ORIGINAL PAPER
Rutile occurrence and trace element behavior
in medium-grade metasedimentary rocks: example
from the Erzgebirge, Germany
George Luiz Luvizotto & Thomas Zack & Silke Triebold &
Hilmar von Eynatten
Received: 29 January 2009 /Accepted: 23 October 2009 /Published online: 13 November 2009
# The Author(s) 2009. This article is published with open access at Springerlink.com
Abstract Metamorphic textures in medium-grade (~500–
550°C) metasedimentary rocks from the Erzgebirge give
evidence of prograde rutile crystallization from ilmenite.
Newly-crystallized grains occur as rutile-rich polycrystal-
line aggregates that pseudomorph the shape of the
ilmenites. In-situ trace element data (EMP and SIMS) show
that rutiles from the higher-grade samples record large
scatter in Nb content and have Nb/Ti ratios higher than
coexisting ilmenite. This behavior can be predicted using
prograde rutile crystallization from ilmenite and indicates
that rutiles are reequilibrating their chemistry with remain-
ing ilmenites. On the contrary, rutiles from the lowest grade
samples (~480°C) have Nb/Ti ratios that are similar to the
ones in ilmenite. Hence, rutiles from these samples did not
equilibrate their chemistry with remaining ilmenites. Our
data suggest that temperature may be one of the main
factors determining whether or not the elements are able to
diffuse between the phases and, therefore, reequilibrate.
Newly-crystallized rutiles yield temperatures (from ~500 to
630°C, Zr-in-rutile thermometry) that are in agreement with
the metamorphic conditions previously determined for the
studied rocks. In quartzites from the medium-grade domain
(~530°C), inherited detrital rutile grains are detected. They
are identified by their distinct chemical composition (high
Zr and Nb contents) and textures (single grains surrounded
by fine grained ilmenites). Preliminary calculation, based
on grain size distribution of rutile in medium-grade
metapelites and quartzites that occur in the studied area,
show that rutiles derived from quartzites can be anticipated
to dominate the detrital rutile population, even if quartzites
are a minor component of the exposure.
Introduction
Several studies have recently promoted the application of
in-situ trace element analyses of accessory minerals as a
tool to monitor geochemical processes in metamorphic and
igneous rocks. This is a reflection of the continuous
development of several in-situ analytical techniques (i.e.,
higher spatial resolution and lower detection limits) and the
fact that accessory minerals are frequently the main carrier
of trace elements used as tracer of geochemical processes
Editorial handling: F. Gaidies and T. John
G. L. Luvizotto (*) : T. Zack
Institut für Geowissenschaften, Mineralogie,
Universität Heidelberg,
Im Neuenheimer Feld 236,
69120 Heidelberg, Germany
e-mail: george.luvizotto@mpic.de
T. Zack
e-mail: zack@uni-mainz.de
G. L. Luvizotto
Geochemie, Max-Planck-Institute für Chemie,
Joh.-Joachim-Becher-Weg 27,
55128 Mainz, Germany
T. Zack
Institut für Geowissenschaften, Universität Mainz,
Becher Weg 21,
55128 Mainz, Germany
S. Triebold :H. von Eynatten
Sedimentologie und Umweltgeologie,
Geowissenschaftliches Zentrum, Universität Göttingen (GZG),
Goldschmidtstr. 3,
37077 Göttingen, Germany
S. Triebold
e-mail: striebo@gwdg.de
H. von Eynatten
e-mail: hilmar.von.eynatten@geo.uni-goettingen.de
Miner Petrol (2009) 97:233–249
DOI 10.1007/s00710-009-0092-z
(e.g., Zr in zircon, Ti in rutile, rare earth elements in
monazite and xenotime).
Rutile is one of the major Ti-phases, frequently occur-
ring as an accessory mineral in diverse metamorphic and
igneous rocks, siliciclastic sediments, placer deposits and
hydrothermal ore deposits. As it incorporates several
highly-charged trace elements (e.g., Ti, Zr, Nb, Ta, Sn,
Sb, W, V, Cr and Mo, see summary in Zack et al. 2002)
rutile has successfully been applied as a tool to monitor
geochemical processes such as subduction-zone metasoma-
tism, magma evolution and element cycling (e.g. Saunders
et al. 1980; McDonough 1991; Brenan et al. 1994; Stalder
et al. 1998; Münker 1998; Foley et al. 2000; Rudnick et al.
2000; Klemme et al. 2005). With the calibration of the Zr-
in-rutile thermometer (Zack et al. 2004b; Watson et al.
2006; Tomkins et al. 2007) rutile has become an important
tool for assessing metamorphic temperatures, especially in
eclogite- and granulite-facies rocks (Zack and Luvizotto
2006; Spear et al. 2006; Harley 2008; Luvizotto and Zack
2009). In provenance studies, Nb and Cr systematics in
rutile can be used to distinguish pelitic from mafic
protoliths (Zack et al. 2004a; Stendal et al. 2006; Triebold
et al. 2007; Meinhold et al. 2008).
Luvizotto and Zack (2009) investigated the behavior of
trace elements during prograde (amphibolite- to granulite-
facies transition) rutile crystallization from a pre-existing
Ti-phase in the amphibolite- to granulite-facies transition.
The authors observe that Nb concentrations in rutile from
lowest grade samples (<850°C) show a larger spread when
compared to those from higher grades (up to 930°C). This
pattern can be predicted using prograde rutile growth
formed from biotite breakdown. Their results support that
elements that are usually interpreted to be immobile at
whole rock scale (e.g., Zr, Nb and Ti) were able to diffuse
and reequilibrate between rutile and biotite under granulite-
facies conditions.
In the present study we investigate whether or not
equilibrium partitioning of trace elements is operating
between rutile and other minerals during metamorphism in
lower-grade conditions. Medium-grade metasedimentary
rocks from the Erzgebirge display textures that support
prograde rutile crystallization associated with ilmenite
breakdown. These textures are similar to the ones described
by Luvizotto and Zack (2009), since in either case rutile is
forming from pre-existing Ti-bearing phases (high-Ti
biotite and ilmenite).
In this study we also address an issue highlighted in a
companion study by Triebold et al. (2007). Several rutiles
from present-day drainage sediments sampled within the
lowest-grade domain (greenschist-facies) of the studied area
record high temperatures (up to 1000°C). These rutiles are
interpreted as inherited detrital grains, preserved in the
metasedimentary rocks of the studied area (source for the
present-day sediments). High temperatures are attributed to
a former metamorphic cycle. In order to shed more light on
the occurrence of such inherited grains we discuss the
temperature records in rutiles from greenschist-facies rocks.
Additionally, we briefly investigate which rock type is
capable of delivering the highest amount of rutile to
sediments derived from low- to medium-grade metasedi-
mentary rocks, taking into account the occurrence of
inherited rutiles as discussed above.
Geological setting and studied samples
The Erzgebirge is situated at the northwestern border of the
Bohemian Massif and is part of the metamorphic basement
of the Mid-European Variscides (Fig. 1). It is characterized
by a large-scale antiformal structure consisting of five
tectonometamorphic units (Willner et al. 1997; Rötzler et
al. 1998). From the base to the top these units are: Red and
Grey Gneisses (RGG); Gneiss/Eclogite Unit (GEU); Mica
schist/Eclogite Unit (MEU); Garnet-Phyllite Unit (GPU);
and Phyllite Unit (PU). The tectonometamorphic stacking is
interpreted as a result of continent-continent collision
processes during the Variscan Orogeny (e.g., Willner et al.
1997; Rötzler et al. 1998; Mingram 1998). Geochemical
discriminations suggest that the protoliths of all metamor-
phic units are similar (mature sediments, exposed to
prolonged tropical weathering and extensive reworking),
leading to the conclusion that they represent a repetition of
metasedimentary sequences (Mingram 1998). Peak pressure
(P) and temperature (T) conditions published for the western
part of the Erzgebirge are presented in Fig. 1 (references are
given in the figure caption) and can be summarized as
follows: PU, 400°C and 2 kbar; GPU, 480°C and 6 to 9 kbar;
MEU, 500 to 550°C and 7 to 12 kbar; GEU, 100 to 800°C
and 12 to 24 kbar; RGG, 600 to 650°C, and 6 to 8 kbar.
The present study focuses on the GPU, MEU and GEU
in the western part of the Erzgebirge, more specifically, on
metasedimentary rocks from the GPU and MEU. Clockwise
P-T paths are documented for the Western Erzgebirge. For
the GEU, decompression at very high temperatures is
accompanied by cooling. P-T paths for the MEU and
GPU indicate heating during early pressure release. P-T
paths of these three units converge at pressures
corresponding to 0.6–0.8 GPa, suggesting that these units
were juxtaposed at the corresponding depths (Willner
et al. 1997; Rötzler et al. 1998). Metasediments from the
GPU are characterized by the occurrence of graphite
phyllites, garnet- and albite-bearing phyllites, feldspar-free,
chloritoid-bearing phyllites, quartzites, marbles and meta-
tuffites. Garnet-free phyllites are the most common rocks in
the GPU. Metasediments from the MEU are characterized
by the occurrence of garnet-bearing mica schists (that may
234 G.L. Luvizotto et al.
contain variable amount of graphite, albite and chloritoid),
paragneisses and marbles. Garnet- and chloritoid-bearing
mica schists are the most common rock types. Metasediments
from the GEU are characterized by the occurrence of
migmatitic paragneisses, feldspar-bearing mica schists and
feldspar-free, kyanite-bearing mica schists (Willner et al.
1997; Rötzler et al. 1998; Mingram 1998). Although mafic
rocks are beyond the scope of the present work, it is worth
mentioning that eclogites occur as local intercalations in both
MEU and GEU.
Key information on the studied samples is presented in
Table 1. Mingram (1996, see Table 1) investigated seven of
the studied samples. Sample EGB04-S56 corresponds to
the quartzite sample presented in Triebold et al. (2007).
Analytical techniques
Electron microprobe (EMP)
Electron microprobe analyses of rutile and ilmenite were
carried out at the Institut für Geowissenschaften, Universität
Heidelberg with a CAMECA SX51 equipped with 5 WDS
detectors. The beamwas set to 20 kVand 100 nA and analyses
followed the method outlined by Luvizotto et al. (2009). The
following elements were analyzed: Si, Ti, V, Cr, Fe, Zr, Nb
and W. With this setup, the detection limits are 220 ppm for
V, 50 ppm for Cr, 40 ppm for Fe and Zr, 60 ppm for Nb and
350 ppm for W. To control zero-concentration peak
intensities and instrument drift, every block of ten analyses
of unknown was bracketed by two analyses of synthetic
rutile with nominal zero-concentration of trace elements.
Concentrations of Si were used to detect and avoid
contamination associated with submicroscopic zircon inclu-
sions (according to the method outlined by Zack et al.
2004b). Rutile measurements with apparent Si concentra-
tions higher than 300 ppm that showed unusually high Zr
contents were excluded from the data set (same procedure
applied to SIMS analyses). EMP beam diameter was set to
5 μm. However, due to secondary fluorescence the minimum
grain size for obtaining reliable analyses (i.e., analyses with
Si content <300 ppm) was ~ 20 μm. For small (ca. 20 μm)
rutile grains and for rutile aggregates, measurements with Si
content above 300 ppm and Zr concentrations similar to
R10
S56
R11
4550 4560 4570 4580
5590
5600
5610
5620
5630
Aue
Geyer
Annaberg-
Buchholz
Marienberg
Zschopau
Oberwiesenthal
Lößnitz
Stollberg
480 ˚C
6-9 kbar ***
500-550 ˚C
7-12 kbar***
700-800 ˚C
12-24 kbar *
400 ˚C
 2 kbar **
600-650 ˚C
6-8 kbar **
Ordovician Sediments
Hercian Granites
Phyllite Unit (PU)
Tectonometamorphic Units
Legend
Sample Location
EGB-R#
Garnet-Phyllite Unit (GPU)
Micaschist / Eclogite Unit (MEU)
Gneiss / Eclogite Unit (GEU)
Red and Gray Gneisses (RGG)
10 km
Samples from Mingram (1998)
Berlin
Germany
Czech Replublic
100 km
52˚N
50˚N
14˚E10˚E
Dresden
Frankfurt Praha
München Wien
N
P2
2/2
2/12
P38c
61c
3/1
A15
Fig. 1 Simplified geological map of the western part of the
Erzgebirge. Coordinates are provided in German coordinate system
(Gauss-Krüger). PT conditions from: *Willner et al. (1997), **Min-
gram and Rötzler (1999) and ***Rötzler et al. (1998). Stars represent
areas where relic rutiles (Zr-in-rutile temperatures strongly exceeding
peak metamorphic temperature reached in these tectonometamorphic
units) were found by Triebold et al. (2007)
Rutile occurrence and trace element behavior in medium-grade metasedimentary rocks 235
rutiles with low Si contents were not excluded (high Si
values were interpreted as secondary fluorescence from
silicates).
Secondary ion mass spectrometry (SIMS)
SIMS measurements of rutile and ilmenite were performed
at the Institut für Geowissenschaften, Universität Heidel-
berg with a CAMECA ims 3 f. Analyses were carried out
using a 14.5 keV / 10–20 nA 16O− primary ion beam, which
resulted in spot sizes of 20–30 μm. By using a field
aperture the effective spot size was reduced to 12 μm. With
this setup, the smallest grain size for obtaining contamina-
tion free analyses was ca. 20 to 30 μm. Positive secondary
ions were nominally accelerated to 4.5 keV (energy
window set to ±20 eV) and the energy filtering technique
was used with an offset of 90 eV at mass resolution m/Δm
(10%) of 370. Count rates were normalized to 47Ti. TiO2 in
rutile is assumed to be 100 wt.%, which introduces an error
of <1%, as elements other than Ti and O occur only in
minor amounts in the studied rutiles. In ilmenite, the Ti
concentration was based on the values obtained by EMP.
The following isotopes were analyzed: 27Al, 30Si, 47Ti,
90Zr, 93Nb, 118Sn, 120Sn, 121Sb, 123Sb, 178Hf, 181Ta, 184W,
186W, 232Th, 238U. Concentrations were calculated based on
relative sensitivity factors (RSF) determined using a set of
rutile reference materials presented by Luvizotto et al.
(2009). Since Th concentrations are not available for the
reference materials used here, no reliable RSF can be
calculated for Th. However, intensity ratios obtained for the
studied rutiles suggest that Th concentrations are extremely
low (below the 0.1 ppm level when using RSF of U).
Micro-Raman spectroscopy
Laser micro-Raman spectroscopy was applied to selected
grains in order to identify the TiO2 structure type. Raman
spectra were obtained using a Horiba Jobin Yvon Labram
HR-UV 800 (equipped with a Peltier-cooled CCD detector)
at the Geowissenschaftliches Zentrum, Universität Göttingen.
Analyses were carried out using 633 nm laser excitation,
20 mW laser power, 1200 l/mm grating and a Peltier-cooled
CCD detector.
Results
Textural evidence for rutile growth in medium-grade
metapelitic rocks
In GPU rocks rutiles occur as polycrystalline aggregates,
which are characterized by a fine-grained intergrowth of
rutile and chlorite that mimic the shape of ilmenites thatTa
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236 G.L. Luvizotto et al.
coexist in the rock. Similar textures, although with a higher
rutile/ilmenite ratio, can still be found in some metasedi-
mentary rocks from the MEU (Fig. 2). These textures
indicate rutile grow from ilmenite breakdown (Fig. 2). As
the content of Ti is higher in rutile than in ilmenite (100 wt.%
TiO2 in rutile vs. ~53 wt.% TiO2 in ilmenite), the physical
volume once occupied by ilmenite is not entirely filled by
rutile (Fig. 2). The Fe released from the breakdown of
ilmenite is used, together with the elements available in
matrix minerals (quartz and phyllosilicates), to crystallize
chlorite according to the simplified metamorphic reaction:
Ilm+silicates+H2O→Rt+Chl (mineral abbreviations after
Kretz 1983). The BSE images presented in Fig. 2 are
arranged according to an increasing rutile/ilmenite ratio,
which we interpret to represent the prograde evolution of the
textures. In Figs. 2a and 2b only minor amounts of rutile are
present and ilmenite grains still preserve their euhedral/
subhedral elongated (lath) habit. Figs. 2c to 2e show more
evolved stages of the texture. The occurrence of a large
polycrystalline rutile aggregate only a few micrometers apart
Ms
ChlGrt
Chl
Rt
Rt
Ilm
1486 ppm
2.5 x 10-3
GPU / MEU
F
Ilm Ilm
Ilm
RtMs
320 ppm
1.0 x 10-3
450 ppm
1.4 x 10-3
1140 ppm
1.9 x 10-3
Chl
A
GPU
GPU
GPU
C
B
Ilm
410 ppm
1.3 x 10-3
242 ppm
4.0 x 10-4
Ms
Chl
Qtz
Chl
Mnz Rt
Ilm
Ilm
GPU
E
Mnz
700 ppm
2.2 x 10-3
Rt
Ms
Chl
Ms
Rt
Chl
Rt
Rt
Ms
Rt
GPU
D
850 ppm
2.7 x 10-3
1180 ppm
2.0 x 10-3 Ms
Chl
Rt
Ilm
Mnz
Chl
Ms
Rt
Chl
Qtz
GPU
G
Fig. 2 BSE images exemplify-
ing the textures observed in
metasedimentary rocks from the
GPU and MEU. The images are
arranged in order of increasing
rutile/ilmenite ratio. Numbers
given in the figures correspond
to Nb concentrations (in ppm)
and Nb/Ti ratios. All scale bars
represent 100 μm. See text for
further information. Samples: A,
B and D–P38c; C and E–P2; G–
2/12; H–2/2
Rutile occurrence and trace element behavior in medium-grade metasedimentary rocks 237
from an apparently unreacted ilmenite (representing different
evolutional stages of the reaction) indicate the small size of
the reaction domain (Fig. 2e). In Figs. 2f and 2g ilmenite is
virtually absent. However, rutiles still occur as aggregates
that have the elongated shape inherited from ilmenites.
Rutiles are often present as inclusions in garnet bearing rocks
from the MEU (Fig. 2f).
An important exception to the samples descrided
above is the only analyzed quartzite (EGB04-S56,
MEU) in this study. This sample contains some large
single crystals of rutile that are surrounded by fine-
grained ilmenite (Fig. 3). These rutiles do not have the
typical lath shape of the newly-grown rutiles. We interpret
these grains as inherited detrital rutiles that are still
preserved in the quartzite.
Metapelitic rocks from the GEU are ilmenite-free. In
these rocks rutiles show no traces of the texture described
above and have a rounded shape (Fig. 4).
Identification of TiO2 polymorphs
Rutile was identified by Raman bands at 242, 449 and
614 cm−1 (for a compilation of Raman bands for Ti
polymorphs see Meinhold et al. 2008) and anatase was
identified by Raman bands at 146, 199, 400, 517 and
642 cm−1 (Fig. 5). Brookite was not found in the studied
samples. In the investigated rocks rutile is brownish/reddish
under the optical microscope (transmitted light) while
anatase is light-brown to colorless. Some Ti-oxides dis-
played cathodoluminescence (CL) emission during EMP
measurements (visible as a bright spot when the mineral
was under the focused electron beam). All of these grains
were identified as anatase by Raman. BSE images of
coexisting Ti-polymorphs show that rutile is brighter than
anatase in the studied samples (Fig. 5). All these character-
istics were used as identification criteria.
The current work focuses only on the textural and
chemical relationships between rutile and ilmenite. A more
detailed work on the identification and chemical composi-
tion of TiO2 polymorphs in Erzgebirge rocks and present-
day drainage sediments will be published by Triebold et al.
(in prep.).
Comparison between Nb concentrations in rutile
and ilmenite
Figure 6 summarizes Nb concentrations obtained for rutiles
and ilmenites (for a complete data set, please refer to
Appendix A, Table 3). Nb contents in ilmenite are rather
constant when compared to those in rutile, with average
concentration of ca. 500 ppm in almost all samples. In
contrast, Nb concentrations in rutile are characterized by
three distinct patterns, closely connected to the metamor-
phic unit from which they derive. Rutiles from the GPU
have lower Nb contents (max. concentration of 1330 ppm)
than those from MEU and GEU (total of 11 grains with
concentrations higher than 2500 ppm; max. concentration
up to 9500 ppm). Moreover, their Nb/Ti ratios are
comparable with values obtained for ilmenites from the
same samples. Rutiles from the MEU have higher Nb
contents and display larger spread in Nb concentrations
with Nb/Ti ratios spanning from values as low as the ones
obtained for the ilmenites to values significantly higher.
Rutiles from the GEU show a narrow spread in Nb
concentration. These samples are ilmenite-free and, there-
fore, no direct comparison can be made.
Zirconium concentrations in rutile
For each analysis, a Zr-in-rutile temperature (Fig. 7 and
Appendix A, Table 3) was calculated (calibration of
Tomkins et al. (2007) at pressure conditions defined in
Fig. 1 for each metamorphic zone). Zr contents in all rutiles
from the GPU are below the EMP detection limit
(<40 ppm, corresponding to ca. <500°C) and are in
agreement with peak temperatures reported for this unit
(<500°C, Rötzler et al. 1998). A SIMS measurement of
46 ppm of Zr obtained for sample P2 match the EMP data.
About half of the rutiles analyzed from the MEU (15 out of
28) have Zr contents below the EMP detection limit. The
other grains have higher Zr contents (60–80 ppm), which
are confirmed through EMP as well as SIMS analyses.
These results are in agreement with concentrations back-
calculated from peak metamorphic conditions known for
this area (500–550°C, 0.7–12. GPa). The only exception is
3920 ppm
60 ppm
6.5 x 10-3
90 ppm
2.8 x 10-4
MEU
QuartziteB) Ms
Qtz
Qtz Zrn
Rt
Rt
Ilm
1950 ppm
390 ppm
3.3 x 10-3
1910 ppm
Zr - bd
3.2 x 10-3
440 ppm
1.4 x 10-3
350 ppm
1.1 x 10-3MEU
QuartziteA)
Qtz
Ms
Rt
Rt
Zrn
Rt
Ilm
Ilm
Fig. 3 BSE images of rutiles
interpreted as inherited detrital
grains in the quartzite. Concen-
trations (in ppm) stand for Nb
and Zr (in italic). Pure numbers
represent Nb/Ti ratios. Scale
bars represent 100 μm. bd -
below detection limit (EMP)
238 G.L. Luvizotto et al.
one rutile grain with Zr concentration of 390 ppm from the
quartzite sample (Fig. 3a).
Only few rutiles from the higher-grade samples (EGB04-
R11e, A15c) have Zr contents below the EMP detection
limit. Zr contents obtained through SIMS and EMP are in
agreement with mineral assemblage and metamorphic
textures observed in these rocks with Zr concentrations up
to 200 ppm for sample A15, corresponding to temperatures
of ca. 630°C.
We would like to note that highest Zr contents in rutiles
from garnet bearing rocks are usually obtained for rutiles
included in garnet (see also discussion in Triebold et al.
2007).
Discussion
Behavior of Nb during rutile formation from ilmenite
Samples from the GPU and MEU record intermediate
stages of a reaction where rutile is forming from ilmenite
breakdown. The prograde evolution of this reaction can be
summarized by the simplified model presented in Fig. 8 and
can be described as follows: Initially, only ilmenite occurs
and hosts the main portion of Nb and Ti of the whole rock
(WR). Under metamorphic conditions of the GPU (~480°C,
0.6–0.9 GPa) rutile starts to grow associated with the
breakdown of ilmenite. With increasing metamorphic
grade, the reaction progresses and the rutile/ilmenite ratio
increases. In these intermediate stages rutiles occur as
polycrystalline aggregates inside the volume previously
occupied by ilmenite. Nb is distributed between both
phases. The excess Fe is used to crystallize chlorite, with
other elements available in the surrounding silicates. At
higher metamorphic grade, rutile is the only Ti-phase and
consequently the main carrier of Nb and Ti. It is coarser
grained as a result of re-crystallization and/or ripening and
forms rounded grains (see, e.g., Fig. 4). Notice that biotite
and phengite can incorporate significant amounts of Ti and
its incoporation is temperature-dependent (Patiño Douce
1993; Henry and Guidotti, 2002; Henry et al. 2005). Hence,
in rocks where rutile coexists with Ti-bearing micas, rutile
may not have the WR Nb/Ta ratio.
A distinct geochemical signature is observed in rutiles
formed from biotite breakdown in felsic granulites from the
Ivrea-Verbano Zone (Luvizotto and Zack 2009). In these
rocks, Nb concentrations in rutiles from lowest-grade
samples (ca. 850°C) show a larger spread when compared
Rt
MsPl
Qtz
Ms
Fe-Sulf
Bt
40µmGEU
Rt
Rt
30µm
Bt
Qtz
Qtz
Pl
Kfs
GEU
Fig. 4 BSE images exemplify-
ing rutiles occurring in metase-
dimentary rocks from the GEU.
Fe-Sulf—Fe sulfide
146
199 400 517
642
147
242
449
614
Anatase
Rutile
In
te
ns
ity
 (a
rbi
tra
ry 
un
its
)
Raman Shift (cm-1) 
200 400 600 800 1000
C
20µm
Rt
Rt
GPU
MEU
B
IlmAnt
Raman
Raman
Ant
Ant
Rt
100µm
Ilm
Rt
Rt
A
Fig. 5 a and b: High-contrast BSE images showing rutile coexisting
with anatase. Notice that rutile is brighter. c Raman spectra of anatase
and rutile (spot location presented in B)
Rutile occurrence and trace element behavior in medium-grade metasedimentary rocks 239
to those from higher grades (up to 930°C). According to the
authors, this behavior can be predicted assuming inter-grain
diffusion of Nb during continuous crystallization of rutile
from biotite and considering that rutile strongly favors Nb
over Ti when compared with biotite ((Nb/Ti)Rt/(Nb/Ti)Bt ratio
is ca. 50, see discussion in Luvizotto and Zack 2009).
Klemme et al. (2005, 2006) presented experimentally
derived rutile/melt and ilmenite/melt partition coefficients for
several elements, including Nb. The experiments were
carried out at atmospheric pressure and temperatures ranging
from 1200 to 1300°C. Results confirm previously obtained
data (e.g., Green and Pearson 1987; Foley et al. 2000; Green
2000; Horng and Hess 2000; Schmidt et al. 2004) and show
that Nb is strongly compatible in rutile (DRt=meltNb ¼ 22 for
andesitic melt composition) and moderately compatible to
incompatible in ilmenite (DIlm=meltNb ¼ 0:88 1:9 for basaltic
and DIlmNb ¼ 0:55 for basaltic andesite melt compositions).
These data show that rutile strongly favors the incorporation
of Nb when compared with ilmenite (assuming similar
partitioning behavior for the andesitic and basaltic andesite
melt composition). In fact, using these partition coefficients
a (Nb/Ti)Rt/(Nb/Ti)Ilm ratio of ca. 50 can be calculated. This
value is identical to the one calculated by Luvizotto and
Zack (2009) for the rutile/biotite pair. Hence, the same Nb
behavior described by the authors is expected to be observed
in the studied rocks (i.e., rutiles coexisting in chemical
equilibrium with ilmenite are expected to have significantly
higher Nb/Ti ratios). As Nb is strongly more compatible in
rutile than in ilmenite, rutiles formed during early stages of
the reaction are expected to have Nb contents significantly
higher than the ilmenite. As the reaction continues, Nb
concentrations in both rutile and ilmenite decrease strongly.
Calculations carried out by Luvizotto and Zack (2009) show
that during the initial stages of the reaction the decrease of
only 3% in the modal proportion of biotite leads to a
reduction of one order of magnitude in the Nb concentration
of both rutile and biotite. Such large variations are also
expected to be recorded in rutiles formed from ilmenite
breakdown.
Niobium concentration data presented in Fig. 6 show
that rutiles from the MEU display the highest variations in
Nb content among all the studied samples. Furthermore,
they have Nb/Ti ratios significantly higher than ilmenite (up
to ~15 times in sample 3/1). According to the partition
coefficients presented above, the Nb behavior in rutiles
from these samples is consistent with rutile crystallization
in equilibrium with ilmenite. The highest Nb concentration
obtained for a rutile from sample 3/1 (9526 ppm) is
consistent with a rutile occurring in equilibrium with an
ilmenite containing ~100 ppm of Nb. Hence, our results
support that Nb locally mobilized and is able to equilibrate
between rutile and ilmenite under the metamorphic con-
ditions of the MEU.
Rutiles from the GEU rocks are ilmenite-free. We
interpret the absence of ilmenite as an indication that the
rutile forming reaction was completed. Rutiles from these
rocks show a small spread in Nb concentrations. Assuming
the analyzed samples to be representative, the data suggest
homogenization of the variable Nb contents generated
during the early stages of rutile crystallization. Such
homogenization can take place through mechanisms like
dynamic recrystallization and/or inter-grain diffusion, in
accordance with the observation of Luvizotto and Zack
(2009). These processes are facilitated by higher temper-
atures and therefore more probable to take place in rocks
from the GEU than in those from the GPU and MEU.
Rutile
0 
P38c 3/1P2a 61c R10dS56 A15c*R11e*
1
2 x 10-2
N
b/
Ti
10
100
1000
10000
N
b 
in
 p
pm
6
6
7
5 7 2097
GPU MEU GEU
Ilmenite
P38c 3/1P2a 61c R10dS56
13 10 15 8
13
GPU MEU
Fig. 6 Summary of Nb concentrations (EMP and SIMS) obtained for
the rutiles and ilmenites. Samples are sorted according to increasing
metamorphic grade. The boxes represent, from bottom to top, the
second and third quartile (25 and 75% of the population). The bar
inside the box represents the median, while the lozenge (just for Nb/
Ti) represents the average. Whiskers represent the 10th and the 90th
percentile. When they occur, outliers are represented by small circles.
Numbers above the boxes refer to the number of analyzed grains (one
spot per grain). As EMP and SIMS results are within error, for grains
analyzed by both techniques only EMP data is plotted (because of the
higher spatial resolution). *: ilmenite-free samples
240 G.L. Luvizotto et al.
Exceptions to the Nb behavior discussed above are
samples from the lower grade GPU. Rutiles from this unit
are characterized by small scatter in Nb content and by
Nb/Ti ratios close to the ones obtained for ilmenites.
Results indicate that these rutiles are not in chemical
equilibrium with ilmenite (higher Nb/Ti ratios in rutile are
expected). One possible interpretation is that at metamorphic
conditions of the GPU (ca. 480°C and <0.9 GPa) chemical
diffusion was too slow and Nb was not able to exchange
between rutile and ilmenite. This observation suggests that
temperature is one of the main factors controlling the Nb
behavior, i.e., chemical mobility. However, other variables
such as presence of fluids and slow cooling rates may favor
the mobility of Nb as well.
Temperature records in rutile from medium-grade
metasedimentary rocks
The textures observed in metasedimentary rocks from the
GPU indicate that rutile crystallization took place under PT
conditions of ca. 480°C and 0.6–0.9 GPa. Zr concentrations
obtained for rutiles from this unit (Fig. 7) confirm previous
geothermometric data as all EMP measurements were below
detection limit (<40 ppm of Zr, <500°C). All but one rutile
from the MEU rocks give temperatures that match the
thermobarometric literature data (500–560°C, Rötzler et al.
1998). Temperatures in the 560–680°C range are obtained
for rutiles from the two investigated samples from the GEU
and are consistent with peak mineral assemblages (garnet
plus biotite, Table 1) and metamorphic textures observed in
these rocks. None of the metamorphically-grown rutiles
record unrealistically high temperatures (i.e., high Zr
contents) and are therefore consistent with metamorphic
condition under which they were formed. Low temperatures
obtained for some rutiles may either be a record of an early
stage during the prograde path or re-equilibration during the
retrograde path.
Detrital rutiles from medium-grade metasedimentary rocks
Triebold et al. (2007) showed that several rutiles from
present day drainage sediments from the catchment area of
PU, GPU and MEU record temperatures up to ca. 1000°C
(Zr-in-rutile, after calibration of Zack et al. 2004b). Since
the sediments are derived from medium-grade metamorphic
rocks (max. T of ca. 600°C for the MEU—see Fig. 1), these
high-T rutiles are interpreted to be inherited detrital grains
0 50 100 150 200 250 300 350 400
Zr in ppm
MEU
MEU
MEU
MEU
GEU
GEU
0
4
8
P2
GPU
<
 4
0 
pp
m
0
4
8
3/1
0
4
8 EGB04-R11e
0
2
4
A15c
0
2
4
EGB04-S56
0
4
8 EGB04-R10d
0
2
4
61c
GPU
0
3
6 P38c
<
 4
0 
pp
m
<
 4
0 
pp
m
<
 4
0 
pp
m
<
 4
0 
pp
m
<
 4
0 
pp
m
<
 4
0 
pp
m
500 550 600 650˚CFig. 7 Summary of Zr concentrations (EMP and SIMS) obtained for
the studied rutiles. Temperatures (on the top of the diagrams) were
calculated after the calibration of Tomkins et al. (2007) for pressure
values within 0.9–1.2 GPa (differences in temperature related to the
pressure effect are minimal within this pressure interval and are not
representable on the scale of the diagrams)
„
Rutile occurrence and trace element behavior in medium-grade metasedimentary rocks 241
that are preserved in these rocks. High temperatures
registered by these grains are further interpreted to be
records of former metamorphic cycles seen by the source
rocks for the sediments that compose the present-day
metasedimentary rocks of the PU, GPU and MEU. Such
high-T rutiles are not found in the catchment area of the
GEU. Based on these observations, the authors concluded
that the complete reequilibration of Zr contents in inherited
detrital rutile grains takes place only above ca. 600°C. The
existence of a minimum reequilibration temperature has
also been discussed by other authors (Stendal et al. 2006;
Meinhold et al. 2008).
Triebold et al. (2007) observed a high frequency of high-
T rutiles (and hence inherited detrital rutiles) in a mineral
separate from a quartzite sample from the MEU (EGB04-
S56, the same investigated in this paper). Such observation
contradicts results showing that highest frequencies of high-
T rutiles are observed in sediments derived from the PU and
GPU, thus raising the hypothesis that quartzites may be the
main source of high-T rutiles in present-day sediments
derived from greenschist-facies metassediments that contain
quartzite. This hypothesis is based on the fact that quartz-
ites are less reactive when comparing to other metamorphic
rocks, as the lack of Ca- and Fe-bearing phases reduces
their ability to crystallize titanite and ilmenite under
conditions where rutile is not stable (e.g., greenschist
facies). The downside of using mineral separates is that
petrographic textures are not preserved. Here, we present
BSE images from the quartzite sample (Fig. 3) showing
how these inherited rutiles occur in the rock. They are
clearly distinguishable from the polycrystalline aggregate
that represent the newly formed rutiles, since they occur as
large single crystals surrounded by fine grain ilmenite
(interpreted to be formed during prograde metamorphism
under green-schist facies or below). In addition, inherited
rutiles have much higher Nb and Zr contents (up to 3900
and 390 ppm respectively, see data in Fig. 3).
The results show, therefore, that quartzites may preserve size
and chemical composition of inherited detrital rutiles up to
higher metamorphic conditions when compared to pelitic
rocks. Preliminary calculations were carried out to evaluate
the impact of our observations for the sediment record of rutile.
More specifically, we evaluate which rock type liberates/
delivers the highest amount of detrital rutile during erosion of a
greenschist-facies metasedimentary catchment. We focus here
on sand-sized grains, because rutile in provenance studies is
mostly related to heavy mineral analyses, which usually con-
centrates on the finer-grained sand fraction. Based on BSE
images (see, e.g., Figs. 2 and 7) and petrographic observation,
average rutile grain sizes (size of the smallest dimension) of
50 μm and 100 μm can be roughly estimated for the
metapelites (phyllites/schists) and quartzites, respectively.
Calculations were performed assuming a Gaussian grain
size distribution and a standard deviation of 20% (in
accordance with results obtained for garnet porphyroblasts
by Hirsch 2008). Probabilities of occurrence of rutiles in
metapelites and quartzites were calculated for three grain
size fractions (Table 2): 63 μm, which corresponds to the
silt-sand threshold, a fraction used in traditional heavy
mineral analyses (see, e.g., Weltje and von Eynatten 2004);
80 μm, grain size fraction employed in our quantitative
provenance studies of rutile (see von Eynatten et al. 2005;
Triebold et al. 2007) and 100 μm, the average rutile
Chl
Initial Early
GPUUnits MEU GEU
Stages
Intermediate Final
Ilm
~100µm
Ilm
Rt
Rt
Ilm
Only Ilm Rt + Ilm Rt + Ilm Only Rt
Ilm is the 
main Nb 
and Ti 
carrier
Rt is the 
main Nb 
and Ti  
carrier
Chemical diffussion of Nb
Increasing metamorphic grade
Fig. 8 Illustration showing the main stages of rutile crystallization
from ilmenite during prograde metamorphism
Table 2 Probabilities of occurrence of rutiles with grains sizes of 63, 80 and 100µm in metapelites and quartzites; and percentage contribution of
quartzites in the sedimentary record of rutiles from low- to medium-grade metasedimentary sequences
Rutile Prob. Prob. Prob. Ratio Percentage contrib. in sediment
Fraction Mpel(%) Qzt(%) Qzt/Mpel (vol.) 1% Qzt %5 Qzt 10% Qzt
63µm 10 96 0.6 0.6 3.0 6.0
80µm 0.14 84 38 38 100 100
100µm <0.003 50 >1000 100 100 100
Parameters: Metapelite (Mpel)–average grain size=50µm, standard deviation=20%, TiO2 (whole rock) 1.0%. Quartzite (Qzt)–average grain size=
100µm, standard deviation=20%, TiO2 (whole rock) 0.5%. Prob (%)–probability of occurrence of rutile (calculated assuming a Gaussian
distribution). Please notice that the probability ratio of quartzite/pelite is expressed in volume (calculated taking into account the probabilities, the
differences in grain sizes (converted to volume) and TiO2 contents in the whole rock)
242 G.L. Luvizotto et al.
diameter in the quartzite, which relates via hydrodynamic
equivalence to a typical fine- to medium-grained sand
sample of average grain size ~200 μm. According to our
results, in a catchment area with a quartzite volume of
1.0%, 38% of the rutile grains larger than 80µm would
derive from the quartzite. With a volume of 2.5 to 3.0%
quartzite, almost all rutile grains larger than 80µm would
come from this rock. For the 100µm fraction the effect is
even more pronounced, as quartzites would virtually be the
only source of rutile, even for quartzite abundances below
1.0%. On the other hand, results show that pelites would
still be the main contributor of rutile for the 63 μm fraction.
Textures and trace element data presented above show
that quartzites may preserve detrital rutile grains (i.e., clastic
grains associated with the sedimentary deposition of the
protolith) up to temperatures higher than those needed to
crystallize new rutiles in metapelitic rocks. Furthermore,
these detrital grains may record information (e.g., Nb and
Cr systematics and T) inherited from an earlier geological
cycle. This observation, combined with the calculations
presented above, suggests that sand-sized rutiles derived
from greenschit-facies metasedimentary sequences that also
contain quartzites may not provide information on the
metapelites, since small volumes of quartzite may dominate
the sedimentary record of rutile (see Table 2).
Conclusions
Textures and trace element data indicate rutile growth from
ilmenite in medium-grade metasedimentary rocks from the
Erzgebirge. In samples from the GPU rutiles occur as
polycrystalline aggregates and pseudomorph the shape and
Nb/Ti of ilmenite. In MEU rocks, rutile aggregates have the
shape inherited from ilmenite. However, rutiles from this
unit display a larger scatter in Nb concentrations and have
higher Nb/Ti than ilmenite. This behavior indicates that Nb
concentrations in rutile are evolving towards equilibration
with relict ilmenites (considering that rutile strongly favors
the incorporation of Nb when compared with ilmenite).
GEU rocks are ilmenite-free. Taking into account that
pelitic rocks from the studied units have similar protoliths
(Mingram 1998) and assuming that they followed a rather
similar prograde path, the absence of ilmenite in GEU rocks
indicate that the rutile forming reaction was completed.
Rutiles from these rocks show a narrow scatter in Nb
contents, are single crystals and do not have the elongated
shape inherited from ilmenite. In these rocks, the homog-
enization of Nb contents in rutile was facilitated by higher
temperature and is probably related with mechanisms like
dynamic recrystalization and/or inter-grain diffusion.
Temperature records on all but one rutile grain are in
accordance with peak metamorphic conditions previously
presented for the studied rocks. Rutiles from the GPU give
temperatures <500°C. Temperatures within 500–560°C and
520–630°C were obtained for rutiles from MEU and GEU
rocks, respectively.
The only rutile with an exceptionally high Zr content
(390 ppm, T=680°C) is from a quartzite from the MEU. This
grain is interpreted to be an inherited detrital relict. Due to the
lack of Fe- Ca-bearing phases, quartzites are less reactive than
other rock types (e.g., phyllites and schists). This strongly
decreases the ability to form ilmenite and/or titanite.
Phyllites and schists are low- to medium-grade meta-
morphic products of pelitic sediments (fine-grained clastic
sediments of less than 1/16 mm grain size; Pettijohn 1975).
On the other hand, quartzites are often the metamorphic
product of coarser grained sediments, e.g., sandstones. In
the investigated phyllites and schists, metamorphically-
grown rutiles are fine-grained (smaller axis <50 μm) and
occur as polycrystalline aggregates (easily disintegrated
during weathering and mechanical transport in sediments).
However, large detrital rutile grains inherited from a
previous cycle may still be preserved in the quartzites.
Preliminary calculations taking into account modal abun-
dance and grain size distribution of rutile in metapelites and
quartzites show that quartzites may often be the main
source for rutiles in sediments derived from low-grade
metamorphic rocks. This seem to be the case of the
Erzgebirge, where high-temperature rutile relicts are fre-
quently found in sediments derived from low- to medium-
grade rocks, even though the volume of quartzite is less
than 5%. If such interpretation is correct, these high-
temperature relicts pre-date the peak metamorphism
achieved by Erzgebirge rocks. It has indeed been discussed
by Triebold et al. (2007) that these high-temperature rutiles
fit into the common picture of a derivation of Early
Paleozoic sediment of central Europe from source rocks
from the West African Craton. Our observations thus
encourage further studies, e.g., U-Pb dating of these high-
temperature relicts.
Acknowledgements The manuscript benefitted from constructive
reviews of Bernard Bingen and Andreas Moeller. Timm John and Fred
Gaidies are thanked for inviting us to contribute to this special issue.
Birgit Plessen (néeMingram) is thanked for providing part of the samples
investigated in the paper. Hans-Peter Meyer and Thomas Ludwig are
thanked for the maintenance of the EMP and SIMS (respectively) at the
Universität Heidelberg and for their assistance during analyses. Burkhard
Schmidt is thanked for his assistence during Raman analyses at the
Universitat Göttingen. Renato de Moraes is thanked for fruitful
discussions. Mauly Bottene is thanked for improving the English style
and grammar of the manuscript. This project was financially supported by
the Deutsche Forschungsgemeinschaft (projects ZA 285/2 and EY 23/3).
Open Access This article is distributed under the terms of the
Creative Commons Attribution Noncommercial License which per-
mits any noncommercial use, distribution, and reproduction in any
medium, provided the original author(s) and source are credited.
Rutile occurrence and trace element behavior in medium-grade metasedimentary rocks 243
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A
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244 G.L. Luvizotto et al.
T
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3
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d)
T
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Rutile occurrence and trace element behavior in medium-grade metasedimentary rocks 245
T
ab
le
3
(c
on
tin
ue
d)
T
ec
hn
iq
ue
S
am
pl
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U
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t4
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3
246 G.L. Luvizotto et al.
T
ab
le
3
(c
on
tin
ue
d)
T
ec
hn
iq
ue
S
am
pl
e
U
ni
t
G
ra
in
T
ex
t.
S
i
V
C
r
F
e
Z
r
N
b
S
n
S
b
H
f
T
a
W
U
T
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E
M
P
E
G
B
04
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M
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90
50
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Rutile occurrence and trace element behavior in medium-grade metasedimentary rocks 247
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