Taetz Et Al., 2016 - CMP

Contrib Mineral Petrol (2016) 171:90
DOI 10.1007/s00410-016-1295-z
ORIGINAL PAPER
Fluid–rock interaction and evolution of a high-pressure/low-

temperature vein system in eclogite from New Caledonia: insights
into intraslab fluid flow processes
Stephan Taetz1 • Timm John2 • Michael Bröcker1 • Carl Spandler3
Received: 1 April 2016 / Accepted: 1 September 2016 / Published online: 15 October 2016
Ó Springer-Verlag Berlin Heidelberg 2016
Abstract A complex high-pressure/low-temperature vein external fluids with slightly different composition that most
system that cross-cuts eclogitic host rocks of the Pouébo likely are related to similar dehydration reactions in other
Eclogite Melange (northern New Caledonia) records the parts of the subducting slab. Due to the source-rock-im-
prograde blueschist-to-eclogite transition and associated posed compositional differences, these fluids are not in
formation of garnet–quartz–phengite veins. Geothermo- equilibrium with the infiltrated rock volume and induce the
barometry (Grt–Cpx–Ph, Zr-in-rutile) and pseudosection formation of distinct metasomatic selvages by dissolution–
calculations indicate peak metamorphic conditions of ca. precipitation processes. Mass-balance calculations show
540 °C and 1.9–2.2 GPa. Petrological and geochemical that Ca, Na and Li are added to the selvage by the external
observations as well as pseudosection modelling suggest fluid. LILE and to a lesser extend also HREE are mobilized
that the main vein network is formed by dehydration pro- and removed from the selvage. The LREE are predomi-
cesses that collected internally derived fluids related to the nantly buffered by newly formed minerals (e.g. epidote).
breakdown of hydrous phases (amphibole, chlorite, epi- Petrological evidence implies that the studied vein system
dote) during prograde metamorphism. The lower solid formed while the sample was still part of a coherent sub-
volume of the newly formed phases and the associated ducting slab. Rb–Sr geochronology indicates that this
increase in pore fluid pressure lead to the formation of occurred at 38.2 ± 0.3 Ma. This age is ca. 6 myr younger
veins that allowed for accumulation and channelized than the hitherto presumed peak metamorphic age, sug-
evacuation of these fluids. Such veins do not show meta- gesting a more complex and protracted metamorphic his-
somatic alteration selvages because the fluid–rock system tory for the PEM.
had been in chemical equilibrium. A second vein type
(transport veins) records the superimposed influx of Keywords Eclogite Slab dehydration Fluid–rock
interaction Metasomatism Rb–Sr geochronology
Mass-balance calculations New Caledonia
Communicated by Othmar Müntener.
Electronic supplementary material The online version of this Introduction

article (doi:10.1007/s00410-016-1295-z) contains supplementary
material, which is available to authorized users.
Subduction zones play an important role in the global
& Stephan Taetz volatile cycle and the interaction among Earth’s geo-
stephan.taetz@uni-muenster.de
chemical reservoirs. During subduction and progressive
1
Institut für Mineralogie, Universität Münster, Corrensstraße heating of the slab, hydrous minerals in the slab become
24, 48149 Münster, Germany progressively unstable, break down and release water
2
Institut für Geologische Wissenschaften, Freie Universität (Schmidt and Poli 1998). The released fluids allow element
Berlin, Malteserstr. 74-100, 12449 Berlin, Germany transport and trigger metamorphic processes within the
3
Economic Geology Research Centre, James Cook University, subducting slab, along the plate interface and in the over-
Townsville 4811, Australia lying mantle wedge (e.g. John and Schenk 2003; Bebout
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90 Page 2 of 27 Contrib Mineral Petrol (2016) 171:90
2007; van der Straaten et al. 2008; Marschall and Schu- opportunity to investigate ‘‘frozen-in’’ stages of dehydra-
macher 2012). A major fluid release pulse occurs during tion and both internal and external fluid flow processes that
the transformation of mafic crustal rocks from ‘‘wet’’ are related to the blueschist-to-eclogite transition in a
blueschist (ca. 4–5 wt% fluid) to ‘‘dry’’ eclogite (\1 wt% subducting slab.
fluid) (Peacock 1993; Gao and Klemd 2001; John et al.
2012). Other potential fluid sources include pelitic sedi-
ments and serpentinites (e.g. Spandler and Pirard 2013). Geological setting
These fluids can reach the mantle wedge, either by chan-
nelized flow (e.g. John et al. 2012) or by rising diapirs of New Caledonia (Fig. 1), located in the south-western
hybridized plate interface rocks (e.g. Marschall and Schu- Pacific, represents the northernmost subaerial exposure of
macher 2012) and locally induce partial melting. The the NNW–SSE trending oceanic ridge structure known as
chemical freight of the fluids is considered to create the the Norfolk Ridge. The basement of this island group is
distinct chemical signature of the resulting arc magmas, built up by a crustal slice that was rifted from Gondwana in
which are characterized by the relative enrichment of fluid- the late Cretaceous (Sdrolias et al. 2004). New Caledonia
mobile elements (e.g. LILE, LREE) over fluid-immobile developed from Permian to Oligocene time in different
elements (HFSE, HREE) (Hawkesworth et al. 1993; John geodynamic settings and comprises several terranes (Clu-
et al. 2004; Spandler and Pirard 2013). Nevertheless, there zel et al. 2001, 2012). The main island can be subdivided
is considerable debate about the general relationships into four tectonostratigraphic domains (Aitchison et al.
between mineral reactions, fluid flow, and mobilization of 1998; Cluzel et al. 2012) including the continental base-
both major and trace elements during fluid–rock interac- ment, the basaltic Poya terrane, a peridotite nappe and a
tion, which have not yet been properly quantified (e.g. HP/LT metamorphic belt.
Scambelluri and Philippot 2001; John et al. 2004; Hermann The basement is comprised of early Permian metasedi-
et al. 2006; Bebout 2007; John et al. 2008; Spandler et al. mentary and metavolcanic rocks as well as Mesozoic
2011; Herms et al. 2012; Spandler and Pirard 2013; pelites (Paris et al. 1981; Brothers and Lillie 1988) that
Angiboust et al. 2014; Konrad-Schmolke and Halama developed along or accreted to the eastern Gondwana
2014). The key to reaching a better understanding of the margin. This rock association is partially overlain by the
subduction zone fluid cycle and its chemical consequences basaltic Poya terrane that is interpreted to have formed in a
is to obtain in-depth understanding of how fluids flow Campanian to late Paleocene back-arc basin located E or
within and out of the descending slab. NE of New Caledonia (Ali and Aitchison 2000; Cluzel
Although the importance of inter- and intraslab fluid et al. 2001). The Poya terrane was juxtaposed onto the
flow for the modification of geochemical reservoirs is basement and subsequently overthrust by an extensive
generally recognized, the details of such processes are not peridotite nappe (‘‘Nappe Ophiolitique’’) representing
yet fully understood. Among the unresolved aspects, the Cretaceous oceanic lithosphere from a paleoridge in the
following questions are of special importance: (a) How Loyality Basin (Prinzhofer et al. 1980). The NE part of the
does rock dehydration and drainage under high-pressure island consists of a Cenozoic HP/LT belt, that is stretching
conditions work? (b) What does the flow pattern of the across a ca. 175 km long and ca. 35 km wide NW–SE
liberated fluids look like? (c) What are the relationships trending anticlinal range (Aitchison et al. 1995; Spandler
between observed flow patterns and chemical changes in et al. 2005; Baldwin et al. 2007). The relationship to the
the adjacent rocks? peridotite nappe is still unclear (c.f. Cluzel et al. 2001;
The major aims of this study are: (1) to document the Spandler et al. 2005; Baldwin et al. 2007) (Fig. 1).
fluid release and flow structure formation induced by the The HP/LT metamorphic belt is the subject of this study.
breakdown of water-bearing phases at the blueschist-to- The belt ranges in metamorphic grade from low-grade
eclogite transition in a subducting slab; (2) to assess the blueschist (0.3 GPa, 250 °C) in the south and west, up to
evolution from initial low fluid flow towards later stage 1.9–2.4 GPa, 500–650 °C in the NE (e.g. Clarke et al.
channelized flow system; and (3) to evaluate the effect of 1997; Carson et al. 1999, 2000; Fitzherbert et al. 2005;
an infiltrating external fluid. For this purpose, we combine Potel 2007; Baldwin et al. 2007; Vitale Brovarone and
bulk and mineral trace-element data, pseudosection mod- Agard 2013). Based on differences in lithology, geo-
elling and Rb–Sr geochronology to examine the fluid–rock chemistry, metamorphic grade and structural features, two
interaction in a well-preserved vein system in high-pres- subunits can be distinguished: (1) the Diahot Blueschist
sure/low-temperature (HP/LT) rocks of the Pouébo Unit (DBU) which comprises mainly blueschist-facies
Eclogite Mélange (PEM), NE New Caledonia. This HP/LT rocks of sedimentary protolith to the southwest (Maurizot
mélange zone represents an excellent natural analogue of et al. 1989) and (2) the Pouébo Eclogite Melange (PEM) in
subducted oceanic crust and hence provides the excellent the north-east of the belt, which consists mainly of
123
Contrib Mineral Petrol (2016) 171:90 Page 3 of 27 90
a New Caledonia - main island b

Mahamate
Pam
peridotite nappe 0 1 2 4km
N
Tiari
basaltic Poya terrane
Pam Peninsula
Pouébo eclogite mélange
Hb
Pouébo
l- i
Diahot blueschists Amoss
n
sedimentary rocks from
Koumac
Gondwana breakup
Hienghene
basement terrane
Col d‘ Amoss
Pandelai
Ep-
in
Grt
-in
Poya
Lw
Diahot River
Na
s-
-A
in
Ouégoa
m
p-
in
22 S
Australia
New
Caledonia N Diahot blueschists Pouébo eclogite mélange
Gln - Lws eclogite + Gln sampling location
0 km 60 Gln - Ab eclogite
New
Zealand Noumea Gln - Ep
Cretaceous to Eocene
Ep - Alm - Gln river sediments
167 E sedimentary rocks
Fig. 1 a Simplified geological map of New Caledonia (after the mineral isogrades, mineral distribution patterns and the position of
Aitchison et al. 1995) showing the main tectonostratigraphic domains. the sampling site (Gln = glaucophane; Lws = lawsonite; Ab = al-
b Close-up of the Pam Peninsula (after Clarke et al. 1997) indicating bite; Ep = epidote; Alm = almandine)
eclogite-facies rocks of mixed protolith (e.g. Black and phengite dating yielded metamorphic ages ranging from
Brothers 1977; Yokoyama et al. 1986; Clarke et al. 1997; 40 Ma in the NE to 36 Ma in the SW, suggesting a regional
Carson et al. 1999; Rawling and Lister 2002; Spandler younging trend (Baldwin et al. 2007). Apatite fission track
et al. 2005) (Fig. 1). The eclogite- and blueschist-facies data led these authors to suppose that cooling to \125 °C
mineral assemblages are well-preserved and show only was accomplished at ca. 34 Ma by rapid exhumation of the
minor indications for greenschist-facies overprinting HP-terrane as a coherent block via ductile shearing asso-
(Carson et al. 2000). The PEM is a heterogeneous associ- ciated with crustal extension. Final exhumation from
ation of mafic rocks that occur as blocks and tectonic slices shallow depths occurred by late-stage normal faulting and
(up to 100 m in size) within a meta-ultramafic (serpentinite erosion (Baldwin et al. 2007). For details on the tectonic
plus talc- and chlorite-schist) or metasedimentary matrix and metamorphic history see Rawling and Lister (1999;
that can be described as a hybrid mélange (Maurizot et al. 2002), Cluzel et al. (2001, 2012), Spandler et al. (2005),
1989; Cluzel et al. 2001; Spandler et al. 2005, 2008; Cluzel Baldwin et al. (2007) and Vitale Brovarone and Agard
et al. 2012). Based on the geochemical characteristics of (2013).
the mafic rocks, this rock association has been interpreted
to represent a dismembered slice of oceanic crust that
originally formed in a Late Cretaceous to Eocene Sample description
(85–55 Ma) back-arc or marginal basin setting (Spandler
et al. 2005). The samples were collected from an isolated outcrop of the
The entire HP/LT belt is interpreted to be a remnant of PEM that is located ca. 2.5 km east of the mouth of Amoss
ocean crust and sediments subducted to depths of up to Creek (S 20 16.748, E 164 26.829, Fig. 1). This outcrop
80 km (Clarke et al. 1997; Carson et al. 1999, 2000; (ca. 2 9 4 m in size) shows a well-preserved HP vein
Spandler et al. 2004). Based on U–Pb zircon ages, Spandler system in amphibole-rich eclogite (Spandler and Hermann
et al. (2005) suggested a lower time limit of ca. 55 Ma for 2006), comprising garnet-rich veins (?Ph, ?Qz; all min.
the onset of subduction. Uranium–Pb ages of ca. 44 Ma for abbr. after Whitney and Evans 2010) that form a discon-
zircon rims were interpreted to date peak eclogite-facies tinuous network without apparent reaction zones (type I
conditions (Spandler et al. 2005). 40Ar/39Ar K-feldspar and veins) and a vein with a distinct omphacite-rich reaction
123
a 41-A b
40-A
unaltered host rock
reference samples selvage-host-transition
18
selvage
17
profile B host rock
16
type II vein
15
selvage-host-transition
14 selvage
type II vein
13
host rock
12
11
10 cm 2 cm
c d type II vein selvage selvage-host transition
type I vein
host rock
2 cm 1 cm
Fig. 2 Outcrop photographs of the studied vein system. a White outlines the transition zone between selvage and host rock. b Close-up
rectangles show the location of the sampling profile. Numbers denote of a type II vein. c Network of type I veins in the host rock. d Cut rock
slabs 11–18 of a continuous profile. White circles indicate drill core slab showing type II vein, selvage and transition to host rock
locations for unaltered host rock samples 41-A and 40-A. Dashed line
selvage (type II vein) that cross-cuts the host rock (Fig. 2). rare in the matrix, and quartz is absent (Figs. 3, 4a–c). The
Type I veins are up to 1 cm thick and reach up to 0.5 m in randomly oriented and intergrown amphiboles are evenly
length. The studied type II vein is up to 5 cm thick and can distributed in the matrix and contain small zircons (\5 lm)
be traced up to a length of ca. 1 m (Figs. 2, 4c). In order to as the only inclusions. Omphacite (up to 1.5 mm) is
document fluid-induced geochemical and petrological apparently in textural equilibrium with amphibole and
modifications, continuous sampling traverses were cut mostly shows random orientation, but locally follows the
across the studied outcrop covering veins, metasomatic main foliation (Fig. 4a, b). In clinopyroxene (Cpx)-rich
selvage zones and host rock. Additional drill cores of domains short-prismatic omphacite contains abundant
samples representing unaltered host rock were taken at a inclusions of epidote and rutile. Slightly smaller, more
distance of ca. 0.5 m from the main eclogitic vein (Fig. 2). acicular Cpx grains with fewer inclusions occur in domains
with less omphacite (Fig. 4b). Porphyroblastic garnet (up to
Petrography 5 mm) is present as single grains. Garnet cores are rich in
fine-grained inclusions of titanite and ilmenite (\15 lm)
The host rock is an amphibole-rich eclogite with a fine- and are surrounded by a zone with abundant inclusions of
grained (\200 lm), weakly foliated matrix of glaucophane, quartz and omphacite (up to 300 lm), as well as minor
barroisitic hornblende, omphacite and epidote. Phengite is rutile and epidote. The outermost rim of such grains (ca.
123
a Grt Qz
Grt
Ph Omp + Ep Rt
Qz Ph
Omp + Amp + Ep
Omp + Amp + Ep
Rt
Grt
Rt
0.5 cm
host rock host-selvage transition selvage vein

Ph Rt
100 100
b Qz
Brs
modal abundance [%]
80 Gln 80
Ep
60 60
Grt
40 40
20 20
Omp
0 0
-50 -40 -30 -20 -10 -6 -5 -4 -3 -2 -1
distance to vein [cm]
Fig. 3 a Microphotographs of samples 17-II and 14-III documenting refinement of XRD data. An uncertainty of ±5 % is assumed for
texture and mineral distribution in a profile across host rock, selvage all mineral abundances. Higher uncertainties are expected for Ph due
and vein. b Variations in modal abundances of major phases across a to possible method specific texture effects
profile including slabs 14–18 (54 cm) determined by Rietveld
50 lm in width) is almost inclusion-free (Fig. 4a). Garnet II veins) is characterized by an inclusion-rich core with
records minor chloritization in some rare cases. Rutile is a ilmenite and titanite (\30 lm). An intermediate zone
common accessory phase in the host rock and occurs in contains omphacite inclusions (50–100 lm) that are
grain clusters (Fig. 4a, c) and as inclusions in omphacite equivalents of those occurring in the selvage matrix sur-
and garnet (Fig. 4b). Some grains are rimmed by retrograde rounding those garnets (Fig. 4d). The outer rim is generally
titanite. Zircon is present as inclusion (1–5 lm) in most almost inclusion-free. Textural characteristics of garnet
other phases. Apatite is a rare accessory phase. cores and outermost rims are identical to those recognized
The mineralogy of type I and II veins is dominated by in host rock garnet. A readily distinguishable feature is the
garnet, quartz and phengite. Garnet in type I veins is presence of the Cpx-rich intermediate zone. Garnet grains
characterized by a heterogeneous distribution of inclusions at the sharp vein-selvage contact inherit this characteristic
(Ttn, Omp, Qz; Fig. 4), whereas garnet in type II veins is inclusion pattern at the contact side, while inclusion-free
generally inclusion-free. Quartz grains are granoblastic (up vein garnet is present at the distant side (Figs. 2, 4e, f).
to 500 lm), and phengite is either present in single Other phases in the selvage are glaucophane, barroisitic
unoriented grains (20–150 lm) or in oriented clusters of hornblende and epidote that are texturally identical to the
grains (50–500 lm) wrapping garnet. Rutile (up to 2 cm), host rock. Rutile clusters are similar to the host rock, but
apatite, omphacite and amphibole can occur as isolated retrograde titanite rims are more distinctly developed.
single grains (up to 500 lm). Phengite (up to 10 lm) is present in minor amounts in the
The mineral assemblage of the metasomatic reaction transition zone between host and selvage, but is completely
zone around the type II vein (ca. 2–4 cm in width) is absent closer to the type II vein. The transition from the
dominated by fine-grained omphacite (ca. 10–50 lm). The selvage into the host rock is characterized by continuously
modal abundance of garnet decreases towards the type II decreasing abundance of omphacite and associated
vein, and garnet in the selvage (and outermost parts of type increase of amphibole (Fig. 4d).
123
a b
Omp
Rt
Ep
Rt Ttn
Grt
Omp
Qz
Amp
Omp + Amp + Ep
Omp
500 µm 100 µm
c d
Omp + Amp + Ep
Grt
Omp + Amp + Ep Grt
Omp
Omp
Qz
Rt Omp
Grt
Rt
500 µm 500 µm
e Rt
f
Omp
Ph
Qz
Grt
Omp
Qz
Grt
500 µm 500 µm
Fig. 4 Microphotographs of samples representing different parts of complex core-to-rim inclusion pattern. e Sharp contact zone at the
the vein system: a Porphyroblastic garnet with a characteristic selvage-vein boundary. Type II garnet is inclusion-free except from
inclusion zoning pattern in host rock matrix. b Tabular omphacite in close to the contact. f Typical Grt-Qz-Ph assemblage of the type II
host rock matrix. c Grt-Qz assemblage of dehydration vein cross- vein
cutting the host rock. d Grt in the fine-grained selvage showing
123
Analytical methods sections were prepared for all rock slabs to correlate petro-
graphic and geochemical characteristics. The cleaned sample
With the exception of whole rock major and trace-element material was crushed and ground in an agate ring mill. For
analysis, all analytical work was carried out at the Institut für mineral separates, a profile parallel to the whole rock sam-
Mineralogie, Universität Münster, Germany. Mineral com- pling traverse was crushed and ground in a disc-mill. The
positions were determined with a JEOL JXA 8600MX resulting material was sieved, washed and hand-picked for
electron microprobe. The operating conditions were set to analysis. Mineral modal abundances have been determined on
15 kV acceleration voltage, 15 nA beam current and a whole rock powders by X-ray diffractometry using a X’Pert
counting time of 5 s each on peak and background for all powder diffractometer [Cu-Ka1 radiation, primary beam Ge-
phases except garnet (20 s peak; 5 s background). For (111) monochromator]. The operating conditions were 45 kV
apatite measurements, the beam current was reduced to and 40 mA. Qualitative phase analyses were done using the
4 nA to minimize F diffusion. Spot sizes were 3–5 lm HIGHSCORE software (PANalytical, Germany). Rietveld
depending on the grain size. Natural mineral standards were refinement was performed using the FullProf Suite (v. 5.60;
used, and the raw data were matrix-corrected with a ZAF Rodriguez-Carvajal 2005). Whole rock major- and trace-
procedure. Zirconium concentrations for Zr-in-rutile ther- element analysis (except Li) was carried out by Activation
mometry have been analysed with a beam current of 120 nA Laboratories, Ancaster, Ontario, using the 4Lithoresearch
and a counting time of 150 s for the background and 300 s analytical protocol incorporating lithium metaborate tetrab-
on the sample. Titanium and Si were monitored to identify orate fusion and acid digestion for ICP-OES (major elements)
inclusions. Natural (RtR10) and synthetic rutile standards and ICP-MS (trace elements) analysis (Table 1).
were used for calibration. Replicate analyses of the R10 Whole rock powders and mineral separates for Rb–Sr
rutile reference material (n = 20; 1r uncertainties) yielded geochronology were spiked with 87Rb–84Sr solutions and
757 ± 13 ppm for Zr and 2775 ± 40 ppm for Nb, which digested in HF-HNO3 (5:1) in a tabletop setup, using ca.
are within error of published values (Zr 768.9 ± 7.7 ppm, 1–100 mg of sample material. After evaporation to dryness,
Nb 2592 ± 103.7 ppm; Luvizotto et al. 2009). the residue was re-dissolved in 6 N HCl and homogenized
Trace-element compositions of selected phases (Amp, on a hot plate overnight. After a second evaporation step,
Omp, Grt, Ph) were determined in thin sections by LA-ICP- Rb and Sr were separated by ion exchange chromatography
MS analysis. Measurements were conducted with a 193-nm (AG 50W-X8 resin) on glass columns using 2.5 N HCl.
ArF Excimer laser system (UP193HE, New Wave Research Rubidium–Sr analysis was carried out by thermal ionization
or Photon Machines Analyte G2) coupled to a sector field mass spectrometric analysis (TIMS) using a Finnigan Triton
ICP-MS (Element2, Thermo Finnigan). Laser energy density TIMS (for Sr) in static mode and a VG Sector 54 TIMS (for
on the sample was set to *4 J/cm2, and the repetition rate Rb). Rubidium was loaded with H2O on Ta filaments; Sr
was set to either 7 or 5 Hz. Analysis times were set to 15 or was loaded with TaF5 on W filaments. Correction for mass
19 s for the background and 40–45 s for analysis of sam- fractionation is based on 86Sr/88Sr = 0.1194. Fractionation
ples/standards, followed by a 15 s washout. The spot size correction of Rb ratios employed a factor deduced from
was varied between 25 and 60 lm depending on grain size multiple measurements of the NBS 607 standard. During
and inclusion abundance. In order to correct for instrumental the course of this study, the external reproducibility of
87
drift and mass bias, 21 spot analyses (including 1 measure- Sr/86Sr ratios for the NBS 987 standard was
ment of BIR-1G standard as an unknown) were bracketed by 0.701256 ± 0.000013 (2r, n = 10). Total procedural
3 measurements of the NIST 612 glass standard. Element blanks for Rb and Sr were\5 and\10 pg, respectively. For
concentration values used for the NIST 612 glass were the age calculation, 2r uncertainties of 1 % and 0.005 % were
GeoREM preferred values 6/2011 (Jochum et al. 2005). Data assigned to the measured 87Rb/86Sr and 87Sr/86Sr ratios,
reduction has been carried out with the software Glitter (v. respectively. Isochron ages were calculated with the Isoplot
4.4.4). Silicon concentrations determined by EMP were used software (version ex 4.15; Ludwig 2012) and are reported
as internal standards for all analyses. with 95 % confidence level (c.l.) in Table 4.
Whole rock powders for bulk-rock geochemistry,
geochronology and determination of the mineral modal
abundance were prepared from a ca. 50-cm long continuous Results
profile subdivided into 14 rock slabs (4.5 9 2.5 9 1 cm, ca.
40 g each), as well as from two drill cores (ca. 100 g each) Mineral chemistry
representing the host rock at a maximum distance from any
type II vein. The position of the drill cores and of individual Only a single phase of amphibole can optically be identi-
samples in the profile is indicated in Table 1 and Fig. 2. Thin fied in the host rock, but this phase ranges in composition
123
90
Table 1 Bulk-rock compositional data of the host rock, selvage and vein
Sample 41-A 40-A 18-II 17-II 16-II 15-C 15-II 15-A 14-C 14-B 14-A 14-IV (1) 14-V 13-II 12-II 11-I
Type Host Host Host Host Host Host Host Host Selvage Selvage Selvage Vein Selvage Host Host Host
123
Dist. from vein (cm) -53 -44 -33 -26 -18 -11.5 -10 -5 -2.8 -1.5 -0.5 0 2 7 14 21
Page 8 of 27
SiO2 48.66 49.78 49.97 48.17 47.29 47.93 47.49 47.14 50.11 50.97 51.82 54.78 48.96 47.01 48.22 46.71
Al2O3 13.28 12.81 13.30 12.67 12.58 12.90 13.22 13.44 10.97 10.04 9.72 14.93 11.17 12.63 13.38 14.17
Fe2O3(T) 16.18 15.80 15.54 15.84 15.81 15.70 16.30 17.75 13.60 12.29 11.14 21.78 14.34 16.63 15.29 14.58
MnO 0.25 0.24 0.32 0.25 0.24 0.21 0.27 0.29 0.15 0.11 0.10 1.11 0.17 0.22 0.22 0.19
MgO 6.11 6.09 5.10 5.92 6.18 6.47 6.34 5.91 5.96 5.69 5.90 1.72 5.86 6.28 5.72 5.48
CaO 9.01 8.30 8.44 8.94 9.88 9.69 9.51 9.06 10.61 11.52 11.79 6.38 10.56 8.61 9.35 9.25
Na2O 3.56 3.54 3.17 3.48 3.72 3.84 3.61 3.17 5.00 5.68 6.01 0.09 4.51 3.24 3.31 3.51
K2O 0.24 0.27 0.48 0.25 0.08 0.14 0.10 0.12 0.03 0.05 0.06 0.41 0.04 0.24 0.51 0.79
TiO2 2.90 2.98 2.74 2.81 2.86 2.86 2.86 2.86 2.94 2.84 2.54 0.18 3.00 2.92 2.97 3.20
P2O5 0.32 0.24 0.24 0.21 0.23 0.30 0.34 0.35 0.03 0.04 0.04 0.18 0.03 0.30 0.32 0.33
LOI (%) 0.14 0.39 0.03 0.24 0.38 0.54 0.20 0.33 0.28 0.42 0.33 -1.56 0.03 0.52 0.49 0.67
Total 100.70 100.40 99.33 98.78 99.24 100.60 100.20 100.40 99.69 99.65 99.45 100.00 98.68 98.60 99.77 98.87
Li 18.7 17.7 18.2 19.2 18.3 19.0 18.1 14.7 30.4 38.0 39.5 3.02 n.d. n.d. n.d. n.d.
Sc 47 47 46 43 44 45 45 47 42 41 42 42 42 46 48 51
V 524 528 486 508 535 534 529 469 597 653 691 130 597 495 545 569
Co 41 44 30 45 53 40 39 44 33 39 21 15 29 47 44 35
Ga 22 23 21 21 23 23 23 20 21 20 21 8 21 21 26 26
Ge 2.3 2.1 1.9 1.8 1.8 1.3 1.8 2 1 1 1 2.6 1.8 1.8 1.9 1.9
Rb 5 6 13 6 \1 2 1 1 1 1 2 13 1 5 13 20
Sr 73 59 51 56 77 82 85 94 47 52 44 4 46 93 105 137
Y 57.3 58.5 60.1 55.1 60.3 54.3 58.1 68.9 43.6 27.5 19.7 110 42.5 57.7 58.2 58.1
Zr 188 198 184 184 191 187 177 197 173 173 198 11 186 185 186 210
Nb 4.7 4.8 4.4 4.1 4.3 4.3 4.1 4.4 4.2 4.1 3.7 \0.2 4.7 4.7 4.9 5.9
Ag 1.4 1.6 1.8 1.7 1.8 1.2 1.7 1.4 1.7 1.5 1.5 \0.5 1.9 1.9 1.9 2.3
Ba 44 47 111 50 8 12 10 6 \3 4 10 109 4 31 101 164
Hf 4.2 4.5 4.7 4.6 5.0 4.1 4.7 4.5 4.5 4.4 5.0 0.4 4.9 5.0 5.0 5.1
Ta 0.36 0.42 0.36 0.29 0.32 0.28 0.33 0.28 0.36 0.35 0.33 \0.01 0.32 0.38 0.36 0.38
W 1.3 0.9 0.6 0.6 0.7 0.6 0.8 8.3 0.7 1.5 1.2 \0.5 1.1 0.9 0.9 0.9
Th 0.23 0.25 0.32 0.33 0.37 0.23 0.38 0.21 0.24 0.28 0.28 \0.05 0.38 0.40 0.39 0.40
U 0.15 0.15 0.12 0.12 0.16 0.15 0.16 0.15 0.10 0.12 0.12 \0.01 0.12 0.17 0.18 0.22
La 6.42 6.51 6.14 5.55 7.19 6.52 7.36 6.49 6.41 7.13 6.38 0.26 6.69 7.00 7.65 7.95
Ce 19.4 19.6 18.7 17.7 22.6 19.4 21.9 19.2 19.3 20.7 18.9 0.3 20.7 22.4 23.7 24.2
Pr 3.44 3.44 3.18 3.17 3.92 3.52 3.69 3.42 3.37 3.52 3.26 0.05 3.60 3.87 4.15 4.20
Nd 18.2 19.1 17.2 16.7 21.0 19.0 19.5 18.1 18.7 19.3 17.1 0.3 19.3 20.6 22.7 22.5
Negative and positive distance values denote sampling to the left and right of the vein, respectively. (Major and minor elements in wt%, trace elements in ppm: n.d. = not determined,
0.873
0.903
from barroisitic hornblende to glaucophane (Fig. S1b;
7.30
2.50
9.44
1.70
9.82
2.00
5.77
5.7
Host
11-I Table 2). There is little variation in the compositional
21 range of amphibole along the studied profile except for
0.857
0.920
slightly higher FeO and lower MgO and Al2O3 contents in
7.53
2.55
9.51
1.73
9.87
1.96
5.70
5.88
12-II
Host
the selvage glaucophane. Trace-element and REE con-

14
centrations are generally low (Table S1). Single spots with
0.919
0.892
elevated Zr (up to 70 ppm) and Hf ([3 ppm) concentra-
6.90
2.19
8.82
1.66
2.11
6.01
5.73
10.30
13-II
Host
tions are probably related to tiny zircon inclusions.

7
Omphacite compositions are homogeneous throughout
0.681
0.703
Selvage
the profile, independent of grain size (Fig. S1a) and are

6.13
1.81
7.09
1.30
7.74
1.52
4.34
4.52
14-V
characterized by a slight core-to-rim increase of jadeite

2
composition (core: Jd31Ac24Di45; rim: Jd37Ac18Di45;

14-IV (1)
Table 2). Omphacite inclusions in garnet are composi-

1.920
1.840
0.20
0.16
1.98
1.15
3.75
13.10
12.40
12.1
Vein
tionally indistinguishable from grains in the matrix
\# = below detection limit). Negative LOI in 14-IV (1) results from the weight gain due to high Fe content and oxidisation during ignition
0
(Table 2). Titanium and Zr concentrations are highly

0.300
0.381
Selvage
variable due to the aforementioned inclusions that could

5.25
1.70
5.93
0.89
4.19
0.72
1.98
2.1
14-A
-0.5
not be avoided during analysis. The LREE concentrations

are predominantly \1 ppm, while HREE concentrations
0.426
0.479
Selvage
reach up to 8 ppm.
6.22
1.96
7.20
1.12
5.84
1.06
2.96
3.04
-1.5
14-B
Garnet porphyroblasts representing different textural

sites in host rock, selvage and type II veins are charac-
0.713
0.701
Selvage
terized by a high almandine component (55–63 %;

6.25
1.97
7.53
1.33
8.24
1.61
4.58
4.55
-2.8
14-C
Table 2) and well-developed major-element zoning pat-

terns (Fig. 11; Table 2). Element distribution maps of
1.060
1.030
6.29
2.23
8.45
1.70
2.38
7.01
6.87
11.40
type II vein garnet show a complex sector-zoning pattern

15-A
Host
-5
perpendicular to the grain boundaries that is best devel-

oped in CaO contents, but is also evident in the FeO and
0.904
0.880
6.51
2.17
8.44
1.56
9.79
2.02
5.91
5.92
MgO contents (Fig. 11; Spandler and Hermann 2006).

15-II
Host
-10
Average compositions for host and selvage garnet are

Alm58Grs22Sps10Prp6And3 in the core, Alm62Grs19Sps3-
0.809
0.776
6.40
2.20
7.94
1.53
9.41
1.88
5.43
5.25
-11.5
Prp13And2 towards the rim, and Alm62Grs22Sps3Prp12-

15-C
Host
And1 in the outer rim (Table 2; Fig. S2). Trace-element

concentrations in host rock, selvage and vein are similar
0.942
0.955
6.85
2.27
8.79
1.62
2.08
6.16
6.08
10.10
(Fig. 5; Table S1). Garnet is the major host for HREE in

16-II
Host
-18
all zones; however, concentrations are slightly lower in

vein garnet. REE also show prominent zoning patterns
0.846
0.847
5.65
1.79
7.12
1.41
9.18
1.91
5.60
5.4
with HREE clearly enriched in garnet cores. Towards the

17-II
Host
-26
rim, a second prominent HREE peak is present in all

grains throughout the profile (Figs. 5, 6a–c). In host rock
0.983
1.020
5.43
1.72
6.96
1.45
9.94
2.10
6.25
6.46
18-II
and selvage grains, this peak is correlated to a distinct

Host
-33
change of inclusion textures (Fig. 10). In garnet from the

0.855
0.854
vein and the vein-selvage contact, a similar peak is pre-

6.38
2.14
8.43
1.57
9.75
1.98
5.84
5.61
40-A
Host
-44
sent but located closer to the garnet rim. Garnet rims

display elevated MREE (Tb, Dy, Ho) and Y concentra-
0.954
0.847
tions (Fig. 5). Other trace elements are generally below

6.35
2.05
8.20
1.53
9.66
1.98
5.91
6.12
41-A
Host
-53
detection limit.
Epidote is identical in major-element composition
Dist. from vein (cm)
throughout host rock and selvage (Table 2). It is a major

Table 1 continued
host for most trace elements (e.g. Sr, Sc) (Table S1),
including LREE (up to 800 ppm). In host rock and selvage,
the REE pattern is complementary to garnet, as has been
Sample
found in other rocks of the PEM (Spandler et al. 2003)

Type
Tm
Sm
Gd
Dy
Ho
Yb
Eu
Tb
Lu
Er
(Fig. 6c).
123
90
Table 2 Electron microprobe data of minerals from host rock, selvage and vein in wt% and structural formula in atoms per formula unit
Sample 15-II 17-II 14-III 17-II 14-III 15-II 14-III 15-II 15-II 17-II 14-III 20-II-2 14-II-11 17-II 14-III 14-III 15-II
123
Location host host selvage host selvage host selvage host host host vein host vein host selvage vein host
Mineral Brs Brs Brs Gln Gln Ep Ep Ep Ph Ph Ph Ap Ap Omp Omp Omp Omp
Grt incl. type I vein Grt incl.
Page 10 of 27
SiO2 51.84 52.97 52.10 54.86 55.64 37.64 37.88 37.73 49.61 49.37 49.52 n.d. n.d. 54.74 54.80 54.96 54.39
TiO2 0.08 0.05 0.22 0.05 0.08 0.10 0.07 0.03 0.39 0.31 0.34 n.d. n.d. 0.07 0.05 0.06 0.03
Al2O3 9.50 9.64 8.24 9.87 9.74 23.96 25.03 25.24 27.21 27.09 26.48 n.d. n.d. 9.08 9.23 9.71 8.79
Cr2O3 0.03 0.04 0.02 0.04 0.04 0.01 0.03 0.01 0.00 0.02 0.03 n.d. n.d. 0.00 0.00 0.02 0.00
FeO 10.84 10.80 10.12 12.36 11.95 n.c. n.c. n.c. 2.77 2.86 3.18 n.d. n.d. 1.87 1.62 2.42 1.27
Fe2O3 1.49 1.76 2.26 1.29 1.36 11.58 10.49 10.52 n.c. n.c. n.c. n.d. n.d. 9.47 9.39 6.88 9.87
MnO 0.07 0.07 0.04 0.04 0.04 0.61 0.45 0.49 0.01 0.00 0.00 n.d. n.d. 0.03 0.01 0.01 0.01
MgO 11.88 11.24 13.02 9.41 9.52 0.03 0.04 0.01 2.97 3.03 3.24 n.d. n.d. 6.36 6.29 7.12 6.60
CaO 6.06 4.62 6.91 2.46 1.82 22.46 23.15 23.36 0.01 0.03 0.01 55.66 56.08 11.17 11.28 12.09 11.94
Na2O 4.94 5.53 4.27 6.55 6.89 0.05 0.04 0.00 1.00 0.93 0.68 n.d. n.d. 8.19 8.24 7.57 7.92
K2O 0.22 0.15 0.14 0.05 0.01 0.01 0.01 0.01 9.83 10.04 10.39 n.d. n.d. 0.00 0.02 0.02 0.00
P2O5 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 43.48 42.61 n.d. n.d. n.d. n.d.
F n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 1.49 1.42 n.d. n.d. n.d. n.d.
Cl n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.02 0.01 n.d. n.d. n.d. n.d.
Total 96.95 96.87 97.34 96.97 97.09 96.46 97.19 97.41 93.80 93.68 93.86 100.02 99.52 100.97 100.94 100.86 100.82
Si 7.426 7.551 7.433 7.781 7.849 3.145 3.131 3.114 3.371 3.365 3.360 - - 1.963 1.964 1.964 1.956
Ti 0.009 0.005 0.024 0.005 0.009 0.006 0.004 0.002 0.020 0.016 0.017 - - 0.002 0.001 0.002 0.001
Al 1.603 1.620 1.386 1.650 1.619 2.360 2.439 2.456 2.179 2.176 2.118 - - 0.384 0.390 0.409 0.372
Cr 0.003 0.004 0.002 0.004 0.004 0.001 0.002 0.001 0.000 0.001 0.001 - - 0.000 0.000 0.001 0.000
Fe2+ 1.298 1.288 1.208 1.466 1.410 - - - 0.158 0.163 0.163 - - 0.056 0.049 0.072 0.038
Fe3+ 0.160 0.189 0.242 0.138 0.144 0.728 0.652 0.653 - - - - - 0.256 0.253 0.185 0.267
Mn 0.008 0.008 0.005 0.005 0.005 0.043 0.032 0.034 0.001 0.000 0.000 - - 0.001 0.000 0.000 0.000
Mg 2.537 2.389 2.769 1.990 2.002 0.004 0.005 0.001 0.301 0.308 0.327 - - 0.340 0.336 0.379 0.354
Ca 0.930 0.706 1.056 0.374 0.275 2.011 2.050 2.066 0.001 0.002 0.001 - - 0.429 0.433 0.463 0.460
Na 1.372 1.528 1.181 1.801 1.884 0.008 0.006 0.000 0.132 0.123 0.089 9.438 9.596 0.569 0.573 0.524 0.552
K 0.040 0.028 0.025 0.009 0.002 0.001 0.001 0.001 0.852 0.873 0.900 - - 0.000 0.001 0.001 0.000
P - - - - - - - - - - - 5.826 5.716 - - - -
F - - - - - - - - - - - 0.747 0.715 - - - -
Cl - - - - - - - - - - - 0.006 0.002 - - - -
Total 15.386 15.316 15.331 15.223 15.203 8.308 8.322 8.329 7.012 7.028 6.976 16.014 16.075 4.000 4.000 4.000 4.000
Oxygens 23 23 23 23 23 13 13 13 11 11 11 24 24 6 6 6 6
Aeg 25.6 25.2 18.7 26.4

Jad 31.4 31.8 34.4 28.2
Di 43.0 43.1 46.9 45.4
Table 2 continued
Sample 14-III 15-II 16-II 16-II 15-II 16-II 16-II 16-II 16-II 14-III 14-III 14-III 14-III 14-II 14-II 14-II 14-II
Location selvage host host host host host host host host selvage selvage selvage selvage vein vein vein vein
Mineral Rt Rt Rt Ttn Ttn Grt Grt Grt Grt Grt Grt Grt Grt Grt Grt Grt Grt
Grt incl. outer rim inner rim mid core outer rim inner rim mid core outer rim inner rim mid core
SiO2 0.04 0.02 0.01 30.27 32.49 37.70 37.77 37.37 37.39 37.50 37.76 37.30 37.16 37.17 37.19 37.07 37.00
TiO2 99.58 99.41 97.93 38.53 35.14 0.06 0.02 0.16 0.16 0.00 0.06 0.15 0.13 0.06 0.18 0.14 0.13
Al2O3 0.01 0.00 0.00 1.21 2.00 21.00 21.09 20.84 20.30 21.04 20.97 20.65 20.42 20.60 20.27 20.30 20.10
Cr2O3 0.04 0.02 0.02 0.00 0.00 0.04 0.00 0.00 0.00 0.02 0.03 0.00 0.00 0.00 0.00 0.01 0.02
FeO 0.84 0.61 0.99 0.56 1.47 27.07 27.81 28.1 25.29 27.55 28.42 28.01 24.89 26.74 27.16 26.51 25.41
Fe2O3 n.c. n.c. n.c. n.c. n.c. 0.7 0.94 0.84 0.86 0.43 0.67 0.48 1.04 1.08 0.61 1.31 1.25
MnO 0.00 0.02 0.02 0.00 0.00 0.25 0.41 1.31 5.11 0.33 0.48 1.48 6.40 0.58 2.36 3.58 4.88
MgO 0.02 0.04 0.00 0.00 0.91 3.54 4.03 2.15 1.62 3.51 3.98 2.08 1.54 3.86 2.16 1.91 1.69
CaO 0.27 0.06 0.09 28.40 26.17 8.98 7.63 9.03 8.98 8.35 7.19 8.99 8.14 8.03 8.76 8.52 8.58
Na2O 0.07 0.01 0.08 0.09 0.31 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
K2O 0.00 0.00 0.00 0.00 0.03 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Total 100.87 100.19 99.14 99.05 98.51 99.35 99.70 99.80 99.71 98.73 99.56 99.14 99.72 98.12 98.69 99.35 99.06
Si 0.001 0.000 0.000 0.998 1.067 2.992 2.988 2.984 3.003 2.996 2.995 2.998 2.992 2.988 3.006 2.987 2.995
Ti 0.990 0.995 0.993 0.955 0.868 0.004 0.001 0.010 0.010 0.000 0.004 0.009 0.008 0.003 0.011 0.009 0.008
Al 0.000 0.000 0.000 0.047 0.077 1.956 1.954 1.946 1.922 1.977 1.955 1.955 1.929 1.940 1.931 1.915 1.912
Cr 0.000 0.000 0.000 0.000 0.000 0.003 0.000 0.000 0.000 0.001 0.002 0.000 0.000 0.000 0.000 0.001 0.001
Fe2+ 0.008 0.007 0.011 0.015 0.040 1.797 1.840 1.877 1.699 1.841 1.885 1.883 1.676 1.798 1.836 1.786 1.720
3+
Fe - - - - - 0.042 0.056 0.051 0.052 0.026 0.040 0.029 0.063 0.065 0.037 0.080 0.076
Mn 0.000 0.000 0.000 0.000 0.000 0.017 0.027 0.089 0.348 0.022 0.032 0.101 0.436 0.039 0.162 0.244 0.335
Mg 0.000 0.001 0.000 0.000 0.044 0.419 0.475 0.256 0.194 0.418 0.471 0.249 0.185 0.463 0.260 0.229 0.204
Ca 0.004 0.001 0.001 1.004 0.921 0.764 0.647 0.773 0.773 0.715 0.611 0.774 0.702 0.692 0.759 0.736 0.744
Na 0.002 0.000 0.002 0.006 0.020 - - - - - - - - - - - -
K 0.000 0.000 0.000 0.000 0.001 - - - - - - - - - - - -
Total 1.006 1.005 1.008 3.026 3.038 7.992 7.988 7.984 8.000 7.996 7.995 7.998 7.992 7.988 8.000 7.987 7.995
Oxygens 2 2 2 5 5 12 12 12 12 12 12 12 12 12 12 12 12
Prp 14.0 15.8 8.5 6.0 13.9 15.7 8.3 6.2 15.4 7.9 7.7 6.8
Alm 59.9 61.3 62.6 56.3 61.4 62.8 62.5 55.9 59.9 60.8 59.6 57.3
Grs 23.4 19.6 23.2 22.2 22.8 18.2 23.6 19.9 20.3 22.4 20.4 20.4
Sps 0.6 0.9 3.0 11.6 0.8 1.1 3.4 14.6 1.3 5.4 8.1 11.2
And 1.7 1.9 2.0 2.6 1.0 1.9 1.5 3.1 2.6 1.9 3.6 3.8
3? 2? 3?
Fe was calculated assuming stoichiometric mineral compositions. For phengite all Fe is assumed to be Fe and for epidote to be Fe
n.d. not determined; n.c. not calculated
Page 11 of 27
90
123
480 core mid-zone shoulder-peak inner rim a core mid-zone shoulder-peak inner rim b
outer rim 500 outer rim
420
Trace elements [ppm]
250 400
REE [ppm]
200 300
150
200
100
100
50
0 0
0 250 500 750 1000 1250 1500 0 250 500 750 1000 1250 1500
distance from garnet core [µm] distance from garnet core [µm]
Li Sc Ti V Cr Co La Ce Pr Nd Sm Eu Gd
Ga Ge Y Hf Zn Tb Dy Ho Er Tm Yb Lu
Fig. 5 Core-to-rim concentration patterns of host rock garnet. a Trace elements showing variable concentrations (Sc, V, Cr, Y) along different
zones. b HREE are accumulated in the garnet core. A prominent additional shoulder peak in MREE/HREE is present further towards the rim
600 a host rock garnet 800 b selvage garnet

500
outer rim
shoulder peak garnet / chondrite
garnet / chondrite
600
400 mid-zone
core
300
400
200
200
100
0 0
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
300 c 1000 d
vein garnet epidote host (41-A)
host (18-II)
800
host (17-II)
garnet / chondrite
host (16-II)
epidote / chondrite
200 selvage (14-III)

600 selvage (14-II)
400
100
200
0 0
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Fig. 6 Chondrite-normalized rare-earth element patterns of garnet earth element patterns for epidote from host rock and selvage show a
from host rock (a), selvage (b) and vein (c) showing the differences in pattern complementary to garnet
trace-element concentrations between the individual zones. d Rare-
White mica in the host rock and the type II vein can be those of the host rock matrix and type I veins (Fig. S1c) most
classified as phengite. The major-element composition of host likely result from chemical differences between the vein-
rock phengite from different textural sites is similar (Table 2) forming fluid and the host rock composition.
with Si p.f.u values ranging from 3.32 to 3.41. Divergent Phengite is the major Li host (10–20 ppm) and LILE in
values from the Si–Al trend in the type II vein phengite from type II vein (Table S1). The LILE distribution indicates a
123
Table 3 P–T estimates for peak metamorphic conditions in the PEM

P (Gpa) P (GPa) T (°C) T (°C) T (°C) T (°C) Method Calibration References
Host rock Type II vein Host rock Transition Selvage Vein
538 ± 12 539 ± 14 539 ± 15 538 ± 12 Zr-in-rutile Watson et al. (2006) This study
540 ± 11 541 ± 14 541 ± 15 540 ± 12 Zr-in-rutile Ferry and Watson (2007) This study
533 ± 23 535 ± 28 535 ± 30 533 ± 24 Zr-in-rutile Zack et al. (2004) This study
592 ± 12 593 ± 14 593 ± 16 591 ± 12 Zr-in-rutile Tomkins et al. (2007) This study
1.9–2.2 *2.0 500–560 – – 550–560 Grt–Cpx–Ph Krogh Ravna and Terry (2004) This study
570–610 – 590–640 550–590 Grt-Omp Krogh Ravna (2000) Spandler and
Hermann
(2006)
2.38 ± 0.4 *600 Thermocalc Powell and Holland (1988) Clarke et al. (1997)
606 Grt-Cpx Krogh (1988) Clarke et al. (1997)
561 Grt-Cpx Ellis and Green (1979) Clarke et al. (1997)
584 Grt-Amp Graham and Powell (1984) Clarke et al. (1997)
1.9 *600 Thermocalc Powell et al. (1998) Carson et al. (1999)
*530–560 RSCM- Beyssac et al. (2002) Vitale Brovarone and
Tmax Agard (2013)
Lahfid et al. (2010)
2.2–2.4 *550 Perple_X Powell et al. (1998) Vitale Brovarone and
Agard (2013)
530–590 Fe2?–Mg Vitale Brovarone and
Agard (2013)
2.7 Grt–Cpx–Ph Waters and Martin (1993) Vitale Brovarone and
Agard (2013)
disparity between phengite grains from the matrix with with maximum Si-content. These parameters are generally
high Sr (100–230 ppm) and Pb (2–5 ppm) concentrations, met in rim compositions. Pressure–T conditions of
and the type I veins with significantly lower concentrations 500–560 °C and 1.9–2.2 GPa have been determined for the
of these elements (20–60; 0–1 ppm, respectively). A con- host rock of the studied outcrop. The P–T conditions of the
trary trend is displayed by Ba and Rb (Table 2). Phengite selvage could not be estimated by Grt–Cpx–Ph thermo-
in the type II vein is similar to that of type I veins except barometry due to the lack of phengite in this zone. Peak
from slightly higher Rb and Sr concentration (Table S1). metamorphic conditions of the type II vein are ca.
REE concentrations in phengite are \1 ppm. 550–560 °C at ca. 2.0 GPa.
Rutile in all zones contains up to 1 wt% FeO and Zr-in-rutile thermometry indicates a temperature of ca.
0.3 wt% CaO. Trace-element concentrations are generally 540 °C for all parts of the profile using the calibrations of
low (\2 ppm) with the exception of Nb (up to 40 ppm) and Zack et al. (2004), Watson et al. (2006) and Ferry and
Zr (50–90 ppm). Apatite in the vein has F contents of ca. Watson (2007). For a pressure of 2 GPa, the calibration of
1.4–1.8 wt% and Cl concentrations \0.06 wt% (Table 1). Tomkins et al. (2007) yields temperatures that are ca. 50 °C
higher (Table 3). Analysis of different spots in single rutile
P–T conditions grains did not reveal systematic Zr zonation patterns.
Metamorphic temperature and pressure conditions were Bulk-rock geochemistry

estimated using the Grt–Cpx–Ph thermobarometer and Zr-
in-rutile thermometry. All phases analysed for geother- Samples 41-A and 40-A, which are considered to represent
mobarometry do not show any retrogression features. For the unaltered host rock, have a broadly basaltic major-
the Grt–Cpx–Ph thermobarometry (Krogh Ravna 2000; element composition with relatively high Na2O (3.5 wt%),
Krogh Ravna and Terry 2004), electron microprobe (EMP) Fe2O3 (15.5–16.5 wt%) and TiO2 (3 wt%) concentrations
data of minerals in direct spatial relationship were used and (Table 1). Niobium/Ta and Zr/Hf ratios (11.2–15 and
data points were selected to record maximum pressure 37–42, respectively) are in the range of typical basaltic
conditions (Carswell et al. 2000): garnet with maximum compositions (Pfänder et al. 2007). REE concentrations are
2
generally enriched by 24–45 times chondrite, and LREE
agrt
gr agrt
py , omphacite with maximum Xjd and phengite
are slightly depleted compared to HREE. Trace-element
123
100 a 41-A host 14-C sht (Spandler & Hermann, 2006) 100 b
40-A host 14-B sht host
16-II host 14-A selvage vein selvage
sample / chondrite
10 14-IV(1) vein N-MORB (Sun & McDonough, 1989)
sample / MORB
10
1
0.1
1
0.01
Ba Sr U Ta Ce Nd Zr Eu Gd Dy Ho Tm Lu
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Rb K2O Th Nb La Pr Sm Hf TiO2 Tb Y Er Yb
Fig. 7 a Chondrite-normalized REE- and b MORB-normalized trace-element composition of host rock, selvage and vein (Sun and McDonough
1989)
patterns (Fig. 7b) are compatible with the assumption of modal amount of garnet. The concentrations of LILE that
enriched MORB-like protoliths, except that Th and Nb are are usually incorporated in phengite also are high. All other
slightly depleted. Strontium is depleted compared to trace elements show very low concentrations or are below
MORB, whereas other usually fluid-mobile LILE (Rb, Ba, detection limit (Th, U, Nb, Ta). These observations are
K20) are strongly enriched in the host rock sampling profile similar to those reported by Spandler and Hermann (2006).
(40-A to 15-A; Table 1) and become increasingly depleted
at a distance of 15–20 cm from the vein (14-A-C; Table 1; Rb–Sr geochronology
Fig. 7). Li and V concentrations, however, increase from
the host rock towards the type II vein. Rubidium–Sr geochronology was conducted on three
Sample 14-A illustrates the bulk compositional charac- samples of profile B (23-b, 22-a, 20-b). Hand-picked
teristics of the selvage sensu stricto. Samples 14-B and mineral separates representing different grain sizes of
14-C represent the transition zone between selvage and phengite, epidote, omphacite, garnet, amphibole and whole
host rock. Compared to the host rock, the SiO2, MgO and rock powder were used for analysis. The analytical data are
TiO2 concentrations in the selvage are largely unchanged summarized in Table 4.
(Table 1). All other major and minor elements show Sample 23-b representing the host rock at a distance of
gradual increasing (CaO, Na2O) or decreasing (Al2O3, ca. 22 cm from the main type II vein yielded an age of
Fe2O3 and MnO) trends from the host rock towards the 38.0 ± 0.7 Ma (MSWD = 9.6; Fig. 8), based on Amp,
vein. P2O5 and K2O are even further depleted to trace Omp, Ep and five Ph-fractions. Sample 22-a is a host rock
concentrations (Table 1). sample that includes a crosscutting type I vein at a distance
There are little variations in most trace-element con- of ca. 13 cm from the main type II vein. The isochron
centrations between host rock and selvage. The strong (including Amp, Omp, Ep and three Ph-fractions) indicates
depletion of HREE in the selvage records the lower modal an age of 38.3 ± 0.8 (MSWD = 3.7; Fig. 8). The type II
proportions of garnet in this part of the profile. Differences vein is represented by sample 20-b. The whole rock powder
are also observed for Ba, Rb and K2O that show lower and three phengite grain-size fractions were used for iso-
concentrations in the selvage with a trend continued from chron calculation, indicating an age of 38.0 ± 0.3
the adjacent host rock. Strontium displays a more variable (MSWD = 0.46). A geologically meaningful Rb–Sr iso-
pattern across the profile, but appears to be more depleted chron could not be calculated for the selvage around the
in the selvage. The Nb/Ta ratio of the selvage (11.2–11.7) type II vein due to the absence of phengite.
is within the range of the host rock.
The compositional characteristics of the vein are sig-
nificantly different from the other parts of the profile Discussion
reflecting the differences in modal abundance of individual
phases (Table 1). The concentrations of SiO2, Al2O3, MnO, Field observations, published P–T information (Clarke
K2O and especially Fe2O3(T) (ca. 22 %) are high compared et al. 1997; Carson et al. 2000; Spandler et al. 2003; Cluzel
to the host rock and selvage, whereas CaO, MgO, Na2O et al. 2012) and new data for the studied profile indicate
and TiO2 are lower. The low LREE concentrations and that the metamorphic history of the PEM records a pro-
enrichment of HREE and Y are consistent with the high grade blueschist- to eclogite-facies transformation that is
123
Table 4 Rb-Sr isotope data for samples of the PEM (23-b, 22-a—host rock ? type I vein; 20-b—type II vein)
87
Sample Mineral Grain size (lm) Rb (ppm) Sr (ppm) Rb/86Sr 87
Sr/86Sr ±2r Age (Ma)
23-b Omp 125–250 0.29 46.5 0.0180 0.704806 0.000010 38.0 ± 0.7
Amp 63–125 1.31 33.9 0.1122 0.704794 0.000011
Ep 63–125 6.44 438 0.0425 0.704669 0.000008
Ph 125–250 238 26.4 26.12 0.718735 0.000010
Ph 250–355 246 27.9 25.53 0.718438 0.000012
Ph 355–500 239 23.3 29.64 0.720854 0.000007
Ph 250–710 240 28.1 24.71 0.718231 0.000014
Ph 500–710 240 21.8 31.77 0.721596 0.000014
22-a Omp 125–250 0.14 51.4 0.0079 0.704667 0.000012 38.3 ± 0.8
Ep 63–125 0.97 354 0.0079 0.704715 0.000009
Amp 125–250 0.52 46.5 0.0326 0.704678 0.000009
Ph 355–500 238 49.1 14.03 0.712360 0.000009
Ph 250–710 215 52.2 11.91 0.711196 0.000014
Ph 500–710 230 69.1 9.616 0.709824 0.000010
20-b WR Powder 31.5 23.6 3.857 0.706914 0.000009 38.0 ± 0.3

Ph 63–125 246 42.1 16.88 0.713959 0.000011
Ph 125–250 261 43.9 17.22 0.714102 0.000008
Ph 250–355 274 43.0 18.44 0.714827 0.000014
Ph 355–500 266 42.3 18.27 0.714662 0.000015
An uncertainty of 1 % (2r) has been assigned to the 87Rb/86Sr ratios. For isochron calculations an uncertainty of 0.005 % (2r) has been assigned
to the 87Sr/86Sr ratios. Errors on isochron ages are reported with 95 % c.l.
associated with the formation of a HP/LT vein system. for chlorite, Omph(GHP2) (Green et al. 2007) for
Below, we discuss the details of the fluid release process, omphacite, Ep(HP) (Holland and Powell 1998) for epidote
the specific P–T evolution of the studied occurrence and and F (Connolly and Trommsdorff 1991) for H2O and CO2
the timing of vein system formation. fluid. Quartz is considered as a pure end-member phase.
The Fe3?/Fe2? ratio was set to 0.25 because subduction
Pseudosection modelling zone eclogites generally have higher Fe3? concentrations
(John and Schenk 2003; John et al. 2010; Rebay et al.
Qualitative estimates of mineral breakdown reactions and 2010; Chen et al. 2013) than unaltered MORB (Fe3?/
associated fluid release in the host rock along a P–T path Fe2? = 0.12–0.16) (Bézos and Humler 2005; Cottrell and
constrained by geothermobarometry can be illustrated by Kelley 2011).
phase equilibrium modelling via pseudosections. For the A critical point for further evaluation and interpretation
present study, the TNMnCaKFMASCHO system (TiO2– is the question whether or not lawsonite was present during
Na2O–MnO–CaO–K2O–FeO–Fe2O3–MgO–Al2O3–SiO2– prograde metamorphism. Elsewhere in the PEM, lawsonite
CO2–H2O) was used. Fe2O3 was included since it affects is widespread in almost all lower-grade metabasic mineral
amphibole and epidote stability, especially at higher P–T assemblages and pseudomorphs after lawsonite, or law-
conditions (e.g. Warren and Waters 2006; Diener and sonite inclusions in garnet, have also been reported (e.g.
Powell 2012). The pseudosections were calculated for the Spandler et al. 2004; Fitzherbert et al. 2005; Vitale Bro-
averaged bulk composition of samples 41-A, 40-A and varone and Agard 2013). However, in the studied samples
18-II (Table 1) using Perple_X (version 6.7.2; Connolly no lawsonite inclusions in garnet or pseudomorphs after
1990, 2005) with the internally consistent database of lawsonite were recognized. Instead, epidote is present as
Holland and Powell (1998) and related updates inclusions in garnet, which suggests that the epidote sta-
(hpver04.dat). The calculations are based on the following bility field was intersected relatively early during prograde
solid-solution models: Amph(DHP) (Dale et al. 2000) for garnet growth. For similar rock types of the PEM, Clarke
glaucophane and barroisitic hornblende, Gt(HP) (Holland et al. (2006) showed that lawsonite formation can be
and Powell 1998) for garnet, Mica(CHA) (Coggon and inhibited under low water activity conditions. Therefore,
Holland 2002) for phengite, Chl(HP) (Holland et al. 1998) for our pseudosection calculations H2O was fixed to a
123
a 23-b - host-rock + type I vein c 20-b - type II vein

0.724
Ph E 0.715
Ph D Ph C
0.720
Ph B Ph D
Ph C 0.713
Ph F Ph B
0.716
Sr/86Sr
Ph A
0.711
0.712
87
0.709
0.708
Omp B 38.0 ± 0.7 Ma 38.0 ± 0.3 Ma
0.704 Amp A Initial 87Sr/86Sr = 0.704726 (77) 0.707 Initial 87Sr/86Sr = 0.704832 (53)
Ep A WR
MSWD = 9.6, n = 8 MSWD = 0.46, n = 5
0.700 0.705
0 10 20 30 40 0 4 8 12 16 20
b 22-a - host-rock + type I vein d 20-b + 22-a + 23-b

0.713 0.724
Ph C
0.720
0.711 Ph F
Ph 23-b
0.716
Sr/86Sr
Ph E
0.709
0.712 Ph 20-b
87
0.707
0.708 Ph 22-a
38.3 ± 0.8 Ma 38.2 ± 0.3 Ma
0.705 Omp B
Initial 87Sr/86Sr = 0.704676 (54) 0.704 Initial 87Sr/86Sr = 0.704702 (38)
Ep A Omp, Amp, Ep
Amp B MSWD = 3.7, n = 6 22-a + 23-b MSWD = 6.3, n = 18
0.703 0.700
0 4 8 12 16 0 10 20 30 40
87
Rb/86Sr 87
Rb/86Sr
Fig. 8 a–c Rb–Sr isochron diagrams for three samples representing B = 125–250 lm, C = 250–355 lm, D = 355–500 lm, E = 500–
different parts of the studied host rock-vein system. d Combined Rb– 710 lm, F = 250–710 lm). Symbols sizes are larger than error bars.
Sr isochron including all data points from a–c. A = 63–125 lm, Numbers in parentheses indicate error on the last two digits
relatively low value of 2.2 wt%. This results in water-un- our Zr-in-rutile data for host rock, selvage and vein
dersaturated conditions at lower grades, with water satu- (540 ± 15 °C) as well as newly determined Grt–Cpx–Ph
ration only occurring once chlorite breakdown is reached. P–T-data for the host rock and vein (500–560 °C; 1.9–2.2
Figure 9 shows a calculated pseudosection for the GPa). These temperatures are interpreted to be the best
average bulk compositions of the samples 41-A, 40-A and estimate for peak metamorphism. As had been observed
18-II in the P–T range of 1.5–2.5 GPa and 400–625 °C. elsewhere for blueschists and lower-grade eclogites
A P–T path for the bulk host rock can be approximated (Tomkins et al. 2007), the pressure-corrected Zr-in-rutile
from literature data of the PEM (Fig. 9a). Pseudosection thermometer of Tomkins et al. (2007) slightly overesti-
modelling (e.g. Clarke et al. 1997; Carson et al. 1999) mates the temperatures. Since the highest temperatures of
indicates similar P–T paths for various HP-assemblages of ca. 540 °C (Grt–Cpx–Ph and Zr-in-rutile) coincide with the
the PEM with peak conditions of 1.9–2.4 GPa and up to highest pressures of 1.9–2.2 GPa (Grt–Cpx–Ph), it is most
600 °C (Table 3). Vitale Brovarone and Agard (2013) likely that they occurred contemporaneously.
proposed a P–T path for their Zone 3–4 assemblage which Modal abundances deduced by the pseudosection are in
represents a rock type equivalent to the samples of this good agreement with the values determined by the Rietveld
study (Omp, Grt, Amph, Ph, Cz, Qz, Rt). The reported method (Table 3). All relevant stability fields along the
maximum temperatures of 530–560 °C determined by proposed path incorporate omphacite, amphibole, garnet,
RSCM thermometry are based on the irreversible trans- epidote, phengite, quartz and rutile as stable phases. The
formation of organic matter and are therefore considered to modal abundance of phengite and rutile is generally con-
be insensitive to retrogression (Beyssac et al. 2002; Lahfid stant over a large P–T range, whereas the modal amounts
et al. 2010). The RSCM temperatures are consistent with of other phases either increase (Grt, Omp) or decrease
123
2.5 2.5
a 4 2
3
b
Ph
3.4
4
in
4
.f.u
ip
5.0
5S
11.0
2.0
Ep Amp Ph Grt
Ep x Qz R
3.3
Cpx Qz Ru H2O
3.3
2.3 Cp 2.3
3.0
Chl
30.
0
Am u H 2O
Zr-in-Rutile
10 .
pP 540 ± 15 °C
0
hG
rt
6 .0
1.8
15
35.0
.0
2.1 2.1 10.0
9 .0
P [GPa]
20
12
.0
18.0
.0
1.6
Grt-Cpx-Ph 40.0
3.4
15
500-560 °C
25
.0
1.9 1.9
.0
1.9-2.2 GPa
30
ol.
.0
%
1.4
35
8.0 vol.%
Ep
Chl
.0
Ph
40
u in
1.2
.f. 45.0 vol.%
.0
45
Si p Amp
.35
.0
3
18
vo
1.0
.0
l.%
Ep Chl Amp Ph Grt
1.7 1.7
50
Cpx Qz Ru
Am
.0
0.8
2.0
4.0
p
0.2
6.0
3.3
0.6
0.4
wt.
50.0
% H2
6.0 2
1 0.
O
0
1.5 1.5
400 450 500 550 600 400 450 500 550 600
T [°C] T [°C]
Fig. 9 P–T pseudosection (Perple_X) in the system TNMnCaKF- rutile thermometry and Grt–Cpx–Ph thermobarometry. Blue lines
MASCHO for the average bulk composition of the reference samples illustrate fluid release from breakdown of hydrous minerals along the
40-A, 41-A, 18-II. Stable phases in numbered fields: (1) Chl, Ep, P–T path. Grey lines show calculated Si p.f.u in phengite correlating
Amp, Ph, Gt, Cpx, Rbk, Qz, Rt; (2) Amp, Ph, Gt, Cpx, Qz, Rt, H2O; with measured values of 3.3–3.4. b Changes in modal abundance of
(3) Ph, Gt, Cpx, Qz, Rt, H2O. Field (4) resembles subjacent fields plus hydrous minerals along the P–T path. Blue amphibole; green chlorite;
Mcar. a P-T path approximated from literature data (Carson et al. magenta epidote
1999; Vitale Brovarone and Agard 2013) and constrained by Zr-in-
(Amp, Ep) at higher P and T. Modal amounts of chlorite et al. 2007). However, previous studies have not provided
rapidly decrease at temperatures above ca. 450 °C, and the isotopic ages for formation of the vein system. It is gener-
chlorite-out isograd shows up at ca. 460–490 °C. The ally advisable to verify the geological significance of
chlorite isograd is very sensitive to changes in the Fe3?/ 40
Ar/39Ar phengite ages of eclogite- and blueschist-facies
Fe2? ratio. Due to the uncertainty of this ratio in the studied rocks by means of other isotopic age systems, due to a
samples, the error on this isograd is relatively high. The Si- potential contamination with excess Ar that might have
in-phengite values (3.3–3.4, Fig. S1c) correlate well with compromised the accuracy of such ages. This problem,
pressure estimates for peak metamorphic conditions that leading to geologically meaningless dates, has been
are based on Grt–Cpx–Ph barometry. described from many HP and UHP occurrences worldwide
The amount of released fluid along the assumed P–T (e.g. Li et al. 1994; El-Shazly et al. 2001; Kelley 2002;
path is illustrated in Fig. 9a. A major pulse of fluid release Warren et al. 2010). In order to avoid such complexities, we
(0.8 wt% H2O) is associated with the chlorite-out isograd have chosen to date the vein system by means of the Rb–Sr
at ca. 480 °C and 2.0 GPa. With increasing P–T conditions method which is a suitable tool for assessing the importance
the amount of fluid release decreases and is presumably of excess Ar (e.g. El-Shazly et al. 2001; Bröcker et al.
related to ongoing amphibole breakdown reaching ca. 2009, 2013) and for dating of fluid sensitive rock systems
1.4 wt% at 540 °C. At peak metamorphic conditions, the (e.g. Glodny et al. 2003, 2007; John et al. 2012).
stable mineral assemblage preserves ca. 0.8 wt% of fluid For all parts of the studied profile, internal Rb–Sr iso-
which is in accordance with the loss on ignition data chrons yielded consistent ages of ca. 38 Ma that overlap
acquired during bulk-rock element analysis (Table 1). within error (Table 4; Fig. 8). It is unclear from the textural
observations whether the dated phengite of sample 23-b is
Time constraints for development of the vein system representative of the pristine host rock before the onset of
dehydration or if this phengite is related to type I vein
White mica geochronology is an important technique to formation. A combination of all data points to a single
date metamorphic rocks, and a comprehensive data set that isochron results in an age of 38.2 ± 0.3 Ma (MSWD 6.3).
is based on the K–Ar and Ar–Ar methods is already avail- The age of ca. 38 Ma is distinctly younger than the
able for the HP/LT rocks from New Caledonia (Baldwin hitherto presumed peak metamorphic age (ca. 44 Ma, U–
123
a 160 b
80 Major elements LILE 1+
120
40
mass change [%]
80
0 40
SiO2 Al2O3 0
-40 Fe2O3(T) MnO
MgO CaO -40 K2O Rb
Na2O P2O5
-80 -80
Ba Li
TiO2
-50 -40 -30 -20 -10 -4 -2 0 -50 -40 -30 -20 -10 -4 -2 0
40
c 60 d
LREE LILE 2+
20 40
mass change [%]
0 20
0
-20
La Ce -20
Pr Nd
-40 -40 MnO MgO
Sm Eu
CaO Sr
-60
-60
-50 -40 -30 -20 -10 -4 -2 0 -50 -40 -30 -20 -10 -4 -2 0
40 80
e f
HREE + MnO TiO2 V HFSE 4+
20 60 Hf Th
U
mass change [%]
0 40
-20 20
MnO Y
-40 Gd Tb 0
Dy Ho
Er Tm
-60 -20
Yb Lu
-80 -40
-50 -40 -30 -20 -10 -4 -2 0 -50 -40 -30 -20 -10 -4 -2 0
40 h hst s v
g distance to vein [cm]
HFSE 5+
20
mass change [%]
-20
-40 Nb Ta
-60
-50 -40 -30 -20 -10 -4 -2 0
h hst s v
distance to vein [cm]
123
b Fig. 10 Concentration ratio diagrams for major and trace elements. balance calculations a geological reference frame has to be
Positive and negative deviations from the reference line indicate mass defined to quantify open-system mass and volume changes
gain or mass loss, respectively, versus the distance from the vein. The
reference line (0 %) is defined by the Zr concentration. The scale of (Ague 1994; Ague and van Haren 1996). Samples 41-A
the y-axis varies between the diagrams to allow illustration of small and 40-A are considered to represent the largely unaltered
changes in individual element groups. The x-axis of all plots has precursor rock and thus were selected for determining the
different scales to emphasize the changes in the narrow selvage. reference frame. Ague and van Haren (1996) defined four
Dashed red and orange lines indicate samples influenced by cross-
cutting type I veins. a Major elements. b LILE with a valence state of types of species that can be eliminated from consideration
1 ? and K2O to show the influence of phengite as the major host as reference elements. Those are elements/species that (1)
mineral. c LREE. d LILE with a valence state of 2? . e HREE are concentrated in minerals growing obviously from
together with MnO to indicate garnet distribution. HFSE with a metasomatic environments, (2) have large analytical
valence state of 4? (f) and 5? (g). h—host rock, hst—host-selvage-
transition, s—selvage, v—vein uncertainties, (3) have a variable concentration in the host
rock or (4) are volatile (e.g. H2O, CO2). A statistical
approach has been used to find a suitable immobile refer-
Pb zircon; Spandler et al. 2005), but is in line with yet ence element in the vein system. The deviation in the
unpublished U–Pb zircon ages from the PEM (ca. 40 Ma; concentration of individual samples from the average
Pirard pers comm.). The Rb–Sr age falls within the range composition of the unaltered precursor samples has been
of previously published K–Ar and Ar–Ar phengite data (ca. determined for selected elements across the studied bulk-
39–37 Ma; Baldwin et al. 2007) and further corroborate rock profile (samples 41-A–12-II). The deviation is pre-
their geological significance. The latter have mostly been sented as r values (Chost/Csample) in per cent (Table S4)
interpreted as cooling and decompression ages representing (Ague and van Haren 1996).
P–T conditions of 450–350 °C and ca. 0.8–0.5 GPa. The Zr, Hf, Ta, Nb, and TiO2 are the elements with the least
commonly cited bulk closure temperatures (Tc) for white deviation over the entire profile. Although TiO2 shows
mica (Rb–Sr; *500 °C; 40Ar/39Ar: *350 °C) are not deviations in r values of \5 %, it has been excluded from
necessarily relevant in metamorphic rocks that record the reference frame, as well as Nb and Ta, because the vein
complex thermal, deformational and fluid infiltration his- locally includes large rutile clusters, suggesting that these
tories (Villa 1998; Glodny et al. 2007). Even so, the cor- elements potentially have been mobilized. Previous studies
responding nearly identical ages of ca. 38 Ma can best be successfully showed that Zr can be used as an immobile
explained by assuming very rapid exhumation, so that reference element (e.g. Ague 2003; Gao et al. 2007; Pen-
differences in the effective closure temperatures cannot be niston-Dorland and Ferry 2008). In the present case, Zr
resolved. This interpretation is further supported by apatite shows a low average deviation in r values of 3.0 %. The
fission track ages of 34 ± 4 Ma (Baldwin et al. 2007), average deviation for Hf is 6.7 %. SEM images and LA-
providing evidence that the lower temperature segment of ICP-MS data (Table S2) indicate that Zr is predominantly
the unroofing history (ca. 110–60 °C) had already been bound in zircon grains that are evenly distributed in both
reached shortly after the time indicated by white mica host rock and the selvage. Type II vein minerals are free of
dating. inclusions and small single zircon grains are very rare. In
this study, the reference frame is defined by the Zr con-
Mass-balance calculations centration and the samples 41-A and 40-A as unaffected
precursor material.
The mineral reactions controlling the blueschist-to- Mass-balance calculations show that significant mass
eclogite transition are responsible for significant fluid transfer occurred between the type II vein and the host rock
release from subduction zones (e.g. Peacock 1993; Sch- that was ultimately linked to the formation of the ompha-
midt and Poli 1998), inducing element mobilization and cite-rich selvage (Fig. 10). The major-element concentra-
redistribution on different scales. Trace-element analysis tions display a compositional change from the selvage over
provides an opportunity to evaluate element mobility the transition zone towards the host rock with a gradual
between host rock and veins and the effect of internal and increase of MnO, Al2O3 and Fe2O3(T) (up to 30–60 %),
external fluids. while CaO and Na2O concentrations are decreasing (up to
For the interpretation of bulk trace-element data, mass- -50 and -80 %, respectively). This can be attributed to a
balance calculations were carried out following the pro- decrease of omphacite and an increase of phengite modal
cedure of Ague (2003). This approach has the advantage of proportions. Relative concentrations of SiO2, TiO2 and
displaying elemental mass transfer independent from MgO display only slight variations between selvage and
overall mass gain or loss, because the calculations rely on a host rock (±10 %). The major-element concentration in the
series of immobile reference elements that are not changed host rock samples along the profile remains relatively
in the metasomatic processes. For applying the mass- unchanged. An exception is MnO with an elevated
123
concentration (up to 40 %) relative to the reference frame In summary, the mass-balance calculations show similar
at a distance of 5–10 cm and 33 cm to the vein. As garnet results to the calculations of Spandler and Hermann (2006)
is the main host for MnO, this is related to garnet-domi- that are based on LREE as reference element and indicated
nated type I veins cross-cutting the sample profile at this that external material has been added to the type II vein.
position (Fig. 2). The effect of this type I vein is also Major- and trace elements which are incorporated in garnet
revealed in the LILE pattern, with an increased relative and phengite (e.g. MnO, HREE, LILE) have been effec-
concentration of Rb, Ba and K2O (up to 160 %) as a result tively mobilized in the host rock on a cm-scale during
of an increased modal abundance of phengite. This prograde mineral reactions and accumulated during the
demonstrates that mass action also occurred to a smaller formation of minerals building the type I vein assemblages.
extent between host rock and type I veins (Fig. 10). Excess fluid in the type I vein network may have been
Monovalent LILE (K, Rb, Ba) are depleted in the sel- discharged into the type II vein. Dissolution–precipitation
vage by up to 80 %. Contrary to all other elements, this reactions at the reaction front resulted in mobilization of
depletion continues into the host rock up to a distance of the bulk of available elements during selvage formation
ca. 20 cm to the vein. (e.g. Putnis and John 2010) in the range of 3–6 cm. Ele-
It seems that garnet-related components precipitated in ments from minerals that became progressively unsta-
the type I vein while the more fluid-mobile LILE were ble under the newly developing equilibrium conditions of
removed from the system through the type I vein network the selvage (e.g., LILE, phengite components) are mobi-
towards the type II vein. The mass change of the mono- lized at a greater distance of up to 20 cm from the vein and
valent LILE reflect the highest mobility, as they are also scavenged into the type II vein, whereas significant
effectively removed from the transition zone between host amounts of CaO, Na2O and Li where added to the selvage
rock and selvage in addition to the selvage itself, whereas system.
the HREE and major elements are only slightly mobilized
at this distance and have been incorporated into the newly Development of the vein system
forming mineral assemblage.
The relative Li concentration, however, is strongly Fluid–rock interaction in oceanic subduction zones is
enriched in the selvage (up to 120 %) showing a trend documented by vein-network systems in HP/LT rocks that
parallel to CaO and Na2O and the omphacite modal represent fossilized fluid pathways formed by free fluid
abundance. After a decrease to ca -20 % at a distance of phases at high P–T conditions (Gao and Klemd 2001; John
5 cm from the vein, the Li concentration remains constant and Schenk 2003; John et al. 2004; Spandler and Hermann
throughout almost the entire profile. 2006; John et al. 2008; Herms et al. 2012; Angiboust et al.
The HREE are depleted (ca. -60 %) in the selvage, and 2014). Such vein systems are either dominated by internal
their relative concentration is gradually increasing through or external fluids (John et al. 2008; van der Straaten et al.
the transition zone into the host rock. A slightly variable 2008; Beinlich et al. 2010). Various models have been
distribution pattern along the profile in the host rock is suggested to explain the combination of both types in an
reflecting the modal abundance of garnet (Fig. 10e). The evolving subducting slab from the initial process of dehy-
mass change in HREE is similar to the trend of MnO and is dration reactions over the channelized flow towards dehy-
most distinct in Lu with the highest atomic number. The dration of the system by fast travelling fluids (Plümper
depletion along the selvage and the enrichment in the vein et al. 2014; e.g. Miller et al. 2003; Zack and John 2007;
indicate a rather effective mobilization/redistribution of Connolly 2010; Skarbek and Rempel 2016). The most
even usually fluid-immobile elements during the formation striking feature of the studied PEM outcrop are two dif-
of the selvage. ferent types of garnet-dominated HP veins that formed at
As with the HREE, the LREE also have variable relative different times, on different time scales and by different
concentrations throughout the host rock, but are not mechanisms (Fig. 2). Type I veins are characterized by
depleted in the host-selvage-transition and only slightly internally buffered widespread and small-scale channelized
depleted in the selvage (Fig. 10c). The LREE are thought flow with limited element transport. The type II vein is
to be buffered by their major host mineral epidote which characterized by channelized flow of external fluids and
occurs equally distributed in host rock and selvage. intense element transport. The external origin of the type II
The relative concentrations of the HFSE vary only vein-forming fluid is based on the following observations
slightly in the host rock (±20 %; Fig. 10f, g). In the sel- and interpretations. Fluid-pressure gradients may cause
vage, V is enriched by up to 40 %. Niobium and Ta vary by flow in open fractures and induce diffusional transport,
up to 20 % along host rock, transition zone and selvage. which may result in the formation of a reaction selvage
Their identical trend to the TiO2 concentration documents a (Oliver and Bons 2001). However, such an internally
relation to the rutile modal abundance. derived and closed system induces that the most soluble
123
elements are transferred into the vein, while the least sol- of ca. 25 °C while releasing significant amounts of
uble components remain in the selvage (Oliver and Bons fluid into the dehydrating host rock (Fig. 9). This
2001). In the type II vein–selvage system, it is the opposite, results in accelerated garnet growth rates and a change
e.g. garnet (composed of rather fluid-immobile compo- in the garnet inclusion pattern from fine-grained
nents) is most abundant in the vein, whereas it is least titanite-dominated towards medium-sized omphacite–
abundant in the selvage (Figs. 2, 3). Additionally, more quartz–epidote-dominated domains going along with a
mobile elements such as Li, Na and Ca occur in higher distinct peak in the HREE/MREE concentration
concentrations in the selvage than in the vein and the host (Fig. 5). This also documents the instability of titanite
rock (Fig. 10; Table 1). A closed system would suggest around ca. 500 °C in water saturated MORB (John
that sources and sinks are balanced, which is not observed et al. 2011) which transfers REE to the product phases
here. The selvage displays a continuous increase of, e.g. (newly forming minerals plus fluid) providing a direct
Ca, Na and Li towards the vein, while the vein itself link to these breakdown reactions and effective
contains only very little of these elements. As the host rock element transport by the fluid within the wall-rock-
is also not showing any evidence of having acted as source selvage-vein system.
of those elements (Fig. 10), it is the most reasonable 4. At ca. 490–500 °C, chlorite is no longer present in the
explanation that an external fluid caused the formation of rock and the amphibole content is decreased to ca.
the type II vein and the related reaction zone. 40 wt%. With ongoing subduction and further increas-
In the following paragraphs, the presence and origin of ing P–T conditions, mineral reaction rates decrease,
both vein systems are outlined in more detail. with reduced garnet growth relative to omphacite
(Fig. 9). The modal abundance of epidote decreases
only slightly throughout the whole P–T range and as
Type I veins (dehydration veins)
epidote can act as a buffer for LREE.
Based on pseudosection calculations and mineral chem- This model of reaction steps is in accordance with the
istry, the formation of the dehydration-vein system can be regional gradient (isograd pattern) and the RSCM tem-
described as follows: perature profile reported by Vitale Brovarone and Agard
(2013). Analogous processes affecting large volumes of
1. The precursor host rock contains ca. 8 wt% chlorite,
similar rocks in other parts of the subducting slab will lead
20 wt% epidote and 47 wt% amphibole as water-
to release and redistribution of large amounts of fluids that
bearing minerals at 1.8 GPa and 400 °C. With
elsewhere may enter the system as an external fluid. Such
increasing P–T, amphibole becomes increasingly
external fluids are not in equilibrium with the surrounding
unstable and fluid is released into the host rock. The
host rock, and thus fluid–rock interaction is triggered along
newly formed phases (Grt, Omp) have a lower volume,
the type II vein—host rock contacts, resulting in the for-
causing a continuous increase of porosity that can
mation of a metasomatic reaction selvage.
accommodate this fluid (Plümper et al. 2014; John
et al. 2012).
Type II veins (transport veins)
2. Ongoing breakdown reactions lead to an increase of pore
fluid pressure and the development of an interconnected
The formation of the type II vein and the associated selvage
porosity (Plümper et al. 2014). This permeability allows
is related to the following processes:
channelized fluid migration at low fluxes within the
dehydrating rock. Increasing fluid fluxes are assumed to 1. Continuous descent into the mantle caused ongoing
be linked to fractures and/or zones with increased eclogitization and thus dehydration of the host rock. At
porosity (e.g. due to originally higher Chl abundance). some stage after the host rock has already been at least
Localized fluid-pressure gradients develop that force partly dehydrated, an external fluid infiltrated the host
fluid flow towards and accumulation in these zones rock with its type I vein system. Garnet grains from the
(Plümper et al. 2014; Yardley 1986; John et al. 2008). edge of type II veins that are in direct contact to the
When a sufficient amount of fluid has accumulated, fluid selvage display distinct zonation and inclusion patterns
can propagate through the host rock by the dynamically (Figs. 4, 11). The cores of these grains are identical to
forming interconnected network of veins (Plümper et al. those recognized in the host rock and selvage. Inclu-
2014; Miller et al. 2003; Zack and John 2007; Connolly sions outside of the core resemble selvage and
2010). During the prograde vein-forming process, gar- transport veins on the respective sides. Also the host
net, phengite and quartz precipitate in these zones. rock areas with abundant type I veins contain fewer
3. With a further increase in temperature ([460 °C), and smaller garnet porphyroblasts, which is similar to
chlorite breaks down rapidly over a temperature range the transport vein selvage.
123
16-II host rock garnet 14-II selvage garnet 14-II vein-selvage contact 20-II vein garnet
500
700 180
250
600 160
400
140
500 200
120
300
Ca 400 150 100
300 80
200 100
60
200
50 40
100
100
20
500 µm 500 µm 500 µm 500 µm
450 180 70
200
400 160
60
350 140
150 50
300 120
Mg
250 100 40
200 100
80 30
150 60
20
100 40 50
50 20 10
500 µm 500 µm 500 µm 500 µm
180
450 450
160 600
400 400
140
350 350 500
120
300 300
400
Fe 100
250 250
80 300
200 200
150 60 150 200
100 40 100
100
50 20 50
500 µm 500 µm 500 µm 500 µm
90 45
25
200
80 40
70 35 20
30 150
60
Mn 15
50 25
20 100
40
10
30 15
10 50
20 5
5
10
500 µm 500 µm 500 µm 500 µm
Fig. 11 a Element distribution maps for Ca, Fe, Mg and Mn showing maps are optimized for maximum contrast to highlight compositional
different zonation and inclusion patterns in garnet grains from host features. Scales display counts per second
rock, selvage, selvage-vein contact and type II vein. Note that all
2. Influx of externally derived fluid was responsible for rock of the external fluid has a slightly different
precipitation of inclusion-free garnet, phengite, quartz protolith (either magmatic or due to seafloor alteration)
and minor omphacite (±Rt, ±Ap) in the central part of composition. This is in accordance with initial
the type II veins. Similar d18O values of ca. ?10 % 87
Sr/86Sr values of vein and wall rock (ca.
reported for the type II vein and other parts of the vein 0.7047–0.7048) suggesting a seawater-altered basalt
system (Spandler and Hermann 2006) suggest that the protolith as the origin of both the host rock, and the
external fluids are derived from a source that is similar source rock of the external fluid. We suggest that both
to the host rock of the studied occurrence. However, source rocks belong to the same coherent part of a
due to chemical differences in major- and trace subducting oceanic crust, but at some distance to each
elements (e.g. Ca, Na, Li), it seems that the source other.
123
3. The released external fluid may have been modified by peak in selvage garnet is located on the inner side of
reactions along its flow path from its source to the site of this distinct change in the inclusion pattern (Figs. 4,
the type II veins. Any chemical difference in the bulk 11). This implies selvage formation and therefore also
rock will cause compositional differences in the equi- external fluid infiltration took place above 500 °C and
librium fluid; fluids from different host rocks are also resulted in accelerated garnet growth rates.
compositionally different (e.g. by different degrees of 5. The outermost rims of host rock, selvage and vein
seafloor alteration). During the formation of the type II garnet are compositionally identical and inclusion-free,
vein, external and internal fluid systems have been which demonstrates that garnet growth continued after
coupled. The large permeability contrast between the fluid infiltration at a rate that allowed inclusion-free
fluid filled low porosity in the wall rock and the high growth. This last growth zone reflects peak metamor-
porosity in the type II vein focuses any advective phic conditions, which in turn implies that both vein
component of fluid flow into the type II vein. The systems developed prior to peak metamorphic condi-
compositional differences and the resulting chemical tions and hence while the rock was still subducting.
gradient between the internal (host rock) and the external
(type II vein) fluids cause fluid-mediated, diffusive
Intraslab fluid flow versus mèlange fluid flow
element exchange in (e.g. Ca, Na, Li) and out (e.g. LILE)
of the immediate wall rock and related mineral reactions.
The studied rocks were collected from a metabasic block
As a consequence, in the developing reaction halo, the
that is part of a hybrid mélange. The external fluid has a
pre-existing mineral assemblage (Chl–Gln–Omp–Ph) is
similar oxygen and strontium isotope composition that is
progressively out of chemical equilibrium with the
similar to the host rock (Spandler and Hermann 2006; this
dynamically changing fluid composition in the immedi-
study) implying a largely similar metabasic source rock. In
ate vicinity of the transport vein. The diffusive element
contrast the mélange matrix is either ultramafic (talc, ser-
transport leads to a gradual change from the selvage to
pentine) or metasedimentary. Such potential protoliths do
the host rock composition. The reaction starts at the
not match the isotope data. Outer rims of garnet grains in
immediate contact to the transport vein and propagates
host rock, selvage and vein show signs of continuous
into the host rock as a smooth reaction front that led to
prograde growth, suggesting ongoing subduction after vein
the replacement of the original paragenesis by an
formation. Additionally, fluid flow in a mélange is sup-
omphacite-dominated mineral assemblage.
posed to get focussed into the matrix and diverted around
4. The timing of type II vein formation can be best
blocks due to permeability contrasts (Ague 2007).
constrained by comparing the garnet growth pattern in
Accordingly, we do not consider the hybrid mélange matrix
the host rock, selvage and type II veins. Distinct sector
in which the outcrop is placed as the external source for the
zoning of Ca and, to a lesser extent, of Fe and Mg in
type II vein-forming fluid. The formation of the vein sys-
vein garnet (Fig. 11) suggests very fast growth from a
tem is considered to have taken place, while the sample
fluid (e.g. John and Schenk 2006; Pollok et al. 2014)
was still part of a coherent and subducting slab. The type II
and hence a short-lived fluid pulse for type II vein
vein-forming fluid originated from similar rocks at some
formation. Garnet cores in host rock and selvage
distance to the studied material at that time. Such intraslab
incorporate identical inclusion assemblages and ele-
transport vein systems often are associated with extensive
ment concentrations, suggesting that both formed
mass transport through the slab (e.g. Secor and Pollard
contemporaneously. Selvage garnet grains are slightly
1975; Molina et al. 2004; Spandler et al. 2011) that had
smaller than to host rock garnet grains; however, no
been induced by short fluid pulses with high fluxes (An-
unambiguous textural evidence for dissolution–precip-
giboust et al. 2012; John et al. 2012; Dragovic et al. 2015).
itation reactions (e.g. sharp chemical boundaries) have
been recognized (e.g. Pollok et al. 2008; Li et al.
2016). The changes in the inclusion patterns during
Summary and conclusions
garnet growth in the host rock and the selvage are
different. Within the selvage, the inclusion-rich garnet
1. A complex HP/LT vein system cross-cutting an eclo-
mantle zone is attributed to faster garnet (re-) growth,
gitic host rock of the PEM records the prograde
likely at elevated element availability and likely
blueschist-to-eclogite transition and includes an
contemporaneously with the growth of the inclusion
extensive network of veins with no or only poorly
forming minerals, which have almost the identical
developed reaction haloes, as well as few larger veins
grain size to those of the selvage matrix (Fig. 3).
that are associated with distinct omphacite-rich meta-
Despite unfavourable surface energy constraints garnet
somatic selvages.
overgrew abundant large minerals. The MREE/HREE
123
2. Based on a much more detailed sampling profile that acted as a buffer for these elements. Ca, Na and Li
compared to previous studies, petrological and geo- are enriched in the selvage and indicate that the
chemical observations suggest an alternative model for external fluid was carrying high concentrations of these
vein formation comprising two separate types of vein. elements.
Type I or ‘‘dehydration’’ veins collected internally
derived fluids related to the breakdown of hydrous Acknowledgments The Deutsche Forschungsgemeinschaft finan-
phases (amphibole, chlorite, epidote) in the host rock cially supported this research through grant JO 349/5-1. We thank H.
during prograde eclogite-facies metamorphism. The Baier for laboratory assistance and support at the mass spectrometer
larger type II veins are considered to represent during Rb–Sr analysis, J. Berndt for his support on the electron
microprobe and the LA-ICP-MS and P. Schmidt-Beurmann for sup-
‘‘transport’’ veins which record superimposed influx port during XRD measurements. Constructive comments by the
of an external Ca-, Na- and Li-rich fluid that is most journal editor Othmar Müntener and two anonymous reviewers con-
likely related to similar dehydration reactions in other siderably improved the manuscript and are greatly appreciated.
parts of the subducting slab.
3. New Zr-in-rutile temperature estimates of ca. 540 °C
for host rock, selvage and type II vein combined with References
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Contrib Mineral Petrol (2016) 171:90

Fluid–rock interaction and evolution of a high-pressure/low-

Electronic supplementary material The online version of this Introduction

a New Caledonia - main island b

c d type II vein selvage selvage-host transition

host rock host-selvage transition selvage vein

the selvage glaucophane. Trace-element and REE con-

centrations are generally low (Table S1). Single spots with

tions are probably related to tiny zircon inclusions.

Omphacite compositions are homogeneous throughout

the profile, independent of grain size (Fig. S1a) and are

characterized by a slight core-to-rim increase of jadeite

composition (core: Jd31Ac24Di45; rim: Jd37Ac18Di45;

Table 2). Omphacite inclusions in garnet are composi-

tionally indistinguishable from grains in the matrix

(Table 2). Titanium and Zr concentrations are highly

variable due to the aforementioned inclusions that could

not be avoided during analysis. The LREE concentrations

Garnet porphyroblasts representing different textural

terized by a high almandine component (55–63 %;

Table 2) and well-developed major-element zoning pat-

type II vein garnet show a complex sector-zoning pattern

perpendicular to the grain boundaries that is best devel-

MgO contents (Fig. 11; Spandler and Hermann 2006).

Average compositions for host and selvage garnet are

Prp13And2 towards the rim, and Alm62Grs22Sps3Prp12-

And1 in the outer rim (Table 2; Fig. S2). Trace-element

(Fig. 5; Table S1). Garnet is the major host for HREE in

all zones; however, concentrations are slightly lower in

with HREE clearly enriched in garnet cores. Towards the

rim, a second prominent HREE peak is present in all

and selvage grains, this peak is correlated to a distinct

change of inclusion textures (Fig. 10). In garnet from the

vein and the vein-selvage contact, a similar peak is pre-

sent but located closer to the garnet rim. Garnet rims

tions (Fig. 5). Other trace elements are generally below

throughout host rock and selvage (Table 2). It is a major

found in other rocks of the PEM (Spandler et al. 2003)

Aeg 25.6 25.2 18.7 26.4

600 a host rock garnet 800 b selvage garnet

200 selvage (14-III)

Table 3 P–T estimates for peak metamorphic conditions in the PEM

Metamorphic temperature and pressure conditions were Bulk-rock geochemistry

20-b WR Powder 31.5 23.6 3.857 0.706914 0.000009 38.0 ± 0.3

a 23-b - host-rock + type I vein c 20-b - type II vein

b 22-a - host-rock + type I vein d 20-b + 22-a + 23-b

500 µm 500 µm 500 µm 500 µm

500 µm 500 µm 500 µm 500 µm

500 µm 500 µm 500 µm 500 µm

500 µm 500 µm 500 µm 500 µm

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