyce,
1990) and Navan (Anderson et al., 1998; Blakeman et al.,
2002). Typical fractionations in natural systems appear to be
around 30 to 40 per mil (Canfield, 2001). However, extreme
fractionations, similar to those shown by the early pyrite, are
observed where low rates of bacterial sulfate reduction are
combined with oxidative cycles (e.g., Canfield and Tham-
drup, 1994). At Navan, it has been suggested that near-sea
floor bacterial sulfate reduction resulted in the formation of
pyrite with low δ34S during more oxidative periods at times of
hydrothermal quiescence (Blakeman et al., 2002). This is con-
sistent with the close paragenetic position of early pyrite and
the silica-hematite alteration (inferred to have formed in the
presence of dissolved free O2; Cruise et al., 1999; Cruise,
2000) that is variably developed in most of the Irish deposits,
including Lisheen.
Main ore-stage sulfides at Lisheen typically have δ34S val-
ues 22 to 38 per mil lower than coexisting sulfate. This repre-
sents a fractionation typical of bacterial sulfate reduction in
natural systems open to sulfate (e.g., Goldhaber and Kaplan,
1975) and supports a bacteriogenic origin for the majority of
ore-stage sulfur. A similar conclusion has been reached for all
the major Irish deposits (Coomer and Robinson, 1976; Boast
et al., 1981; Boyce et al., 1983; Anderson et al., 1998; Fallick
et al., 2001). The predominance of bacteriogenic sulfide with
low δ34S in Ireland is in marked contrast to the Gays River
and Jubilee deposits of Nova Scotia (Sangster et al., 1998),
which otherwise bear some resemblance to the Irish deposits.
This characteristic sets the Irish deposits apart from Missis-
sippi Valley-type deposits such as Pine Point (Rhodes et al.,
1984) and in this respect they have more in common with the
large massive sulfide deposits of the Iberian Pyrite Belt (Ve-
lasco et al., 1998; Sáez et al., 1999). This feature implies that
during both the preore and main-ore stages bacterial sulfate
reduction occurred in an open system; this is only likely to
have been possible at, or close to, the sediment-seawater in-
terface. However, the temperature in the immediate environ-
ment of ore deposition (ca. 140°–220°C) is likely to have been
too high for sulfate-reducing bacteria, which are only known
to metabolize up to 110°C (Jørgensen et al., 1999; Stetter,
1999). Therefore, bacteriogenic sulfur is most likely to have
been transported to the site of ore deposition from near-sea
floor sediments above or on the fringes of the deposit.
In general, there is no systematic difference in δ34S values
between galena and sphalerite at Lisheen. Individual spha-
lerite-galena pairs in apparent textural equilibrium do not
show fractionations consistent with isotopic equilibrium at
temperatures between 240° and 100°C, the range inferred for
the Irish deposits (Wilkinson et al., 2003). Similarly, all pyrite
δ34S values are lower than those of coexisting galena or spha-
lerite in all of the ore stages in contrast to the higher values
that would be expected for isotopic equilibrium (Sakai, 1968).
0361-0128/98/000/000-00 $6.00
These results indicate that isotopic equilibrium was not at-
tained during any of the ore stages at Lisheen.
Although bacterially reduced sulfate is considered to be the
dominant source of ore-stage sulfur at Lisheen, variations in
sulfur isotope compositions indicate that a second sulfur
source with higher δ34S was involved. The sulfur isotope com-
positions of sphalerite and galena show trends toward higher
values with depth, irrespective of textural type or ore stage
(Fig. 11a-b). This is best explained by an increasing contribu-
tion, deeper in the system, from a sulfur source characterized
by δ34S values above 0 per mil. This source appears to domi-
nate the late ore-stage and sub-Waulsortian sulfides at
Lisheen (values of 0–12‰) with the highest δ34S values ob-
served in more coarsely crystalline and/or euhedral sphalerite
and galena (Fig. 11a-b). Such sulfur isotope compositions
form a distinct grouping that has been recognized in most of
the Irish deposits (Caulfield et al., 1986; Samson and Russell,
1987; Anderson et al., 1998). It has been suggested that this
represents reduced sulfur, derived from diagenetic sulfides in
the lower Paleozoic sequence and transported from depth by
the principal ore fluid (Anderson et al., 1989; Boyce et al.,
1994). Recent coupled sulfur isotope and fluid inclusion
analyses on sphalerite have confirmed this association (Eyre,
1998; Everett et al., 1999b).
The trend toward higher δ34S values with depth in the main
ore-stage sulfides, particularly galena, suggests that there was
an important contribution from this source during the main
stage of economic mineralization. It is noteworthy that the
mean δ34S value for ore-stage sulfides is higher than at Sil-
vermines (e.g., Hitzman and Beaty, 1996), consistent with a
greater input of hydrothermal sulfur at Lisheen. In addition,
δ34S values from the Main zone are generally higher than
those from the Derryville zone, implying a greater contribu-
tion from the hydrothermal source, perhaps as a consequence
of longer lived hydrothermal flow into the larger orebody.
The greater homogeneity of sulfur isotope compositions in
the Main zone could also be a product of an extended period
of fluid flow and associated recrystallization.
Spatial variations in sulfur isotope compositions of main
ore-stage sphalerite and galena (Fig. 14) show that higher
δ34S values (>–10 per mil) are located in the footwall of the
Killoran fault in the Main zone, in the east Main zone, and in
the southwestern part of Derryville zone, close to the Der-
ryville fault. The distribution of high δ34S values (>0‰) in
late ore-stage sphalerite and galena follows a similar pattern
(Fig. 14), suggesting that these zones were the foci of the
principal ore fluid throughout the ore-forming event. These
areas coincide with high Pb, Zn, and Ni concentrations (Hitz-
man et al., 2002; Fusciardi et al., 2003) and Pb-rich ores have
been shown to correspond with feeder zones in other Irish
deposits (Taylor, 1984; Ashton et al., 1992; Lowther et al.,
2003).
In addition to the implied control by the main east-west
faults, the distribution of the sulfur data also suggests that
northwest-trending structures may have been important (Fig.
14). This is consistent with underground observations that
show northwest faults play a role in localizing mineralization
both at Lisheen (Carboni et al., 2003; Fusciardi et al., 2003)
and Galmoy (Lowther et al., 1999, 2003). At Lisheen, two
main foci of fluid flow are suggested (Fig. 14) close to the
78
 ORE-FORMING PROCESSES, LISHEEN CARBONATE-HOSTED Zn-Pb DEPOSITS, IRELAND 79

FIG. 14. Spatial variations in sulfur isotope composition of sphalerite and galena from the main and late ore stages at
Lisheen. Average values for multiple analyses from each drill hole sampled are shown. Main ore-stage δ34S values are sub-
divided into those dominated by bacteriogenic sulfur (plain numbers) and those with an inferred hydrothermal sulfur com-
ponent (δ34S > –7‰), shown in gray boxes. Late to postore-stage values are shown in black boxes. Higher values for both
main- and late ore-stage sulfides are observed near the main east-west–trending faults and/or northwest-trending structures,
suggesting that these are the main conduits for fluids transporting hydrothermal sulfur from depth. Two principal subverti-
cal conduits for hydrothermal fluid ingress into the ore zones are suggested, one in the east Main zone and one in the west
Derryville zone.

intersection of northwest-trending structures and the Killo-
ran and Derryville faults. Alternatively, the entire area be-
tween the tips of the Killoran and Derryville faults could have
been a major damage zone that acted as the primary vertical
conduit for hydrothermal fluids to access the two main
orebodies.
The generally low δ34S values of pyrite and lack of variation
with depth (with the exception of two sub-Waulsortian vein
pyrite samples) are significant (Fig. 11c). Given that much of
the pyrite is paragenetically early, it may be that the principal
ore fluid was only a minor contributor to the system at this
stage. We suggest that low-temperature brines from a shallow
source (see below) were largely responsible for early iron-rich
mineralization (possibly including the silica ironstones) that
was formed under more oxidizing conditions than the main
ore-stage sulfides.
Evidence for fluid mixing
The presence of dendritic, skeletal, layered geopetal, and
colloform textures are commonly interpreted to represent
sulfide deposition in open space and/or by rapid precipitation
of sulfides from supersaturated solution (Roedder, 1968;
Honjo and Sawada, 1982). The observation of such textures in
the main ore stage at Lisheen, together with the lack of cor-
relation between trace element concentrations in colloform
sphalerite and sulfur isotope disequilibrium, are suggestive of
rapid precipitation at high degrees of supersaturation. The
evidence from the δ34S data for two main sulfur sources im-
plies that mixing between two fluids was the likely cause of
sulfide supersaturation. Fluid mixing is also required to ac-
count for barite precipitation since significant concentrations
of both sulfate and barium cannot be transported by the same
fluid. This conclusion is supported by fluid inclusion data that
suggest mixing between the principal ore fluid and a low-tem-
perature brine occurred during the main- to late ore-stage at
Lisheen (Eyre et al., 1996; Eyre, 1998). Fluid inclusion halo-
gen data (Everett et al., 1999, 2001; Gleeson et al., 1999;
Everett and Wilkinson, 2000; Banks et al., 2002) suggest that
this brine is likely to have been of evaporitic origin and may
have acquired H2S while migrating through the carbonate se-
quence, perhaps analogous to brines reported from Cenozoic
shelf carbonates on the Australian Bight (Swart et al., 2000).
The relatively uniform δ34S values that characterize collo-
form sphalerite can be accounted for if bacteriogenic sulfide
dominated the total sulfur budget during its precipitation.
This would have been the case for the vast majority of fluid
mixtures if, as is assumed, the brine contained concentrations
of (bacteriogenic) H2S at least an order of magnitude higher
than the principal ore fluid. Massive, fine-grained galena is
also isotopically homogeneous and could be explained in the
same way, although isotopic homogenization via recrystalliza-
tion is an alternative explanation. Other types of sphalerite

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80 WILKINSON ET AL.
show much more variability (Fig. 11a) and this, together with
the occurrence of intimately intergrown sulfides with widely
varying compositions in some samples, is consistent with de-
position from fluid mixtures dominated by the principal ore
fluid. Late ore-stage euhedral sphalerite probably crystal-
lized at low degrees of supersaturation in open vugs. The
high δ34S values that characterize these samples suggest that
only the principal ore fluid was infiltrating the system at this
time, consistent with fluid inclusion data (Eyre, 1998). Thus,
there appears to have been a temporal evolution from a sys-
tem initially dominated by the bacteriogenic sulfur-trans-
porting fluid (metal limited), through a main stage of fluid
mixing and ore formation, to a system dominated by the
deep-source hydrothermal fluid (sulfur limited). The cessa-
tion of mixing due to a cut-off of the brine supply is therefore
postulated as the cause of the termination of the main ore-
forming event.
Postore-stage sulfides are most likely the result of remobi-
lization of ore-stage sulfur during the pink dolomite precipi-
tation event. Fluid inclusion data show that the fluids respon-
sible were low-temperature Na-Ca-Cl brines (Eyre, 1998)
that may have been mobilized during the onset of Variscan
compression (Everett et al., 1999a).
a PREORE DOLOMITIZATION
Carboniferous sea
c MAIN STAGE SULFIDE MIINERALIZATION
H 2S H S
2
H2S
Zn,Pb,Fe,Cd
LEGEND
Brine flow path Fracture-controlled sulphide
Principal ore fluid flow path Massive sulphide
Late mineralized fractures Seawater
White matrix breccia Supra-Waulsortian
0361-0128/98/000/000-00 $6.00
Model for Mineralization
The evidence presented here, together with literature in-
formation, has been used to develop a model for mineraliza-
tion (Fig. 15). Five main stages are envisaged: (1) a preore
ground preparation in which the preferentially permeable
and reactive host rocks were developed; (2) and (3) two stages
in which fluid mixing resulted in the development of hy-
drothermal dolomite that was progressively overprinted by
sulfides; (4) a late ore stage in which residual porosity was
sealed and hydrothermal veins and breccias formed; and (5) a
postore brine overprint associated with carbonate dissolution
and sulfide remobilization.
Conclusions
Lisheen is a strata-bound zinc-lead deposit formed by re-
placement of hydrothermally dolomitized, broadly stratiform
breccia bodies located near the base of the Mississippian
Waulsortian Limestone. Multiple stages of sulfide deposition
occurred below the sea floor, with hydrothermal dolomitiza-
tion and early Fe mineralization dominated by low-tempera-
ture evaporitic brines transporting bacteriogenic H2S. The
main ore stage involved rapid precipitation of sulfides driven
b FLUID FLOW INTO HOST ROCKS
H 2S
H 2S
H 2S H2S
Cu,As
Ni,Co
Fe,Zn,Pb,Cd
d LATE STAGE SULFIDE MINERALIZATION
Dolomite breccia Lisduff Oolite
Dolomitized Waulsortian Sub-Waulsortian
Waulsortian equivalent facies Old Red Sandstone (/altered)
Waulsortian Limestone Lower Paleozoic
80
 ORE-FORMING PROCESSES, LISHEEN CARBONATE-HOSTED Zn-Pb DEPOSITS, IRELAND 81

by mixing between these brines and higher temperature,
metal-bearing (Zn, Pb, Fe, Cd) fluids derived from a base-
ment-equilibrated fluid reservoir. Some elements (Cu, As,
Co, Ni) may have been released during alteration of the foot-
wall red sandstones. Fluid flow was focused both within dam-
age zones associated with the main Lisheen extensional fault
array and northwest-trending fractures in its hanging wall.
Ore formation ceased due to exhaustion of the brine reservoir
or blocking of the brine flow path. Late ore-stage sulfides pre-
cipitated from higher temperature hydrothermal fluids in hy-
draulic fractures and breccias as the system became sealed.
This ore-forming process is consistent with geologic and geo-
chemical evidence from the other economic deposits of the
Irish ore field.
Acknowledgments
We thank staff and management, past and present, at
Lisheen for their support during the course of this research.
In particular, we are grateful to John Elmes, Leo Fusciardi,
Dave Hough, and Pat Redmond for their assistance through-
out the life of the project. Garth Earls helped to instigate the
study and stimulated many ideas in numerous discussions of
Irish mineralization, and Tony Fallick and Chris Stanley con-
tributed scientific input, logistical support, and encourage-
ment. Rob Ellam is thanked for supervision of the Pb isotope
work at Scottish Universities Environmental Research Centre
(SUERC). Lizzie Morris provided exemplary technical sup-
port. The financial assistance of Imperial College in the form
of a Ph.D. studentship to SLE and the field support provided
by the Natural History Museum and Rio Tinto Mining and
Exploration are gratefully acknowledged. All isotope work
was funded through the National Environment Research
Council (NERC) Facilities grant IP/495/1096 to JJW.
SUERC is funded by NERC and the Scottish Universities
Consortium. AJB is funded by NERC support of the Isotope
Communities Support Facility at SUERC. We thank the
Lisheen Mine Partnership for permission to publish this
paper. Reviews by Don Sangster and Kevin Shelton assisted
greatly in improving the manuscript. This work would never
have been undertaken without the inspiration and support of
the late Dave Johnston.
December 31, 2002; September 16, 2004
REFERENCES
Anderson, I.K., Andrew, C.J., Ashton, J.H., Boyce, A.J., Caulfield, J.B.D.,
Fallick, A.E., and Russell, M.J., 1989, A sulphur isotopic reconnaissance
study of mineralization in the lower Palaeozoic strata of Ireland and the
Southern Uplands of Scotland: Implications for Zn-Pb-Ba mineralization in
the Lower Carboniferous of Ireland: Journal of the Geological Society
[London], v. 146, p. 715–720.
Anderson, I.K., Ashton, J.H., Boyce, A.J., Fallick, A.E., and Russell, M.J.,
1998, Ore depositional processes in the Navan Zn + Pb deposit, Ireland:
ECONOMIC GEOLOGY, v. 93, p. 535–563.
Andrew, C.J.,1993, Mineralization in the Irish Midlands, in Pattrick, R.A.D.,
and Polya, D.A., eds., Mineralization in the British Isles: London, Chap-
man and Hall, p. 208–269.
Ashton, J.H., Black, A., Geraghty, J., Holdstock, M., and Hyland, E., 1992,
The geological setting and metal distribution patterns of the Zn-Pb-Fe
mineralization in the Navan Boulder Conglomerate, in Bowden, A.A.,
Earls, G., O’Connor, P.G., and Pyne, J.F., eds., The Irish minerals industry
1980–1990: Dublin, Irish Association for Economic Geology, p. 171–210.
Blakeman, R., Ashton, J.H., Boyce, A.J., Fallick, A.E., and Russell, M.J.,
2002, Timing of interplay between hydrothermal and surface fluids in the

FIG. 15. Model for mineralization at Lisheen. (a). Stage 1: Preore dolomitization. Early diagenetic regional dolomitiza-
tion of the Waulsortian Limestone driven by brine reflux from the shelf area bordering the Leinster massif predated or may
have been partly synchronous with brecciation of the Waulsortian Limestone. Lisheen is located at the northwestern fringe
of a zone of pervasive dolomitization, probably close to a shelf basin break controlled by propagation of Caledonian base-
ment structures up into the overlying cover in the late Courceyan. (b). Stage 2: Fluid flow into the ore-forming environment.
The high intergranular matrix porosity developed as a result of synsedimentary and/or the onset of hydrothermal brecciation
was a critical ground preparation, producing a permeable lithology into which later mineralizing fluids were focused. Brec-
ciation coupled with sufficient development of fault-related permeability resulted in connectivity between the two main fluid
reservoirs (deep hydrothermal and shallow H2S-rich brine). This allowed the two fluids to penetrate into, and mix within, the
breccia units. Alteration and stripping of Cu, As, Co, and Ni from the Old Red Sandstone adjacent to the main east-
west–trending fault array was likely the result of focusing and upward flow of relatively reduced lower Paleozoic-equilibrated
metal-bearing fluids within fault-related damage zones. Flow into the basal Waulsortian breccias was via the main Lisheen
fault array and northwest-trending faults in the hanging wall. Downward flow of low-temperature saline brines occurred by
migration down the upper parts of the Lisheen fault array or laterally along stratigraphy, within the dolomitized Waulsortian,
the Lisduff Oolite, and also possibly along the regional dolomite front. Brine flow could have been driven by local convec-
tion induced by thermal anomalies associated with the upwelling, high-temperature fluids or by simple density contrast. (c).
Stage 3: Fluid mixing. The onset of fluid mixing within the breccias led to rapid precipitation of sulfides in isotopic disequi-
librium in any available pore space. Acid generated by sulfide deposition enabled dolomite dissolution, thereby creating ad-
ditional porosity. The volume reduction associated with dolomite replacement by sulfide could have caused as much as a 25
percent increase in porosity, enabling further mixing and ore deposition. This, together with the elevated initial porosity and
nonstoichiometry of the matrix dolomite, may explain why the lithology was such a favorable host rock to ore. Abundant ev-
idence for multiple stages of sulfide deposition, reworking, and brecciation suggests a protracted evolution of the system in
tandem with active faulting. Zone-refining processes may have led to some of the metal zonation and textural complexity ob-
served. White matrix breccia may have developed above the ore zones due to limited downward collapse caused by the vol-
ume loss associated with sulfide replacement. (d). Stage 4: Hydrothermal sealing and progressive burial. Sulfur isotope data
suggest that mineralization terminated due to exhaustion of the main H2S source and brine reservoir or blocking of brine in-
filtration pathways, possibly by deposition of supra-Waulsortian argillaceous sediments. The late ore stage involved choking
of residual porosity by precipitation of calcite, dolomite, and sulfides from the principal ore fluid alone. Sulfide deposition at
this time was probably driven by simple cooling. The late-stage calcite (C4) and dolomite (D4) veins and breccias may reflect
overpressuring of the principal ore fluid in the main-flow conduits caused by progressive burial and hydrothermal sealing. A
late overprint by low-temperature, high-salinity fluids resulted in remobilization of preore or main ore-stage sulfides and
precipitation of D5 pink dolomite. It is suggested that these fluids represent evolved basin formation waters, mobilized as a
result of the onset of Variscan compression to the south of Ireland in the Mid- to Late Carboniferous.

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82 WILKINSON ET AL.
Navan Zn + Pb orebody, Ireland: Evidence from metal distribution trends,
mineral textures, and δ34S analyses: ECONOMIC GEOLOGY, v. 97, p. 73–91.
Boast, A.M., Coleman, M.L., and Halls, C., 1981, Textural and stable isotope
evidence for the genesis of the Tynagh base metal deposit, Ireland: ECO-
NOMIC GEOLOGY, v. 76, p. 27–55.
Boyce, A.J., 1990, Sedimentation, exhalation and sulphur isotope geochem-
istry of the Silvermines Zn + Pb + Ba deposits, County Tipperary, Ireland:
Unpublished Ph.D thesis, Glasgow, Scotland, University of Strathclyde,
354 p.
Boyce, A.J., Anderton, R., and Russell, M.J., 1983, Rapid subsidence and
Early Carboniferous mineralisation in Ireland: Transactions of the Institu-
tion of Mining and Metallurgy, v. 92, p. 55–66.
Boyce, A.J., Fallick, A.E., Fetcher, T.J., Russell, M.J., and Ashton, J.H., 1994,
Detailed sulphur isotope studies of lower Paleozoic-hosted pyrite below
the giant Navan Zn + Pb mine, Ireland: Evidence of mass transport of
crustal S to a sediment-hosted deposit: Mineralogical Magazine, v. 58A, p.
109–110.
Canfield, D.E., 2001, Isotope fractionation by natural populations of sulfate-
reducing bacteria: Geochimica et Cosmochimica Acta, v. 65, p. 1117–1124.
Canfield, D.E., and Thamdrup, B., 1994, The production of 34S-depleted sul-
fide during bacterial disproportionation of elemental sulfur: Science, v. 266,
p. 1973–1975.
Carboni, V., Walsh, J.J., Stewart, D.R.A., and Güven, J.F., 2003, Timing and
geometry of normal faults and associated structures at the Lisheen Zn/Pb
deposit, Ireland—investigating their role in the transport and trapping of:
Society for Geology Applied to Mineral Deposits Meeting, 7th biennial,
Athens, Greece, Proceedings, p. 665–668.
Caulfield, J.B.D., LeHuray, A.P., and Rye, D.M., 1986, A review of lead and
sulphur isotope investigations of Irish sediment-hosted base metal deposits,
with new data from Keel, Ballinalack, Moyvoughly and Tatestown deposits,
in Andrew, C.J., Crowe, R.W.A., Finlay, S., Pennell, W.M., and Pyne, J.,
eds., Geology and genesis of mineral deposits in Ireland: Dublin, Irish As-
sociation for Economic Geology, p. 591–616.
Claypool, C.E., Holser, W.T., Sakai, I.R., and Zak, I., 1980, The age curves
for sulfur and oxygen isotopes in marine sulfate and their mutual interpre-
tation: Chemical Geology, v. 28, p. 199–260.
Coleman, M.L., and Moore, M.P., 1978, Direct reduction of sulphates to sul-
phur dioxide for isotopic analysis: Analytical Chemistry, v. 28, p. 199–260.
Coomer, P.G., and Robinson, B.W., 1976, Sulphur and sulphate-oxygen iso-
topes and the origin of the Silvermines deposits, Ireland: Mineralium De-
posita, v. 11, p. 155–169.
Craig, H., 1957, Isotopic standards for carbon and oxygen and correction fac-
tors for mass-spectrometric analysis of carbon dioxide: Geochimica et Cos-
mochimica Acta, v. 12, p. 133–149.
Cruise, M.D., 2000, Iron oxide and associated base metal mineralization in
the Central Midlands basin, Ireland: Unpublished Ph.D thesis, Dublin,
Trinity College, 651 p.
Cruise, M.D., Boyce, A.J., and Fallick, A.E., 1999, Iron oxide alteration as-
sociated with the carbonate-hosted Tynagh and Crinkill base-metal de-
posits, Ireland: Evidence of the involvement of dissolved atmospheric oxy-
gen, in Stanley, C.J. et al., eds., Mineral deposits: Processes to processing:
Rotterdam, Balkema, v. 2, p. 833–836.
Czamanske, G.K., 1974, The FeS content of sphalerite along the chalcopy-
rite-pyrite-bornite sulfur fugacity buffer: ECONOMIC GEOLOGY, v. 69, p.
1328–1334.
Dixon, P.R., LeHuray, A.P., and Rye, D.M., 1990, Basement geology and tec-
tonic evolution of Ireland as deduced from Pb isotopes: Journal of the Ge-
ological Society [London], v. 147, p. 121–132.
Doyle, E., Bowden, A.A., Jones, G.V., and Stanley, G.A., 1992, The geology
of the Galmoy deposits, in Bowden, A.A., Earls, G., O’Connor, P.G., and
Pyne, J.F., eds., The Irish minerals industry 1980–1990: Dublin, Irish As-
sociation for Economic Geology, p. 211–225.
Earls, G., 1994, The Lisheen Zn-Pb deposit: Mining Magazine, July 1994, p.
6–8.
Elmes, J.D., Fusciardi, L.P., and Guven, J.F., 2000, Geology of the Lisheen
zinc/lead deposit: first impressions, in Europe’s major base metal deposits
[abs.]: Dublin, Irish Association for Economic Geology, Abstracts Volume,
3 p.
Everett, C.E., 1999, Tracing ancient fluid flow pathways: A study of the
Lower Carboniferous base metal ore field in Ireland: Unpublished Ph.D
thesis, New Haven, CT, Yale University, 354 p.
Everett, C.E., and Wilkinson, J.J., 2000, What makes an orebody? A com-
parison of fluid inclusion and sulfur isotope data from prospects and de-
0361-0128/98/000/000-00 $6.00
posits in the Irish Zn-Pb ore field [abs]: Geological Society of America Ab-
stracts with Programs, v. 32, no. 7, p. A-282.
Everett C.E., Wilkinson, J.J., and Rye, D.M., 1999a, Fracture-controlled
fluid flow in the lower Palaeozoic basement rocks of Ireland: Implications
for the genesis of Irish-type Zn-Pb deposits: Geological Society of London
Special Publications, v. 155, p. 247–276.
Everett, C.E., Wilkinson, J.J., Boyce, A.J., Ellam, R.M., Fallick, A.E., and
Gleeson, S.A., 1999b, The genesis of Irish-type Zn-Pb deposits: Character-
isation and origin of the principal ore fluid, in Stanley, C.J. et al., eds., Min-
eral deposits: Processes to processing: Rotterdam, Balkema, v. 2, p.
845–848.
Everett, C.E., Wilkinson, J.J., Boyce, A.J., and Gleeson, S.A., 2001, The role
of bittern brines and fluid mixing in the genesis of the Navan Zn-Pb de-
posit, Ireland [abs]: Geological Society of America Abstracts with Pro-
grams, v. 33, no. 7.
Everett, C.E., Rye, D.M., and Ellam, R.M., 2003, Source or sink? An assess-
ment of the role of the Old Red Sandstone in the genesis of the Irish Zn-
Pb deposits: ECONOMIC GEOLOGY, v. 98, p. 31–50.
Eyre, S.L., 1998, Geochemistry of dolomitization and Zn-Pb mineralization
in the Rathdowney trend, Ireland: Unpublished Ph.D thesis, University of
London, 414 p.
Eyre, S.L., Wilkinson, J.J., Stanley, C.J., and Boyce, A.J., 1996, Geochemistry
of dolomitization and zinc-lead mineralization in the Rathdowney trend,
Ireland [abs.]: Geological Society of America Abstracts with Programs, v.
28, p. A210–A211.
Fallick, A.E., Ashton, J.H., Boyce, A.J., Ellam, R.M., and Russell, M.J., 2001,
Bacteria were responsible for the magnitude of the world-class hydrother-
mal base-metal orebody at Navan, Ireland: ECONOMIC GEOLOGY, v. 96, p.
883–888.
Fusciardi, L.P., Guven, J.F., Stewart, D.R.A., Carboni, V., and Walshe, J.J.,
2003, The geology and genesis of the Lisheen Zn-Pb deposit, Co. Tipper-
ary, Ireland, in Kelly, J.G., Andrew, C.J., Ashton, J.H., Boland, M.B., Earls,
G., Fusciardi, L., and Stanley, G., eds., Europe’s major base metal deposits:
Dublin, Irish Association for Economic Geology, p. 455–481.
Gleeson, S.A., Banks, D.A., Everett, C.E., Wilkinson, J.J., Samson I. M., and
Boyce, A.J., 1999, Origin of mineralising fluids in Irish type deposits: Con-
straints from halogens, in Stanley, C.J. et al., eds., Mineral deposits:
Processes to processing: Rotterdam, Balkema, v. 2, p. 857–860.
Goldhaber, M.B., and Kaplan, I.R., 1975, Controls and consequences of sul-
fate reduction in recent marine sediments: Soil Science, v. 119, p. 42–55.
Graham, R.A.F., 1970, The Mogul base metal deposits, Co. Tipperary, Ire-
land: Unpublished Ph.D. thesis, London, ON, University of Western On-
tario, 235 p.
Gregg, J.M., Shelton, K.L., Johnson, A.W., Somerville, I.D., and Wright,
W.R., 2001, Dolomitization of the Waulsortian Limestone (Lower Car-
boniferous) in the Irish Midlands: Sedimentology, v. 48, p. 745–766.
Greig, J.A., Baadsgard, H., Cumming, G.L., Folinsbee, R.E., Krouse, H.R.,
Ohmoto, H., Sasaki, A., and Smejkal, V., 1971, Lead and sulfur isotopes of
the Irish base metal mines in Carboniferous carbonate host rocks: Tokyo,
Society of the Mining Geologists of Japan Special Issue 2, p. 84–92.
Hitzman, M.W., 1995, Mineralization in the Irish Zn-Pb-(Ba-Ag) orefield:
Society of Economic Geologists Guidebook Series, v. 21, p. 25–61.
Hitzman, M.W., and Beaty, D.W., 1996, The Irish Zn-Pb-(Ba) orefield: Soci-
ety of Economic Geologists Special Publication, v. 4, p. 112–143.
Hitzman, M.W., and Large, D.E., 1986, A review and classification of the
Irish carbonate-hosted base metal deposits, in Andrew, C.J., Crowe,
R.W.A., Finlay, S., Pennell, W.M., and Pyne, J., eds., Geology and genesis
of mineral deposits in Ireland: Dublin, Irish Association for Economic Ge-
ology, p. 217–238.
Hitzman, M.W., O’Connor, P.G., Shearley, E., Schaffalitzky, C., Beatty, D.W.,
Allan, J.R., and Thompson, T., 1992, Discovery and geology of the Lisheen
Zn-Pb-Ag prospect, Rathdowney trend, Ireland, in Bowden, A.A., Earls,
G., O’Connor, P.G., and Pyne, J.F., eds., The Irish minerals industry
1980–1990: Dublin, Irish Association for Economic Geology, p. 227–246.
Hitzman, M.W., Allan, J.R., and Beaty, D.W., 1998, Regional dolomitization
of the Waulsortian Limestone in southeastern Ireland: Evidence of large-
scale fluid flow driven by the Hercynian orogeny: Geology, v. 26, p. 547–550.
Hitzman, M.W., Redmond, P.B., and Beaty, D.W., 2002, The carbonate-
hosted Lisheen Zn-Pb-Ag deposit, County Tipperary, Ireland: ECONOMIC
GEOLOGY, v. 97, p. 1627–1655.
Honjo, H., and Sawada, Y., 1982, Quantitative measurements on the mor-
phology of NH4Br dendritic crystal growth in a capillary: Journal of Crystal
Growth, v. 58, p. 297–303.
82
 ORE-FORMING PROCESSES, LISHEEN CARBONATE-HOSTED Zn-Pb DEPOSITS, IRELAND
Jørgensen, B.B., Isaksen, M.F., and Jannasch, H.W., 1999, Bacterial sulfate
reduction above 100°C in deep-sea hydrothermal vent sediments: Science,
v. 258, p. 1756–1757.
Lee, M.J., 2002, Origin and Zn-Pb mineralization of dolomite breccias in the
Irish Midlands: Unpublished Ph.D thesis, University of London, 256 p.
Lee, M.J., and Wilkinson, J.J., 2002, Cementation, hydrothermal alteration,
and Zn-Pb mineralization of carbonate breccias in the Irish Midlands: Tex-
tural evidence from the Cooleen zone, near Silvermines, County Tipperary:
ECONOMIC GEOLOGY, v. 97, p. 653–662.
Lee, M.J., Wilkinson, J.J., and Earls, G., 2001, Textural and cathodolumines-
cence evidence for the origin of black dolomite matrix breccias in the Irish
Zn-Pb ore field, in Piestrzñski, A. et al., eds., Mineral deposits at the be-
ginning of the 21st century: Lisse, Swets and Zeitlinger, p. 161–164.
Lowther, J.M., Balding, A.B., Dunphy, S., and McEvoy, F.M., 1999, The Gal-
moy mine: Some geological aspects of development from 1995 to 1999, in
Stanley, C.J. et al., eds., Mineral deposits: Processes to processing: Rotter-
dam, Balkema, v. 2, p. 881–884.
Lowther, J.M., Balding, A.B., McEvoy, F.M., Dunphy, S, MacEoin, P.M., and
Bowden, A.A., 2003, The Galmoy zinc-lead orebodies: Structure and metal
distribution—clues to the genesis of the deposit, in Kelly, J.G., Andrew,
C.J., Ashton, J.H., Boland, M.B., Earls, G., Fusciardi, L., and Stanley, G.,
eds., Europe’s major base metal deposits: Dublin, Irish Association for Eco-
nomic Geology, p. 437–454.
Mallon, A.J., 1997, Petrological and mineralogical characteristics of the Old
Red Sandstone facies rocks beneath base metal deposits as a guide to the
setting of mineralisation in the Irish Midlands: Unpublished Ph.D. thesis,
Ireland, University College Cork, 636 p.
O’Keeffe, W.G., 1986, Age and postulated source rocks for mineralization in
central Ireland as indicated by lead isotopes, in Andrew, C.J., Crowe,
R.W.A., Finlay, S., Pennell, W.M., and Pyne, J., eds., Geology and genesis
of mineral deposits in Ireland: Dublin, Irish Association for Economic Ge-
ology, p. 617–624.
Philcox, M.E., 1983, Lower Carboniferous stratigraphy of the Irish Midlands:
Dublin, Irish Association for Economic Geology, 89 p.
Phillips, W.E.A., and Sevastopulo, G.D., 1986, The stratigraphic and struc-
tural setting of Irish mineral deposits, in Andrew, C.J., Crowe, R.W.A., Fin-
lay, S., Pennell, W.M., and Pyne, J., eds., Geology and genesis of mineral
deposits in Ireland: Dublin, Irish Association for Economic Geology, p.
1–30.
Reed, C.P., and Wallace, M.W., 2003, Cementation, hydrothermal alteration,
and Zn-Pb mineralization of carbonate breccias in the Irish Midlands—a
discussion: ECONOMIC GEOLOGY, v. 98, 191–193.
Rhoden, N.H., 1960, Mineralogy of the Silvermines district, Co. Tipperary,
Eire: Mineralogical Magazine, v. 32, p. 128–139.
Rhodes, D., Lantos, E.A., Lantos, J.A., Webb, R.J., and Owens, D.C., 1984,
Pine Point orebodies and their relationship to the stratigraphy, structure,
dolomitization, and karstification of the Middle Devonian barrier complex:
ECONOMIC GEOLOGY, v. 79, p. 991–1055.
Robinson, B.W., and Kusakabe, M., 1975, Quantitative preparation of sulfur
dioxide, for 34S/32S analyses, from sulfides by combustion with cuprous
oxide: Analytical Chemistry, v. 47, p. 1179–1181.
Roedder, E., 1968, The noncolloidal origin of “colloform” textures in spha-
lerite ores: ECONOMIC GEOLOGY, v. 63, p. 451–471.
Sáez, R., Pascual, E., Toscano, M., and Almodóvar, G.R., 1999, The Iberian
type of volcano-sedimentary massive sulphide deposits: Mineralium De-
posita, v. 34, p. 549–570.
Sakai, H., 1968, Isotopic properties of sulfur compounds in hydrothermal
processes: Geochemical Journal (Japan), v. 2, p. 29–49.
Samson, I.M., and Russell, M.J., 1987, Genesis of the Silvermines zinc-lead-
barite deposit Ireland: Fluid inclusion and stable isotope evidence: ECO-
NOMIC GEOLOGY, v. 82, p. 371–394.
0361-0128/98/000/000-00 $6.00
83
Sangster, D.F., Savard, M.M., and Kontak, D.J., 1998, A genetic model for
mineralization of lower Windsor (Visean) carbonate rocks of Nova Scotia,
Canada: ECONOMIC GEOLOGY, v. 93, p. 932–952.
Sevastopulo, G.D., and Redmond, P., 1999, Age of mineralization of carbon-
ate-hosted, base metal deposits in the Rathdowney trend, Ireland: Geolog-
ical Society of London Special Publication, v. 155, p. 303–311.
Shearley, E., Redmond, P., Goodman, R., and King, M., 1995, A guide to the
Lisheen Zn-Pb deposit: Society of Economic Geologists Guidebook Series,
v. 21, p. 123–137.
Shearley, E., Redmond, P., King, M., and Goodman, R., 1996, Geological
controls on mineralization and dolomitization of the Lisheen Zn-Pb-Ag de-
posit, Co. Tipperary, Ireland: Geological Society of London Special Publi-
cations, v. 107, p. 23–33.
Sheridan, D.J.R., 1977, The hydrocarbons and mineralization proved in the
Carboniferous strata of deep boreholes in Ireland, in Garrard, P., ed., Pro-
ceedings of the forum on oil and ore in sediments: London, Department of
Geology, Imperial College, p. 113–146.
Stacey, J.S., and Kramers, J.D., 1975, Approximation of terrestrial lead iso-
topic evolution by a two-stage model: Earth and Planetary Science Letters,
v. 26, p. 207–221.
Stetter, K.O., 1999, Extremophiles and their adaptation to hot environments:
FEBS (Federation of European Biochemical Societies) Letters, v. 452, p.
22–25.
Sverjensky, D.A., 1981, The origin of a Mississippi Valley-type deposit in the
Viburnum Trend, Southeast Missouri: ECONOMIC GEOLOGY, v. 76, p.
1848–1872.
Swart, P.K., Wortmann, U.G., Mitterer, R.M., Malone, M.J., Smart, P.L.,
Feary, D.A., and Hine, A.C., 2000, Hydrogen sulfide-rich hydrates and
saline fluids in the continental margin of South Australia: Geology, v. 28, p.
1039–1042.
Taylor, S., 1984, Structural and paleotopographic controls of lead-zinc min-
eralization in the Silvermines orebodies, Republic of Ireland: ECONOMIC
GEOLOGY, v. 79, p. 529–548.
Tucker, M.E., and Wright, V.P., 1990, Carbonate sedimentology: Oxford,
Blackwell Science, 482 p.
Velasco, F., Sanchez-Espana, J., Boyce, A.J., Fallick, A.E., Sáez, R., and
Almodovar, G.R., 1998, A new sulphur isotopic study of some Iberian
pyrite belt deposits: Evidence of a textural control on sulphur isotope com-
position: Mineralium Deposita, v. 34, p. 4–18.
Wilkinson, J.J., 2003, On diagenesis, dolomitisation and mineralisation in the
Irish Zn-Pb orefield: Mineralium Deposita, v. 38, p. 968–983.
Wilkinson, J.J., and Earls, G., 2000, A high temperature hydrothermal origin
for black dolomite matrix breccias in the Irish Zn-Pb ore field: Mineralog-
ical Magazine, v. 64, p. 1077–1096.
Wilkinson, J.J., Boyce, A.J., Everett, C.E., and Lee, M.J., 2003, Timing and
depth of mineralization in the Irish Zn-Pb ore field, in Kelly, J.G., Andrew,
C.J., Ashton, J.H., Boland, M.B., Earls, G., Fusciardi, L., and Stanley, G.,
eds., Europe’s major base metal deposits: Dublin, Irish Association for Eco-
nomic Geology, p. 483–497.
Wright, W.R., Somerville, I.D., Gregg, J.M., Shelton, K.L., and Johnson,
A.W., 1999, Dolomite CL and 18O, 13C data from Irish Midlands and
Dublin basin, Carboniferous, in Stanley, C.J. et al., eds., Mineral deposits:
Processes to processing: Rotterdam, Balkema, v. 2, p. 913–917.
Wright, W.R., Johnson, A.W., Shelton, K.L., and Gregg, J.M., 2000, Fluid mi-
gration and rock interactions during dolomitisation of the Dinantian Irish
Midlands and Dublin basin: Journal of Geochemical Exploration, v. 69–70,
159–164.
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84 WILKINSON ET AL.

APPENDIX
Lisheen Sulfur Isotope Data

Sample no. Ore zone Line no. Mineral Description Stage δ34S (‰)

171/172.5 Derryville SA4401 Barite White Main +18.1

171/172.5 R Derryville SA4404 Barite White Main +17.2
105/185.65 Main-S SA4402 Barite White Main +14.5
105/185.65 R Main-S SA4405 Barite White Main +14.3
179/176.25 Main-S SA4358 Chalcopyrite Massive sulfide with bornite proximal to cpy Main –8.3
179/176.25 R Main-S SA4412 Chalcopyrite Massive sulfide with bornite proximal to cpy Main –7.4
235/167.0 Main-S SA4411 Chalcopyrite Massive sulfide Main –6.6
361/223.4 Bog SA4366 Galena Fine grained, calcarenite/oolite hosted Late? +1.6
361/223.4 R Bog SA4410 Galena Fine grained, calcarenite/oolite hosted Late? +3.2
451/139.10 Bog SA4388 Galena Euhedral galena in white dol. vug Late –23.2
449/95.5 Bog-S SA4782 Galena Calcite vein-hosted euhedral galena Late –1.7
262/159.1 Derryville SA4059 Galena Euhedral galena, postdated? by pale brown Main –10.9
colloform sphalerite
262/162.1 Derryville SA4074 Galena Vein-hosted galena associated with tennantite Late/post –26.1
262/162.1 R Derryville SA4214 Galena Vein-hosted galena associated with tennantite Late/post –26.7
262/162.1 Derryville SA4089 Galena Dolomite vein-hosted galena associated with tennantite Late/post –24.9
262/162.1 R Derryville SA4213 Galena Dolomite vein-hosted galena associated with tennantite Late/post –24.2
275/175.65 Derryville SA4344 Galena Galena intergrown with pyrite in black matrix dol. Early-main –19.6
325/149.3 Derryville SA4340 Galena Fine-grained galena intergrown with pyrite Main –9.2
359/148.65 Derryville SA4382 Galena Galena associated with fine crystalline pink sphalerite Main –15.1
394/164.4 Derryville SA4353 Galena Anhedral galena associated with sphalerite Main –9.8
395/194.05 Derryville SA4351 Galena Massive sulfide-coarse subhedral galena Main –12.2
402/196.0 Derryville SA4395 Galena Euhedral galena assoc. pale sphalerite rim, Late –5.6
in late white dol. vug
416/195.5 Derryville SA4350 Galena Anhedral galena Main –10.2
420/190.70 Derryville SA4346 Galena Vein-hosted galena assoc. pale crystalline sphalerite Late –16.6
137/130.0 Derryville-S SA4365 Galena Galena intergrown with pyrite Main –14.8
121/189.3 Main SA4058 Galena Euhedral galena associated with late calcite vug Late –14.8
121/190.2 Main SA4080 Galena Euhedral galena with associated sphalerite rim, Late –7.7
in late white dol. vug
121/190.2 Main SA4099 Galena Galena grain in white dolomite vug, pre- and postdated Late –5.5
by sphalerite?
121/192.8 Main SA4050 Galena Euhedral galena assoc. pale sphalerite rim, in late Late –10.5
white dol. vug
121/192.8 R Main SA4104 Galena Euhedral galena assoc. pale sphalerite rim, in late Late –10.5
white dol. vug
121/192.8 Main SA4082 Galena Coarse euhedral galena assoc. sphalerite, pyrite, and Late –11.9
white dol.
121/192.8 Main SA4224 Galena Massive fine-grained, anhedral galena Main –14.2
121/192.8 Main SA4053 Galena Massive galena-anhedral grains with embayments Main –13.9
431/199.65 Main SA4371 Galena Euhedral galena Main –10.8
431/205.70 Main SA4375 Galena Massive colloform galena, sphalerite, pyrite Main –11.2
431/207.15 Main SA4373 Galena Sub- to euhedral galena Main –11.3
457/212.6 Main SA4779 Galena Vein-hosted galena intergrown with sphalerite Main/Late –0.9
045/215.2 Main-S SA4357 Galena Euhedral galena Main –7.2
045/215.2 R Main-S SA4409 Galena Euhedral galena Main –4.9
179/176.25 Main-S SA4359 Galena Massive sulfide-fine-grained galena Main –6.4
235/167.0 Main-S SA4361 Galena Massive sulfide-fine-grained galena Main –10.0
451/135.65 Bog SA4392 Pyrite Massive pyrite with interstitial fine crystalline pale sphalerite Main –24.3
451/139.10 Bog SA4390 Pyrite Massive pyrite Late –30.0
171/172.5 Derryville SA4356 Pyrite Massive pyrite/marcasite-anhedral grains Main –14.9
095/335.0 Derryville SA4396 Pyrite Coarse-grained pyrite assoc. late brown sphalerite in Late +11.8
white dol. vug in oolite
095/335.0 Derryville SA4413 Pyrite Coarse-grained pyrite assoc. late brown sphalerite in Late +11.7
white dol. vug in oolite
262/129.8 Derryville SA4210 Pyrite Disseminated fine-grained pyrite hosted in black Pre- –39.3
dolomite matrix
262/152.3 Derryville SA4061 Pyrite Subhedral pyrite, hosted in pink dolomite-remobilized? Post- –37.9
262/153.6 Derryville SA4075 Pyrite Fine-grained disseminated pyrite, in black matrix dol. Pre –43.7
262/153.6 R Derryville SA4105 Pyrite Fine-grained disseminated pyrite, in black matrix dol. Pre –44.1
262/153.6 Derryville SA4055 Pyrite Subhedral pyrite grains in black matrix dol. postdated Pre- –40.3
by sph. veins
262/162.1 Derryville SA4071 Pyrite Massive pyrite/marcasite Early-main –29.2
262/162.1 Derryville SA4072 Pyrite Massive pyrite/marcasite Early-main –27.6
264/172.4 Derryville SA4343 Pyrite Pyrite intergrown with sphalerite Main –13.8
275/175.65 Derryville SA4345 Pyrite Pyrite intergrown with galena in black matrix dol. Pre- –38.5
325/149.3 Derryville SA4341 Pyrite Massive pyrite-anhedral grains Main –19.6

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APPENDIX (Cont.)

Sample no. Ore zone Line no. Mineral Description Stage δ34S (‰)

359/133.2 Derryville SA4384 Pyrite Fine-grained disseminated pyrite, in black matrix dol. Pre- –38.1
359/143.6 Derryville SA4386 Pyrite Massive pyrite, intergrown with sphalerite Main –8.7
359/152.0 Derryville SA4788 Pyrite ABL vein-hosted pyrite Late –20.2
395/194.05 Derryville SA4352 Pyrite Massive pyrite Main –19.5
420/190.7 Derryville SA4348 Pyrite Fine-grained anhedral pyrite Main –19.4
137/130.0 Derryville-S SA4363 Pyrite Massive pyrite/marcasite-anhedral grains Early-main –17.2
121/189.3 Main SA4078 Pyrite Pyrite veinlets-stockwork type Main? –12.9
121/189.3 Main SA4218 Pyrite Pyrite veinlets Main? –13.2
121/190.2 Main SA4049 Pyrite Massive pyrite/marcasite-anhedral grains Early-main –35.1
121/190.2 Main SA4051 Pyrite Massive pyrite/marcasite-anhedral grains Early-main –33.6
121/192.8 Main SA4095 Pyrite Massive-banded pyrite Main –16.3
121/192.8 Main SA4220 Pyrite Fine-grained banded pyrite Main –16.7
121/192.8 Main SA4222 Pyrite Fine-grained banded pyrite Main –18.4
121/192.8 Main SA4223 Pyrite Massive pyrite Main –23.9
121/194.0 Main SA4212 Pyrite Massive anhedral pyrite Main –12.8
121/319.2 Main SA4207 Pyrite ABL-hosted white dolomite vein-minor pyrite Late? –9.7
137/134.9 Main SA4090 Pyrite Massive pyrite-anhedral grains Main –17.5
137/134.9 Main SA4206 Pyrite Massive, fine-grained pyrite Main –16.9
431/191.5 Main SA4379 Pyrite Massive pyrite Early-main –26.1
431/205.70 Main SA4378 Pyrite Massive colloform galena, sphalerite, pyrite Main –14.9
431/210.35 Main SA4380 Pyrite ABL-hosted dolomite vein?-minor pyrite Late? –17.4
400/205.0 Main-N SA4393 Pyrite Fine-grained disseminated pyrite, in black dol. matrix Pre –40.7
451/135.65 Bog SA4391 Sphalerite Fine crystalline pale sphalerite Main –13.6
451/139.10 Bog SA4387 Sphalerite Coarse crystalline sphalerite in white dol./calcite vug Late –31.5
with galena
451/139.10 R Bog April 98 Sphalerite Coarse crystalline sphalerite in white dol./calcite vug Late –23.0
with galena
529/246.6 Bog-E SA4774 Sphalerite ABL calcite vein-hosted crystalline brown sphalerite Late +6.5
529/246.6 R Bog-E SA4787 Sphalerite ABL calcite vein-hosted crystalline brown sphalerite Late +6.4
449/95.5 Bog-S SA4780 Sphalerite Calcite vein-hosted fine crystalline sphalerite associated Late –8.4
with galena
095/335.0 Derryville SA4397 Sphalerite Coarse crystalline sphalerite in white dolomite vug/vein Late +8.6
assoc. py in oolite
095/335.0 R Derryville SA4414 Sphalerite Coarse crystalline sphalerite in white dolomite vug/vein Late +8.6
assoc. py in oolite
171/160.0 Derryville April 98 Sphalerite Crystalline brown sph. with minor galena, postdated by Late +2.3
white dol.
262/159.1 Derryville SA4057 Sphalerite Pale-brown colloform sphalerite associated with galena Main –10.3
grains-late
262/159.1 Derryville SA4203 Sphalerite Dark-brown to amber colloform sphalerite Main –11.6
262/159.1 Derryville SA4076 Sphalerite Dark-brown colloform sphalerite with minor pyrite Main –9.5
262/159.1 R Derryville SA4091 Sphalerite Dark-brown colloform sphalerite with minor pyrite Main –9.3
262/159.1 Derryville SA4216 Sphalerite Pale-brown colloform sphalerite Main –14.9
262/162.1 Derryville SA4077 Sphalerite Pale-brown colloform sphalerite Main –15.1
264/172.4 Derryville SA4342 Sphalerite Colloform sphalerite Main –9.6
325/135.0 Derryville SA4338 Sphalerite Fine crystalline pale sphalerite Main –17.2
325/146.2 Derryville SA4339 Sphalerite Fine crystalline pink sphalerite Main –8.1
325/149.30 Derryville April 98 Sphalerite Crystalline yellow sphalerite Main –4.5
359/143.6 Derryville SA4385 Sphalerite Massive sulfide-pale yellow, fine crystalline sphalerite Main –18.7
359/148.65 Derryville SA4383 Sphalerite Fine crystalline pale sphalerite associated with galena Main –7.7
394/164.4 Derryville SA4354 Sphalerite Fine crystalline pink sphalerite associated with galena Main/late –7.5
394/164.4 Derryville SA4355 Sphalerite Colloform sphalerite Main –12.3
416/195.5 Derryville SA4349 Sphalerite Fine crystalline pale sphalerite Main –6.1
137/130.0 Derryville-S SA4364 Sphalerite Fine crystalline pink sphalerite Main –16.1
463/173.0 Derryville-S SA4771 Sphalerite ABL calcite vein-hosted brown crystalline sphalerite Late +1.3
463/173.0 R Derryville-S SA4784 Sphalerite ABL calcite vein-hosted brown crystalline sphalerite Late +1.4
121/189.3 Main SA4221 Sphalerite Pale pink-brown colloform sphalerite Main –11.3
121/189.3 Main SA4052 Sphalerite Fine colloform, brown matrix type sphalerite, with Main –11.8
minor pyrite
121/189.3 R Main SA4100 Sphalerite Fine colloform, brown matrix type sphalerite, with Main –10.0
minor pyrite
431/199.65 Main SA4372 Sphalerite Fine crystalline pale sphalerite, finely layered Main –12.8
431/205.70 Main SA4376 Sphalerite Massive colloform galena, sphalerite, pyrite Main –13.9
431/207.15 Main SA4374 Sphalerite Brown sphalerite Main –6.4
457/212.6 Main SA4778 Sphalerite Calcite vein-hosted fine crystalline pink-brown sphalerite Late +0.5
471/210.4 Main SA4770 Sphalerite Red crystalline sphalerite associated with fine-grained Main –5.5
massive sulfide
475/223.2 Main SA4777 Sphalerite Coarse crystalline yellow sphalerite in white dol/calc? Late +2.3
515/173.7 Main April 98 Sphalerite Crystalline amber sphalerite associated with pink dolomite vug Late/post +0.3

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APPENDIX (Cont.)

Sample no. Ore zone Line no. Mineral Description Stage δ34S (‰)

514/182.5 Main-S SA4762 Sphalerite Very coarse, euhedral, pale yellow sphalerite in calcite vug Late –8.8
400/205.65 Main-N SA4394 Sphalerite Pale, colloform sphalerite Main –13.2
517/204.9 Main-N SA4773 Sphalerite Coarse crystalline yellow sphalerite in white dolomite vug Late –5.9
517/205.0 Main-N SA4772 Sphalerite Coarse crystalline yellow sphalerite in white dolomite vug Late –5.8

Notes: Sample numbers are given as drill hole number/depth (meters); R denotes repeat analysis of same sulfide separate; all results are given relative to
the Vienna-CDT standard

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