Appendix S1 auxiliary material Figures Tables Methodology

Auxiliary materials
Figure S1. As Figure 5 (a)–(c) but for the Yangtze and Cathaysia blocks of the
South China craton.
Figure S2. (a)–(f) Photomicrographs of samples from the North–Qinling complex.
(a), (c), and (f) plane polarized light, (b), (d), and (e) cross-polarized light. Mineral
abbreviations follow Kretz [1983 and Spear [1993]. (a) Recrystallized garnet together
with an omphacite prism and late amphibole, retrogressed eclogite 811084A. (b) Relic
omphacite encased in amphibole, retrogressed eclogite Q09B. (c) Euhedral inclusionrich garnet together with aligned omphacite and amphibole prisms, retrogressed
eclogite 811081A. (d) Phengite flakes, retrogressed eclogite 811084A. (e) Coarse
phengite flakes and albite porphyroblasts including garnet, garnet-bearing phengite
gneiss 75223A. (f) Garnet poikiloblasts in a weakly foliated matrix of biotite,
plagioclase and quartz, garnet gneiss 75214D. (g)–(h) Photographs of outcrop 76163
showing typical structures of migmatite of the Qinling complex. (g) Folded felsic
migmatite. (h) Resorption zone at the margin of a garnet amphibolite embedded in
leucosome. (i)–(r) Photomicrographs of migmatitic gneisses and intercalated
metabasites of the Qinling complex. (i), (k), (l), (m), (p), and (q) cross-polarized light;
(j), (n), (o), and (r) plane polarized light. (i) K-feldspar grains together with
plagioclase, quartz and biotite; garnet-bearing sillimanite gneiss 75247F. (j)
Sillimanite intensively intergrown with plagioclase; garnet-sillimanite gneiss 75248C.
(k) Randomly oriented cummingtonite prisms in a matrix of plagioclase, biotite and
quartz, garnet-cummingtonite gneiss 75254A. (l) Late muscovite mantels peak
metamorphic sillimanite, garnet-sillimanite gneiss 75251E. (m) Monazite grain
included in biotite, garnet-sillimanite gneiss 75248C. (n) Massive inhomogeneous
garnet-sillimanite gneiss 75247F. (o) Compositional banding of garnet gneiss
76172C. (p) Garnet clasts in a mylonitic matrix, garnet gneiss 76163B. (q) Granular
leucosome in contact to foliated melanosome, garnet gneiss 76175A. (r) Euhedral
garnet porphyroblast in a matrix of amphibole, biotite, plagioclase, and quartz, garnet
amphibolite 76163F. (s)–(v) Photomicrographs of Songshugou ultra-mafic rocks; (s)
and (t) cross-polarized light, (u) and (v) plane polarized light. (s) Amphibole prisms
and spinel in a granular olivine matrix; spinel dunite 75295A. (t) Clinopyroxene with
orthopyroxene prisms in serpentinized matrix; spinel harzburgite 75257A. (v)
Cummingtonite, zoned phlogopite and relic olivine in serpentinized matrix; spinel
harzburgite 75257A.
Figure S3. Equilibrium assemblage diagram and dependency on pressure and
temperature of garnet composition, its molar amount, the XAn of plagioclase, and the
composition of muscovite-phengite of sample 75223A. Bulk rock composition (in
mol): Si 24.176, Ti 0.179, Al 7.388, Fe 0.987, Mg 0.545, Ca, 0.179, Na, 1.324, K,
2.036, O 63.183.
Figure S4. Equilibrium assemblage diagram and dependency of garnet
composition, its molar amount, and the XAn of plagioclase of sample 75214D on
pressure and temperature. Bulk rock composition (in mol): Si 26.272, Ti 0.127, Al
4.528, Fe 1.071, Mg 0.955, Ca 0.743, Na 1.889, K 0.702, O 63.6545.
Figure S5. Equilibrium assemblage diagram and dependency of garnet
composition, garnet molar amount, and the XTi of biotite of sample Q33B on pressure
and temperature. Bulk rock composition (in mol): Si 20.139, Ti 0.115, Al 9.013 Fe
3.487, Mg 1.841, Ca 0.860, Na 1.367, K 1.489, O 61.6435.
Figure S6. Equilibrium assemblage diagram and dependency of garnet
composition, garnet molar amount, and the XTi of biotite of sample 75247F on
pressure and temperature. Bulk rock composition (in mol): Si 23.476, Ti 0.136, Al
6.247, Fe 1.873, Mg 0.598, Ca 0.880, Na 1.738, K 1.282, O 61.4555.
Figure S7. Equilibrium assemblage diagram and dependency of garnet
composition, garnet molar amount, and the XTi of biotite of sample 75248C on
pressure and temperature. Bulk rock composition (in mol): Si 24.019, Ti 0.284, Al
5.980, Fe 2.643, Mg 1.086, Ca 0.367, Na 0.818, K 1.555, O 62.8585.
Figure S8. Equilibrium assemblage diagram and dependency of garnet
composition, garnet molar amount, and the XTi of biotite of sample 75251E on
pressure and temperature. Bulk rock composition (in mol): Si 23.379, Ti 0.399, Al
6.745, Fe 1.887, Mg 0.582, Ca 0.667, Na 1.580, K 2.084, O 62.6415.
Figure S9. Equilibrium assemblage diagram and dependency of garnet
composition, garnet molar amount, and the XTi of biotite of sample 76172C on
pressure and temperature. Bulk rock composition (in mol): Si 23.842, Ti 0.346, Al
5.786, Fe 2.246, Mg 0.900, Ca 0.741, Na 1.952, K 1.435, O 62.6355.
Figure S10. Equilibrium assemblage diagram and dependency of garnet
composition, garnet molar amount, and the XTi of biotite of sample 76175A on
pressure and temperature. Bulk rock composition (in mol): Si 23.842, Ti 0.346, Al
5.786, Fe 2.246, Mg 0.900, Ca 0.741, Na 1.952, K 1.435, 62.6355.
Figure S11. Equilibrium assemblage diagram and dependency of garnet
composition, garnet molar amount, and the XTi of biotite of sample 75254A on
pressure and temperature. Bulk rock composition (in mol): Si 20.373, Ti 0.233, Al
6.573, Fe 2.207, Mg 2.212, Ca 1.364, Na 1.977, K 1.000, O 58.343.
Figure S12. Equilibrium assemblage diagram and dependency of garnet
composition, garnet molar amount, and the XTi of biotite of sample 76163B on
pressure and temperature. Bulk rock composition (in mol): Si 24.300, Ti 0.221, Al
5.741, Fe 1.871, Mg 0.957, Ca 0.923, Na 2.116, K 0.866, O 62.8955.
Figure S13. Equilibrium assemblage diagram and dependency of garnet
composition, garnet molar amount, and the XTi of biotite of sample 76163F on
pressure and temperature. Bulk rock composition (in mol): Si 19.345, Ti 0.693, Al
6.613, Fe 5.194, Mg 3.594, Ca 1.603, Na 0.166, K 1.548, O 61.2435.
Figure S14. Equilibrium assemblage diagram and dependency of garnet
composition, garnet molar amount, and the XTi of biotite of sample 75271B on
pressure and temperature. Bulk rock composition (in mol): Si 23.336, Ti 0.206, Al
6.002, Fe 2.223, Mg 0.777, Ca 0.495, Na 1.511, K 1.358, O 61.0165.
Figure S15. Equilibrium assemblage diagram and dependency of garnet
composition, garnet molar amount, and the XTi of biotite of sample 811102F on
pressure and temperature. Bulk rock composition (in mol): Si 22.133, Ti 0.223, Al
7.034, Fe 2.904, Mg 1.304, Ca 0.695, Na 2.095, K 1.570, O 61.9985.
Figure S16. Equilibrium assemblage diagram and dependency of garnet
composition, garnet molar amount, and the XTi of biotite of sample 811079A on
pressure and temperature. Bulk rock composition (in mol): Si 23.287, Ti 0.209, Al
6.069, Fe 1.800, Mg 0.970, Ca 1.176, Na 2.168, K 1.016, O 61.6335.
Figure S17. Representative cathodo-luminescence images of zircons dated in this
Table S1. Auxiliary material summarizing published (partly re-calculated) U/Th–
Pb geochronology of the Qinling orogenic collage.
Table S2. Auxiliary material summarizing sample locations and sample
Table S3. Auxiliary material summarizing representative microprobe analyses of
garnet. Cations based on a 12 oxygen basis. Ferric iron calculated after method of
Droop [1987].
Table S4. Representative microprobe analyses of pyroxene. Cations based on a 6
oxygen basis. Ferric iron estimated after method of Droop [1987].
Table S5. Representative microprobe analyses of white micas. Cations based on a
12 oxygen basis. End members follow Schliestedt [1980].
Table S6. Representative microprobe analyses of amphibole. Cations based on a
23 oxygen basis. Ferric iron estimated by minmax-midpoint method [Schumacher,
Table S7. Representative microprobe analyses of feldspar. Cations based on an 8
oxygen basis.
Table S8. Representative microprobe analyses of biotite. Cations based on a 12
oxygen basis. Water was iteratively estimated assuming F + Cl + OH = 2. 23.
Table S9. Representative microprobe analyses of olivine. Cations based on a 4
oxygen basis.
Table S10. Representative microprobe analyses of spinel. Cations based on a 4
oxygen basis. Ferric iron was calculated after method of Droop [1987].
Table S11. New U/Th–Pb zircon, monazite, and titanite and
Ar–39Ar phengite
data from this study.
Appendix S1
Description of analytical methods used in this study
300 samples were studied mainly along N–S trending traverses; sample localities
are summarized in Figure 2 and Table S2.
Microprobe analysis
Nineteen samples were analyzed with the electron microprobe (EMP) at
GeoForschungsZentrum Potsdam, TU Bergakademie Freiberg, and UC Santa
Barbara. The operation conditions were as follows: (1) Four-spectrometer CAMECA
SX-100 at Potsdam: 15 kV accelerating voltage; 20 nA beam current; 1-15 µm beam
diameter; 10–20 s major and 20–40 s minor elements peak-counting time. (2) Fivespectrometer JEOL JXA-8900R at Freiberg: 15 kV accelerating voltage; 20 nA
beam current; Si, Al, Mg, Ca, Sr, Ba, and K 20 s and Fe, Ni, Na, Cr, Mn, Ti 30 s
peak-counting time. (3) Five-spectrometer CAMECA SX50 at Santa Barbara: 15 kV
accelerating voltage; 15 nA beam current; 10–20 s major and 20–40 s minor
elements peak-counting time. We used natural and synthetic mineral standards of the
Smithsonian Institute, MAC™, and CAMECA. Raw intensity data were corrected
with the PAP program [Pouchou and Pichoir, 1985]. Representative analyses of
major phases are shown in Tables S3–S10.
Bulk-rock geochemistry
Bulk-rock geochemistry was analyzed by X-ray fluorescence using a Bruker
SRS 3000 WDS-XRF at Basel University on fused glass discs made of 300 mg
ignited rock powder and 4700 mg ultrapure Li2B4O7. Accuracy was checked against
USGS, NIM, and SARM standards.
Determination of metamorphic conditions
Theriak/Domino-program package [de Capitani and Brown, 1987; de Capitani,
1994; de Capitani and Petrakakis, 2010]; the program package is available at It uses Gibbs free-energy
minimization to calculate equilibrium assemblages together with the modal
proportions and compositions of individual stable phases at given T and P based on
bulk-rock composition and thermodynamic models of rock-forming minerals.
Equilibrium assemblage and isopleth diagrams, showing the compositions of major
phases such as garnet, plagioclase, phengite, biotite or amphiboles, were computed
and interpreted by comparing observed assemblages and intersections of isopleths.
For all equilibrium-assemblage calculations, we used the thermodynamic
database of Holland and Powell [1998; version tcds55] together with activity
models of thermocalc 3.30 (see below). Model systems are CaO-K2O-FeO-MgOAl2O3-SiO2-H2O (CKFMASH), and TiO2-Na2O-CaO-K2O-FeO-MgO-Al2O3-SiO2H2O (NCKFMASHT). Generally, H2O was in excess.
An essential aspect of the equilibrium-assemblage calculations is the choice of a
proper bulk-rock composition for the equilibrium-mineral assemblage. In case of
homogeneous samples (i.e., the investigated ultra-mafic rocks), we used bulk-rock
chemical analysis data. As several accessory phases, which are not considered in the
calculation (e.g., apatite, pyrite), contribute to the bulk, P and S were subtracted
from the chemical data before modeling. In samples with distinct compositional
layering or other inhomogeneities, we modeled the local chemical composition
using microprobe analyses of the equilibrium-mineral assemblage and counting of
typically 700 points. Apart from thermodynamic modeling, we applied winTWQ
multi-equilibrium calculations ([Berman, 1991, 2007]; see below for solution
models) as well as conventional thermobarometers.
Garnet growth modeling
The zoning of a garnet porphyroblasts reflects their evolution [e.g., Spear, 1993]
and allows the reconstruction of the P–T history of metamorphic rocks [e.g., Evans,
2004; Tinkham and Ghent, 2005; Gaidies et al., 2006; 2008a]. A key aspect for
garnet-growth modeling is the thorough examination of the observed zoning, i.e.
whether it results from prograde, possibly multi-stage growth with minor or
negligible influence of diffusion, or whether diffusion strongly modified the garnet
zoning. For example, core isopleths of a zoned garnet may intersect far away from
the calculated garnet-in isograde. If the zoning is restricted to rims, garnet-isopleth
thermobarometry can still be used, as the homogeneous core results from
homogenization or reaction overstepping. In any other case, the application of the
method is doubtful, because (i) the chosen bulk-rock composition might be
inappropriate; (ii) the garnet-core composition could have undergone strong
modification by diffusion; (iii) the garnet core might be inherited. On the other
hand, if distinct rimward decreasing pyrope and increasing spessartine contents
reflect a strong retrograde zoning, or, if the calculated amount of garnet implies
resorption instead of growth along the suggested P–T path, the garnet zoning has
been distinctly modified by diffusion. However, the core of the crystal could still
preserve its original composition, thus a P–T estimate for garnet-core growth via
isopleth thermobarometry is still possible. However, it is questionable to derive P–T
data for intermediate or rim compositions; although the influence of diffusion can be
calculated (e.g., with the Theria_g program; Gaidies et al. [2008a,b]), the reactivity
of the rock matrix must be considered. During prograde growth, the matrix usually
is considered to be fluid-saturated due to dehydration reactions with rising T, which
ensures quick ion-exchange and equilibration. But this may not be valid for a
retrograde P–T evolution. Furthermore, different matrix minerals have different
diffusivities and closure temperatures. If the corresponding matrix phase is a ferromagnesian sheet silicate, the Fe-Mg exchange between garnet and the matrix is
limited by the garnet as sheet silicates re-equilibrate easier and at lower
temperatures. Mn is well known to back-diffuse into garnet [e.g., Kohn and Spear,
2000], because matrix phases cannot incorporate (enough) Mn into their lattice; the
same could happen with Ca. In felsic metamorphic rocks, the other relevant Caphase is plagioclase. However, Ca-diffusion in plagioclase is distinctly lower than in
garnet due to coupled substitution with Si, Al and Na and therefore retrograde Ca
exchange with garnet might be hampered. As a consequence, different elements
could stop retrograde equilibration at different P–T conditions and an isopleth
intersection may deviate distinctly from the actual P–T conditions.
Solution models used to calculate equilibrium assemblage diagrams and
Solid solutions: Garnet, melt, biotite, spinell: White et al. [2007]; white mica:
Coggon and Holland [2002]; amphibole: Diener et al. [2007]; clinopyroxene: Green
et al. [2007]; chlorite, chloritoid, staurolite, cordierite, ilmenite: Holland and Powell
[1998]; orthopyroxene: White et al. [2002]. Non-solution phases: unless otherwise
noted all other included into the database of Holland and Powell [1998].
Solution models used for winTWQ 3.34 multi-equilibrium calculations
For winTWQ calculations, we used the mineral data file “DEC06.DAT” together
with the solution data file “DEC06.SLN” and the solution models: Garnet: BA07
(based on Berman and Aranovich, [1996]); clinopyroxene: BAP95 [Berman et al.,
U/Th–Pb geochronology
We performed U/Th–Pb zircon geochronology on grain mounts; multiple grains
and several spots within some grains were analyzed in each sample. Grain liberation
employed high-voltage pulse power fragmentation in the TU Bergakademie Freiberg
SELFRAG facility (specifications see Final separation was by
magnetic, heavy liquid, and optical methods; grains were mounted in resin blocks
by optical
microscopy and
cathodoluminescence before analysis. The U/Th–Pb analyses were conducted (i) on
monazite by secondary-ion mass spectrometry (SIMS) at UCLA following Robinson
et al. [2004] and (ii) on zircon by LA-ICPMS methods in three different
laboratories: the University of Arizona, USA (marked as LA-ICPMS (UA) in the
data Figures), the Senckenberg Naturhistorische Sammlungen Dresden, Germany
(LA-ICPMS (DD)), and the University of California, Santa Barbara, USA (LAICPMS (UCSB)). Laser-ablation multi-collector inductively coupled plasma mass
spectrometry (LA-MCICPMS) at the University of Arizona followed procedures
outlined in Hacker et al. [2006]. The Dresden laboratory uses a Thermo-Scientific
Element 2 XR sector field ICP-MS coupled to a New Wave UP-193 Excimer Laser
System. As this facility is relative new, we provide a more detailed analytical
description below. The analyses at UCSB were conducted using a Nu Instruments
Plasma MCICPMS and a Photon Machines 193 nm ArF excimer laser ablation
system. The analytical method is detailed in Schmidt et al. [2011].
U/Th–Pb LA-ICPMS geochronology at the Senckenberg Naturhistorische
Sammlungen, Dresden
Zircons were analyzed for U, Th, and Pb isotopes by LA-ICPMS techniques using
a Thermo-Scientific Element 2 XR sector field ICP-MS coupled to a New Wave UP193 Excimer Laser System. A teardrop-shaped, low volume laser cell constructed by
Ben Jähne (Dresden) and Axel Gerdes (Frankfurt/M.) was used to enable sequential
sampling of heterogeneous grains (e.g., growth zones) during time resolved data
acquisition. Each analysis consisted of approximately 15 s background acquisition
followed by 30 s data acquisition, using a laser spot-size of 20 to 35 µm. A commonPb correction based on the interference- and background-corrected 204Pb signal and a
model Pb composition [Stacey and Kramers, 1975] was carried out if necessary. The
necessity of the correction is judged on whether the corrected
Pb/206Pb lies outside
of the internal errors of the measured ratios. Discordant analyses were generally
interpreted with care. Raw data were corrected for background signal, common Pb,
laser induced elemental fractionation, instrumental mass discrimination, and timedependant elemental fractionation of Pb/Th and Pb/U using an Excel® spreadsheet
program developed by Axel Gerdes (Institute of Geosciences, Johann Wolfgang
Goethe-University Frankfurt, Frankfurt am Main, Germany). Reported uncertainties
were propagated by quadratic addition of the external reproducibility obtained from
the standard zircon GJ-1 (~0.6% and 0.5-1% for the
Pb/206Pb and
respectively) during individual analytical sessions and the within-run precision of
each analysis. Further details of the instruments settings are available in the Table
below. For further details on analytical protocol and data processing see Gerdes and
Zeh [2006].
The uncertainty in the degree of concordance of Precambrian–Paleozoic grains
dated by the LA-ICPMS method is relatively large and results obtained from just a
single analysis have to be interpreted with care. A typical uncertainty of 2–3% (2σ) in
Pb/206Pb for a Late Neoproterozoic grain (e.g., 560 Ma) relates to an absolute error
on the
Pb/206Pb age of 45–65 Ma. Such a result gives space for interpretation of
concordance or slight discordance. The latter one could be caused by episodic lead
loss, fractionation, or infiltration Pb isotopes by a fluid or on micro-cracks. Thus,
zircons showing a degree of concordance in the range of 90–110 % in this paper are
classified as concordant because of the overlap of the error ellipse with the concordia
[e.g., Linnemann et al., 2011]. Th/U ratios are obtained from the LA-ICP-MS
measurements of investigated zircon grains. U and Pb content and Th/U ratio were
calculated relative to the GJ-1 zircon standard and are accurate to approximately 10%.
Settings for the instruments used in the geochronological Laboratory
(GeoPlasmaLab Dresden) of the Senckenberg Naturhistorische Sammlungen Dresden
(Excimer Laser, New Wave, UP 193) and (ICP-MS, Thermo Fisher, Element 2 XR).
Finnigan Element 2 XR
Forward Power
1390 W
15.0 l min-1 (plasma)
Gas flow rate
1.07 l min-1 (aux)
Scan mode
Scanned masses
202, 204, 206, 207,
208, 232, 235, 238
Mass resolution
Dead time
18 ns
Oxide UO /U
< 1%
Dwell time
4 ms
≤ 1 ms/amu
Settling time
Number of scans
15 s
Ablation time
30 s
Integration time
Laser system
1.4 s (=25 scans)
UP193 New Wave
193 nm, excimer
Nominal spot diameter
25-35 µm (unknowns)
35 µm (standard)
0.25 l min-1 He
Carrier gas
1.1 l min-1 Ar
Laser settings
10 Hz, 55% LP
Drill speed (DS) /
~ 0.5 µm/s (DS)
Raster scan speed (RSS)
c. 3 cm3
Cell volume
6 x 106 counts/pg U
Ar–39Ar geochronology
Ar/39Ar analysis was carried out at Argonlabor Freiberg (ALF) at TU
Bergakademie Freiberg, Germany. Phengites were repeatedly ultrasonicated in
alcohol and de-ionized water, dried, and subsequently wrapped into Al foil. The Al-
sample packets were loaded in 5 × 5 mm wells on 33 mm Al-discs for irradiation,
which was done under Cd shielding for 120 hours at the FRG II reactor in Geesthacht,
Germany, at a thermal neutron fluence of ~5x1013 n/cm2s and a thermal to fast
neutron ratio of ~40. Irradiated samples were unwrapped and loaded in 3 × 1 mm
(diameter × depth) wells on an oxygen free copper disc for measurements. Step
heating was performed using an energy controlled floating 30W CO2 laser system at
10.6 µm wavelength with a defocused beam at 3 mm diameter, followed by gas
purification applying two AP10N getter pumps, one at room temperature and one at
400°C. Laser heating time was 5 minutes; cleaning time was 10 minutes per step. Ar
isotope compositions were measured in static mode using a GV Instruments ARGUS
noble gas mass spectrometer equipped with five faraday cups and 1012 Ohm resistors
on mass positions 36-39 and a 1011 Ohm resistor on mass position 40. Typical blank
levels are 2.5×10-16 mol
Ar and 8.1×10-18 mol
Ar. Measurement time was 7.5
minutes per step acquiring 45 scans at 10 seconds integration time each. Mass bias
was corrected assuming linear mass dependent fractionation and using an atmospheric
Ar/36Ar ratio of 295.5. For raw data reduction an in-house developed Matlab toolbox
was used; isochron, inverse isochron and plateau ages have been calculated using
ISOPLOT 3.7 [Ludwig, 2008]. All ages were calculated against Fish Canyon sanidine
as flux monitor (28.305 ± 0.036 Ma; Renne et al. [2010]), errors on ages are 1σ.
Corrections for interfering Ar isotopes have been done using (36Ar/37Ar)Ca = 0.000261,
(39Ar/37Ar)Ca = 0.000709, (38Ar/39Ar)K = 0.0107, (40Ar/39Ar)K = 0.0024 and applying
5% uncertainty.
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