Search ScienceDirect

Download PDF Export Advanced

Journals & Books Register Sign in

Outline Recommended articles

Abstract
Geochimica et Cosmochimica Acta Magnesium isotope record of fluid metasomati…
Keywords Volume 240, 1 November 2018, Pages 64-79 Geochimica et Cosmochimica Acta, Volume 237, 2…
1. Introduction Download PDF View details
2. Geological background and the studied samples
3. Analytical methods Lithium isotope fractionation during magmatic differentiation The magmatic–hydrothermal transition in rare-…
Geochimica et Cosmochimica Acta, Volume 240, 2…
4. Results
5. Discussion
and hydrothermal processes in rare-metal granites Download PDF View details

6. Conclusion Jie Li a, b, Xiao-Long Huang a , Gang-Jian Wei a, Ying Liu a, Jin-Long Ma a, Li Han a, Peng-Li He a
Evolution of nascent mantle wedges during su…
Acknowledgments Show more
Geochimica et Cosmochimica Acta, Volume 245, 2…
Appendix A. Supplementary material
https://doi.org/10.1016/j.gca.2018.08.021 Get rights and content Download PDF View details
References
1 2 Next
Show full outline
Abstract
Citing articles (0)
Lithium isotope composition is potentially an effective geochemical tracer for
Figures (7)
hydrothermal processes and magmatic differentiation associated with rare-metal Article Metrics
granitic rocks. The Yashan and Xihuashan plutons in South China are extraordinarily
Li-F rich rare-metal granites that contain niobium-tantalum and tungsten deposits, Captures
respectively. As a moderately incompatible trace element in a felsic melt system, Li
Readers: 5
notably increases from protolithionite granite and Li-mica granite (88.7–175 μg/g) to
topaz-lepidolite granite (7430–8080 μg/g) in the Yanshan pluton. Despite a large
variation in Li concentrations, the δ7Li values of the Yashan pluton vary within in a View details

narrow range from −1.5‰ to 1.5‰. In contrast, the δ7Li values of the Xihuashan
pluton notably increase from biotite granite and two-mica granite (−0.2‰ to +0.7‰) to
Show all figures
muscovite granite (+1.9‰ to +4.4‰) with much less variation in the Li concentrations
(37.8–209 μg/g), which is best explained by the high diffusion rate of 6Li relative to 7Li
during disequilibrium fluid-rock interaction. The Xihuashan greisen has negative δ7Li
Tables (4)
values (from −2.7‰ to −2.1‰), which are attributed to extensive fluid-rock interaction
Table 1 in an open system.
Table 2
Table 3 Lithium isotope fractionations are consistent with a diversity of mineralization in the
Table 4 rare-metal granitic rocks. Tungsten mineralization is likely associated with an open
hydrothermal process. Fluid-rock interaction has a much stronger effect on Li isotope
fractionation than does magmatic differentiation in a highly evolved magmatic system.
Extras (1)
Ta-Nb mineralization is related to the magmatic differentiation in a closed magmatic-
Supplementary data hydrothermal system. The exsolution of a supercritical fluid during magmatic
differentiation and fluid-rock interaction in a closed magmatic-hydrothermal system is
insufficient for producing notable Li isotope fractionation.

Previous article in issue Next article in issue

Keywords
Lithium isotope fractionation; Rare-metal granite; Hydrothermal processes; Magmatic
differentiation; Fluid-rock interaction; South China

1. Introduction
Lithium-rich rare-metal granitic rocks have undergone extensive magmatic
differentiation and hydrothermal processes (e.g., Linnen, 1998, Linnen and Cuney,
2005, Li et al., 2015, Xie et al., 2016). These processes play an important role in
producing the diversity of mineralization in rare-metal granites (Li et al., 2015).
Understanding the magmatic differentiation and hydrothermal processes is thus an
essential step to better understanding the mechanisms of enrichment of rare-metal
elements and final mineralization within rare-metal granitic rocks.

Lithium, as a key volatile element for magmatic differentiation and accumulation of Ta

and Nb (especially Ta) in highly evolved magmas (Van Lichtervelde et al., 2010),
varies during the magmatic differentiation and hydrothermal processes in rare-metal
granitic rocks (e.g., Teng et al., 2006, Barnes et al., 2012, Masukawa et al., 2013,
Deveaud et al., 2015). There is a significant relative mass difference (∼17%) between
6Li and 7Li with the capability of large fractionation (>80‰ for δ7Li values; Tomascak

et al., 2016). Therefore, Li isotope composition is potentially an effective geochemical

tracer for the hydrothermal and magmatic differentiation processes. However, in
contrast to wide applications of Li isotope geochemistry in the investigation of
hydrothermal alteration, weathering processes and crust-mantle recycling (e.g.,
Pistiner and Henderson, 2003, Bouman et al., 2004, Virgier et al., 2008), very few
studies have addressed Li isotope fractionation during granite differentiation and late-
stage magmatic-hydrothermal evolution. For fractional crystallization, significant
isotopic fractionation only occurs during the terminal stage of granitic differentiation at
relatively low temperatures (Teng et al., 2006, Magna et al., 2010). Model calculations
show that granitic melts should evolve to isotopically heavier δ7Li values, if the extent
of fractional crystallization or magmatic differentiation is sufficiently large (Teng et al.,
2006). However, the magnitude of Li isotope fractionation during hydrothermal
processes is still disputed. Lynton et al. (2005) showed that hydrothermal fluids have
isotopically lighter Li when in equilibrium with quartz and muscovite. In contrast,
Wunder et al., 2006, Wunder et al., 2007 observed a relative preference of isotopically
heavy Li in fluids compared to that for coexisting minerals such as spodumene and Li-
mica; even so, this observation may not be fully adequate as evidenced by Li isotope
data from individual mineral phases of pegmatites (Magna et al., 2016). In a
pegmatite, the late solidus to early subsolidus phases (e.g., petalite, amblygonite and
spodumene) have relatively uniform δ7Li values in comparison with those of the early
crystallization phases (e.g., muscovite and beryl) and the late hydrothermal phases
(e.g., lithiophosphate and cookeite) show the highest δ7Li variability (Magna et al.,
2016). Overall, Li isotope fractionation in highly evolved rare-metal granitic rocks
remains poorly understood in contrast with its great potential as an effective
geochemical tracer for magmatic differentiation and hydrothermal processes.

The Yashan and Xihuashan granitic plutons in South China represent two typical
examples of Li-F rich rare-metal granites and contain Nb-Ta deposits and W deposits,
respectively (Huang et al., 2002, Wang et al., 2004, Li and Huang, 2013, Li et al.,
2013a, Li et al., 2015). In previous studies, we reported the bulk-rock major and trace
elements and in situ mineral compositions of micas and zircons in the Yashan and
Xihuashan plutons, showing that Ta-Nb enrichment is associated with highly evolved
magmas, but W mineralization is closely related to hydrothermal fluids (Li and Huang,
2013, Li et al., 2013a, Li et al., 2015). Thus, this is a good opportunity to investigate Li
isotope fractionation during the granitic differentiation and hydrothermal processes. In
this paper, we present Li isotopic and concentration data of the Yashan Ta-Nb granite
and the Xihuashan tungsten granite, with the aim to show the essence of the Li
isotope fractionation related to magmatic differentiation and hydrothermal processes
of the rare-metal granite, further illustrating the mechanism behind the diversity of
mineralization in the rare-metal granites.

2. Geological background and the studied samples

The South China Block (SCB) is traditionally divided into the Yangtze Block in the
northwest and the Cathaysia Block in the southeast with the boundary being the
northeasterly striking Jiangshan-Shaoxing fault (Fig. 1a). Throughout the Phanerozoic,
the Cathaysia Block was characterized by intense and widespread polyphase
orogenesis and magmatism that predominantly produced granites and rhyolites with
subordinate mafic and rare intermediate lithologies (e.g., Zhou et al., 2006, Li et al.,
2012). Jurassic to Cretaceous magmatism occurred in large parts of the Cathaysia
Block and the northeastern part of the Yangtze Block (Fig. 1a). In the Nanling area,
the Jurassic granitic rocks are highly evolved and peraluminous, and are associated
with W–Sn–Mo–Bi–Be–Nb–Ta mineralization (termed “Nanling tungsten-tin
polymetallic mineralization region” in Chinese literature; Fig. 1a) (e.g., Wang et al.,
1982, Pei and Hong, 1995).

Download high-res image (2MB) Download full-size image

Fig. 1. (a) Distribution of Cretaceous and Jurassic granites and volcanic rocks in SE China
(modified from Li et al., 2012), denoting the Nanling polymetallic mineralization region and the
locations of the Yashan Ta-Nb deposit and Xihuashan tungsten deposit; (b) simplified geological
map of the Yashan granitic pluton (modified from Yin et al., 1995); (c) simplified geological map of
the Xihuashan granitic pluton (modified from Guo et al., 2012).

The Yashan granitic pluton (or Yichun granites) in western Jiangxi province is
associated with Nb-Ta mineralization and consists of several multistage intrusive units
from oldest to youngest as follows (Fig. 1b): protolithionite ± muscovite granite,
muscovite granite, Li-mica granite and topaz-lepidolite granite (Yin et al., 1995,
Belkasmi et al., 2000, Huang et al., 2002). The muscovite granite is covered by the
protolithionite ± muscovite granite (Fig. 1b) but disclosed via underground mineral
exploration (Yin et al., 1995), whereas the other intrusive units crop out at the surface.
The detailed petrographic characteristics of these units are described in Yin et al.,
1995, Huang et al., 2002. Both Li-mica granite and topaz-lepidolite granite have the
highest content of rare-metal minerals such as lepidolite, columbite-group minerals,
cassiterite, amblygonite and microlite (Belkasmi et al., 2000, Huang et al., 2002). The
Ta-Nb-Li mineralization mainly occurred in the lepidolite granites as a result of
extreme fractionation (Yin et al., 1995). The studied samples were collected from three
outcropping units (protolithionite ± muscovite granite, Li-mica granite and topaz-
lepidolite granite). Li et al. (2015) described the detailed petrographic features of the
studied samples and showed a progressive shift of the mica compositions from
protolithionite to Li-mica to lepidolite. The protolithionite ± muscovite granite samples
consist predominantly of protolithionite with minor muscovite; the Li-mica granite
samples have mainly Li-mica and subordinately muscovite; and the topaz-lepidolite
granite samples are most lepidolite. Li-mica shows faint pleochroism from colorless to
pale pinkish, making it easily distinguishable from the muscovite and protolithionite.

The Xihuashan granitic pluton intruded into early Paleozoic low-grade

metamorphosed flysch-like sedimentary rocks (Fig. 1c). The Xihuashan mining district,
hosting the largest wolframite vein-type deposit in the Nanling region, consists of more
than 700 individual ore veins. These veins are mostly distributed in Xihuashan,
Shenglongkou, Dangping, Luokeng, Xialuogushan and Niuzishi (Fig. 1c). The largest
Xihuashan mine is associated with granites dated at 162–153 Ma (Zhang et al., 2009,
Wang et al., 2011, Guo et al., 2012, Bai et al., 2013, Li et al., 2013b) and belonging to
the major Jurassic magmatism and mineralization of the Nanling region (Fig. 1c).
Faults associated with the tungsten-ore veins are widespread in the Xihuashan pluton
(Fig. 1c) in contrast with the limited faults of the Yashan pluton (Fig. 1b). The
precipitation of wolframite was likely because of the mixing of magmatic and meteoric
fluids (Wei et al., 2012). The Xihuashan pluton has been subdivided into four intrusive
phases (phases A, B, C and D; Fig. 1c) based on detailed geological mapping and
exploratory drilling (Maruéjol et al., 1990, Wang et al., 2003). Phase A consists of
medium- to coarse-grained porphyritic granite (garnet-free) with minor mineralization;
it occurs as the outermost part of the pluton. Phase B is a medium-grained, garnet-
bearing porphyritic granite and hosts the major tungsten ore deposits of the
Xihuashan Mine. Phase C is a medium- to fine-grained, garnet-bearing porphyritic
granite and hosts the tungsten mineralization exploited at the Dangping Mine. Phase
D is a fine-grained, ore-barren granite. The studied samples were collected from
Phase B, including biotite granite, two-mica (biotite-muscovite) granite, muscovite
granite and greisen. The mica types in the samples progressively changed, i.e.
predominant biotite and minor muscovite in the biotite granite, dominant protolithionite
and subordinate muscovite in the two-mica granite, predominant zinnwaldite and
minor muscovite in the muscovite granite, and predominant Li-mica and minor
zinnwaldite in the greisen.

3. Analytical methods
All the analyses were performed at the State Key Laboratory of Isotope Geochemistry,
Guangzhou Institute of Geochemistry, Chinese Academy of Sciences.

3.1. Mica composition and BSE image analyses

Back-scattered-electron (BSE) images were obtained using a Zeiss Supra 55 field-
emission scanning electron microscope. Line analyses and mineral compositions of
diverse mica minerals were obtained using a JEOL JXA 8100 electron microprobe.
The operational conditions and standards used for calibration were the same as those
described in Li et al. (2015).

In situ trace element concentrations were measured in the micas using an Agilent
7500a Quadrupole inductively coupled plasma mass spectrometer (ICP-MS) coupled
with a RESOlution M-50 laser ablation system. The operating conditions were as
follows: a spot size of 42 μm, repetition rate of 5 Hz, and maximum energy of 90 mJ.
Calibration was externally completed using the NIST SRM 610 and 612 glasses with
Al (determined by EPMA) as the internal standard to correct for instrumental drift.
Quantifications were performed using the commercial software ICPMSDataCal 6.7
(Liu et al., 2008). The relative standard deviations (RSDs) of Li, Rb, Cs, Nb, Ta, W and
Sn ranged from 1% to 10%.

3.2. Lithium isotope analyses

Bulk-rock powders prepared for Li isotope analyses were the aliquots of the same
samples used in the previous studies, which were measured for bulk-rock major and
trace elements (Li et al., 2013a, Li et al., 2015). The minerals (i.e., quartz, mica, and
feldspars) of 11 samples were carefully hand-picked under a binocular microscope
from crushed rocks. The mica separates of some samples were a mixture of different
types of micas because they were nearly indistinguishable under a binocular
microscope. The mineral samples were cleaned with Milli-Q water in an ultrasonic
bath for 15 min and then dried at 90 °C and powdered in an agate mortar.

The procedure for chemical separation/purification was performed via ion

chromatography in a clean laboratory, as required to obtain a pure single-element
solution. The detailed chemical separation and analytical procedures are described in
the Appendix. Li isotopic data for international reference materials are listed in Table
1. The results are calculated relative to the L-SVEC as follows:

δ7Li (‰) = {[(7Li/6Li)sample/(7Li/6Li)L-SVEC] − 1} × 1000

Table 1. Comparison of measured δ7Li values analyzed in this study to the literature values.

Sample Instrument δ7Li (‰) 2 S.D. n Reference

Basalt

BCR-2 MC-ICP-MS 4.1 1.0 9 This study

BCR-2 n.a. 4.40 0.30 n.a. GeoRem value

BCR-2a MC-ICP-MS 4.40 0.57 2 Jochum et al. (2006)

BCR-2 MC-ICP-MS 3.19 0.12 4 Košler et al. (2009)

BCR-2 MC-ICP-MS 2.60 0.3 19 Penniston-Dorland et al. (2012)

BCR-2 MC-ICP-MS 2.87 0.39 2 Rosner et al. (2007)

BCR-2 ICP-MS 3.0 0.3 n.a. Janoušek et al. (2010)

Andesite

AGV-2 MC-ICP-MS 8.3 0. 5 11 This study

AGV-2 MC-ICP-MS 7.92 0.34 7 Choi et al. (2013)

AGV-2 MC-ICP-MS 7.98 0.19 n.a. Huang et al. (2010)

AGV-2 MC-ICP-MS 7.94 0.64 19 Magna et al. (2004)

AGV-2 MC-ICP-MS 8.14 0.66 2 Magna et al. (2006)

Granite

JG-2 MC-ICPMS 0.3 0.5 9 This study

JG-2 MC-ICPMS 0.2 0.15 12 Jeffcoate et al. (2004)

JG-2 MC-ICPMS 0.30 0.62 4 Bouman et al. (2004)

JG-2 MC-ICPMS -0.70 0.4 2 Pistiner and Henderson (2003)

JG-2 TIMS 0.4 0.2 3 James and Palmer (2000)

Li-gig MC-ICPMS 77.1 0.7 4 This study

a
The result is recalculated according to the original data in Jochum et al. (2006).

Replicated measurements of the reference materials AGV-2, JG-2 and BCR-2 yielded
δ7Li of +8.3 ± 0.5‰ (2σ, n = 11), +0.3 ± 0.5‰ (2σ, n = 9) and +4.1 ± 1.0‰ (2σ, n = 9),
respectively. The measured δ7Li of AGV-2 and JG-2 are in agreement with previously
published data (Table 1; Fig. 2). The measured δ7Li of BCR-2 is also within the
previously reported range of +2.60 to +4.40‰ (Jochum et al., 2006, Rosner et al.,
2007, Košler et al., 2009, Janoušek et al., 2010, Penniston-Dorland et al., 2012). The
measured δ7Li of the laboratory standard Li-gig is +77.1 ± 0.7‰ (2σ, n = 4). The
external reproducibility is ± 1.0‰ (2 S.D.) based on replicated measurements of the
reference materials.

Download high-res image (126KB) Download full-size image

Fig. 2. Comparison of the Li isotope composition of the rock reference materials (AGV-2, JG-2,
BCR-2) to previously reported data. Data sources: (1) Choi et al. (2013); (2) Huang et al. (2010);
(3) Magna et al. (2004); (4) Magna et al. (2006); (5) Jeffcoate et al. (2004); (6) Bouman et al.
(2004); (7) Pistiner and Henderson (2003); (8) James and Palmer (2000); (9) GeoRem at
http://georem.mpch-mainz.gwdg.de (Jochum et al., 2005); (10) Jochum et al. (2006); (11) Košler
et al. (2009); (12) Penniston-Dorland et al. (2012); (13) Rosner et al. (2007); (14) Janoušek et al.
(2010).

4. Results

4.1. Lithium isotope composition of the Yashan and Xihuashan granitic plutons
Bulk-rock Li concentration and isotope composition of the Yashan and Xihuashan
granitic plutons are shown in Table 2, combined with previously published bulk-rock F,
Rb, Cs, Zr, Hf, Nb and Ta data (Li and Huang, 2013, Li et al., 2013a, Li et al., 2015).

Table 2. Mineral models, some elements concentrations and bulk-rock Li isotopic data of the
Xihuashan and Yashan plutons.

Sample Rock Type Mineral model (%) Mica F Rb Cs Zr Hf(μg/g) Nb(μg/g

Type (wt%) μg/g) μg/g) μg/g)
Qtz Pl Kfs Mica

Xihuashan

XHS-03 biotite 36 32 19 13 Bt 0.67 496 25.8 122 4.35 15.6

granite

XHS-04 biotite 38 34 20 8 Bt 0.22 312 24.0 113 4.30 13.3

granite

XHS-09 two-mica 30 49 15 6 Prl+Ms 0.21 721 29.9 59.5 4.59 27.2

granite

XHS-11 two-mica 35 43 14 8 Prl+Ms 0.34 472 30.5 85.5 3.71 11.9

granite

XHS-06 muscovite 45 32 19 4 Zwd+Ms 0.08 854 63.7 74.2 7.19 25.1

granite

XHS-07 muscovite 39 35 22 4 Zwd+Ms 0.32 503 11.1 42.8 4.71 17.6

granite

XHS-01 greisen 55 – – 45 Zwd+Li- 1.22 1010 73.5 49.7 4.24 23.3

ms

XHS-02 greisen 51 49 Zwd+Li- 983 90.8 4.86 28.8

ms

XHS-12 greisen 51 – – 49 Zwd+Li- 1.05 1020 51.7 50.8 4.01 13.8

ms

Yashan

HYS-4 protolithionite 35 25 31 9 Prl 0.08 483 21.3 67.5 2.15 16.9

granite

HYS-5 protolithionite 40 21 27 12 Prl 0.13 472 21.9 18.4 1.13 29.2

granite

YC-1 Li-mica 26 41 29 4 Li- 0.06 992 32.1 13.6 1.61 73.9

granite ms+Ms

YC-2 Li-mica 27 43 25 5 Li- 0.09 1140 49.8 13.0 1.41 72.5

granite ms+Ms

YC10- topaz- 21 53 7 19 Lpd 1.82 3130 1711 21.0 3.85 61.1

10 lepidolite
granite

YC10- topaz- 25 48 11 16 Lpd 1.69 3190 1670 17.0 3.11 52.1

11 lepidolite
granite

δ7Li (‰) = {[(7Li/6Li)sample/(7Li/6Li)L-SVEC] − 1} × 1000; the δ7Li values in brackets are mean values of

replicated analyses.

2 S.D. is the error of δ7Li. Most samples were analyzed only once. The error estimated from repeated
analyses of reference materials is between 0.5 and 1.0‰.

Mineral abbreviations: quartz (Qtz); plagioclase (Pl); K-feldspar (Kfs); biotite (Bt); protolithionite (Prl);
muscovite (Ms); zinnwaldite (Zwd); Li-mica (Li-ms); lepidolite (Lpd).

Li concentrations of the Xihuashan samples vary from 37.8 μg/g to 1160 μg/g,

whereas those of the Yashan samples are extremely variable from 88.7 μg/g to
8080 μg/g (Table 2). The Xihuashan samples have more variable δ7Li values (−2.7‰
to +4.4‰; Table 2) than those of the Yashan samples (δ7Li = −1.5‰ to +1.5‰; Table
2). In particular, three greisen samples from the Xihuashan pluton (XHS01, XHS02
and XHS12) have remarkably negative δ7Li values (−2.7‰ to −2.1‰; Table 2).

Rock-forming minerals of the Yashan and Xihuashan plutons such as quartz, micas
and feldspars show very different Li concentrations and isotope compositions (Table
3). Quartz has low Li concentrations (24.6–42.5 μg/g) except for two topaz-lepidolite
granite samples of the Yashan pluton (168–191 μg/g), and they show high and
variable δ7Li values (from +8.2‰ to +19.8‰; Table 3). The micas have extremely high
Li concentrations (1620–54500 μg/g) and show low δ7Li values (from −2.1‰ to
+4.7‰) relative to that of quartz. Feldspars (including plagioclase and K-feldspar) also
have overall low Li concentrations (13.8–118 μg/g), except for two topaz-lepidolite
granite samples in the Yashan pluton (2270–3120 μg/g) and show a narrow range of
δ7Li values (from −0.5‰ to +3.6‰) relative to that of the micas (Table 3).

Table 3. Li concentration and isotopic data of the major minerals of the Xihuashan and Yashan
plutons.

Sample quartz mica feldspar Calculated bulk-rocka

Li (μg/g) δ7Li (‰) Li (μg/g) δ7Li (‰) Li (μg/g) δ7Li (‰) Li (μg/g) δ7Li (‰)

Xihuashan

XHS-03 24.6 17.0 2830 0.7 41.6 0.3 398 1.0

XHS-04 27.1 18.3 3470 0.8 35.0 −0.5 306 1.3

XHS-11 41.3 16.6 4910 0.3 73.7 0.9 449 0.9

XHS-07 26.0 13.7 4240 4.7 13.8 −0.0 188 5.0

XHS-01 40.4 11.0 4010 −1.3 1830 −1.2

XHS-02 35.1 8.2 3860 −2.1 1910 −2.0

Yashan

HYS-5 38.6 10.6 1620 −1.0 101 3.1 259 0.4

YC-1 27.5 9.7 2080 −1.2 19.5 −0.4 104 −0.3

YC-2 42.5 10.5 1910 −2.0 118 3.6 187 1.1

YC-10 191 19.2 35,500 0.8 3120 2.2 8660 1.2

YC-11 168 19.8 54,500 2.0 2270 1.9 10,100 2.1

a
Lithium concentrations and isotopes were calculated based on mineral models (Table 2) and
measured Li concentrations and δ7Li values of major rock-forming minerals (quartz, feldspars and
micas).

4.2. Zoned micas of the Xihuashan muscovite granite and greisen

The micas in the Xihuashan muscovite granite and greisen samples all show
compositional zoning in the BSE images (Fig. 3). In the Tischendorf et al. (1997)
diagram, the central part is similar to zinnwaldite and the rim is Li-muscovite or
muscovite. The zoned mica of the muscovite granite sample has a compositional
gradient from mantle to rim (Figs. 3a, b, 4a, b), while the greisen sample shows a
homogeneous core and rim with a sharp compositional boundary (Figs. 3c, d, 4c, d).
The rim contains higher Si and Al but lower Fe, F, Li, Rb and Cs than that of the core
(Fig. 3, Fig. 4; Table 4).

Download high-res image (989KB) Download full-size image

Fig. 3. Backscattered images of the Xihuashan zoned micas from muscovite granite (a, b) and
greisen (c, d). The open holes with numbers from 1 to 8 are the positions of the LA-ICPMS
analyses, and the results are listed in Table 4. The lines with white rims are the paths for the line
analyses shown in Fig. 4.

Download high-res image (717KB) Download full-size image

Fig. 4. Compositional changes in the Xihuashan zoned micas in terms of some representative
major elements from core to rim in the (a, b) muscovite granite, and (c, d) greisen samples.

Table 4. Representative EPMA and LA-ICP-MS analysis data for the zoned micas in the
Xihuashan pluton.

Rock Muscovite granite Greisen

Sitea 1-core 2-rim 3-core 4-rim 5-core 6-rim 7-core 8-rim

EPMA (wt%)

SiO2 42.45 46.69 43.34 46.45 38.22 45.49 42.09 45.67

TiO2 0.09 0.01 0.09 0.08 0.18 0.08 bdlb 0.04

Al2O3 25.80 30.28 27.91 30.68 24.11 29.74 25.38 29.96

FeO 13.43 6.37 11.51 5.96 19.00 8.51 13.97 7.46

MnO 1.12 0.55 0.90 0.43 1.11 0.51 0.90 0.44

MgO 0.21 0.16 0.18 0.14 0.15 0.15 0.17 0.13

Na2O 0.15 0.22 0.39 0.38 0.23 0.33 0.30 0.48

K2O 9.84 10.47 9.84 10.16 9.61 9.91 9.90 10.16

Rb2O 1.05 0.73 1.06 0.57 0.98 0.55 0.88 0.50

Cs2O 0.06 0.05 0.07 0.03 bdlb bdlb bdlb bdlb

F 1.38 0.70 2.11 1.46 3.87 2.84 3.98 2.77

2F O −0.58 −0.30 −0.89 −0.61 −1.63 −1.20 −1.68 −1.17

Total 95.00 95.93 96.51 95.73 95.82 96.91 95.89 96.44

LA-ICP-MS (μg/g)

Li 4510 743 3100 2710 7670 4190 7540 3030

Rb 5790 3310 5180 4540 4810 3850 4750 3670

Cs 956 441 1690 605 915 221 626 175

Sc 115 18.6 154 97.3 20.1 62.9 30.4 43.8

Sr 3.99 2.45 1.17 0.28 8.00 3.39 0.32 0.45

Y 0.18 0.19 0.04 0.09 0.08 0.04 bdlb 0.08

Zr 0.39 0.68 0.32 0.81 0.84 0.69 0.49 0.87

Hf 0.19 0.02 0.11 bdlb 0.31 0.20 0.14 0.24

Ta 142 5.69 83.0 126 78.1 18.5 15.8 10.0

Nb 138 32.0 107 195 139 43.3 33.9 26.0

Pb 13.6 17.3 12.0 14.7 6.22 6.82 6.07 6.80

Sn 694 265 848 694 518 683 537 621

W 69.7 14.9 71.9 63.0 46.6 63.6 46.2 54.4

Ba 2.30 3.83 2.17 0.87 23.1 23.0 14.4 23.1

Types Zwd Ms Zwd Ms Zwd Li-ms Zwd Li-ms

Mineral abbreviation: zinnwaldite (Zwd), muscovite (Ms), Li-ms (Li-mica).

a
The site positions are shown in Fig. 3.

b
bdl means below the detection limit.

5. Discussion

5.1. Lithium variation during magmatic differentiation of rare-metal granitic rocks

Lithium concentrations in granites largely depend on modal mineralogy (Teng et al.,
2009). Mica is the most important carrier of lithium in granitic rocks because of its
much higher partition coefficient for lithium than that of other minerals such as
feldspars and quartz (Bea et al., 1994, Icenhower and London, 1995). In highly
evolved rare-metal granitic rocks, such as the Yashan and Xihuashan plutons, bulk-
rock Li concentrations significantly vary according to the variable proportion of micas
and Li concentrations in the micas within the rocks (Table 2, Table 3).

Lithium is compatible in biotite and slightly incompatible in muscovite in the

peraluminous melt system (DLiBt/melt = 1.01–1.67 and DLiMus/melt = ∼0.8; Bea et al.,
1994, Icenhower and London, 1995), and the partition coefficient for Li between the
feldspar and felsic melt covers a wide range of 0.09–0.68 (Bindeman et al., 1998,
Bindeman and Davis, 2000, Aigner-Torres et al., 2007, Dohmen and Blundy, 2014).
Although lacking measured partition coefficients between the quartz and felsic melts,
lithium is assumed to be highly incompatible in quartz (DLiQtz/melt < 0.01) according to
the much lower Li concentrations in quartz than those in the coexisting micas in the
granite (0.8% of mica’s Li concentrations; Barnes et al., 2012, Breiter et al., 2013).
Collectively, lithium is essentially moderately to highly incompatible in a felsic system.
Li concentrations in rare-metal granitic rocks is thus expected to increase with
progressive differentiation.

In the Yashan pluton, bulk-rock Zr/Hf and Nb/Ta ratios decrease but Ta, Cs and Rb
concentrations increase from the protolithionite granite to Li-mica granite to topaz-
lepidolite granite (Table 2), which denotes a trend of magmatic differentiation.
Consistently, the Li and F concentrations of the micas gradually increase from
protolithionite to Li-mica to lepidolite (Li et al., 2015). Therefore, the topaz-lepidolite
granite contains very high Li concentrations, corresponding to its highly evolved
nature (Fig. 5), which is consistent with very high Li concentrations of lepidolite (Table
3).

Download high-res image (494KB) Download full-size image

Fig. 5. Plots of (a) Nb/Ta versus Zr/Hf, (b) whole rock δ7Li versus lithium concentration, (c) whole
rock δ7Li versus Nb/Ta, and (d) whole rock δ7Li versus Zr/Hf.

In the Xihuashan pluton, bulk-rock Zr/Hf and Nb/Ta ratios decrease from the biotite
granite to two-mica granite to muscovite granite (Fig. 5a), and Li and F concentrations
of mica accordingly increase (Li et al., 2013a), which is also consistent with a trend of
magmatic differentiation. However, bulk-rock Li concentrations of the Xihuashan
granites are independent of the differentiation trend (Fig. 5). Similarly, the Yashan Li-
mica granite contains even lower bulk-rock Li concentrations than those of the
protolithionite granite, inconsistent with its relatively highly evolved features such as
higher Li concentrations of mica and lower bulk-rock Zr/Hf and Nb/Ta ratios. The
discrepancy between the bulk-rock Li concentrations and magmatic differentiation can
be attributed to the strong fluid-rock interaction (Wang et al., 2003, Li et al., 2015). It is
evident that the micas in the Xihuashan muscovite granite and Yashan Li-mica granite
generally show compositional zoning and that the rims of the zoned mica grains have
a much lower content of Li and F than do the cores (Table 4; Li and Huang, 2013, Li et
al., 2013a, Li et al., 2015). In addition, both the Xihuashan muscovite granite and
Yashan Li-mica granite samples contain relatively less mica than that of the other
samples (Table 2), probably because of the separation of micas during differentiation,
which is also responsible for their relatively lower bulk-rock Li concentrations.

5.2. Lithium isotope fractionation during magmatic differentiation

Lithium isotope fractionation is principally controlled by its coordination in the mineral
structure and the partition coefficient between solid and melt (Wunder et al., 2011,
Magna et al., 2016). 7Li is preferentially incorporated into a lower-coordinated phase,
while 6Li favors a more highly coordinated site (e.g., Wunder et al., 2007). Essentially,
lithium is octahedrally coordinated in mica (Brigatti et al., 2000, Brigatti et al., 2003)
but is tetrahedrally coordinated in silicate melts (Wenger and Armbruster, 1991, Soltay
and Henderson, 2005, Maloney et al., 2008), indicating that mica incorporates 6Li over
7Li in felsic melts (Deveaud et al., 2015). Therefore, residual melts have a heavier Li

isotope composition if mica acts as the dominant fractionating phase during

differentiation.

However, Li generally behaves as a moderately to highly incompatible element in a

felsic igneous system. The bulk partition coefficient for mineral assemblages such as
those of Yashan granite samples are lower than 0.5 according to the partition
coefficients for mica, feldspars and quartz (DLimica/melt = ∼0.8–1.67;
DLifeldspars/melt = 0.09–0.68; DLiquartz/melt < 0.01). If DLisolid/melt < 0.5, fractional
crystallization can only produce a negligible shift of δ7Li (<1‰) even given a high
degree of differentiation (ca. 50% FC; Fig. 6). In the Yashan pluton, bulk-rock δ7Li
values of protolithionite and Li-mica granites vary in a narrow range from −1.5‰ to
−0.4‰ despite a large variation in the Nb/Ta and Zr/Hf values (Table 2; Fig. 5). This
finding demonstrates that magmatic differentiation is incapable of producing notable Li
isotope fractionation if mica is not a predominant fractionated phase. In contrast, the
topaz-lepidolite granite has slightly higher bulk-rock δ7Li values (+0.8‰ to +1.5‰)
than those of the other samples, a result of magmatic differentiation, consistent with
its high mica mode, very low Nb/Ta and Zr/Hf values (Table 2) and high δ7Li values of
lepidolite (Table 3).

Download high-res image (166KB) Download full-size image

Fig. 6. Lithium isotope fractionation modeled by Rayleigh distillation during crystallization when 6Li
prefers to incorporate into crystals (α < 1) (numbers on curves denote the partition coefficients in
the calculation). Equations and lithium isotopic values in the calculation are according to Teng et
al. (2006). Lithium isotopes in melt are expressed as δ7Limelt = (δ7Liinitial + 1000)f(α−1) − 1000,
where α is the ratio of the fraction of the Li isotope (α = 7Li/6Licrystal/7Li/6Limelt) and f is the fraction
of the Li remaining in the melt.

In the Xihuashan pluton, the greisen samples have very high modal mica but show
much lower δ7Li values than those of the granitic samples (Fig. 5). Such a Li isotope
fractionation is apparently inconsistent with magmatic differentiation but can be
attributed to strong fluid-rock interaction.

5.3. Lithium isotope fractionation during hydrothermal processes

Lithium is a fluid-mobile element that strongly fractionates into aqueous fluids during
fluid–rock interaction (e.g., Brenan et al., 1998, Tomascak et al., 2016). Thus, in
addition to magmatic differentiation, hydrothermal processes can also affect Li
concentration and result in strong Li isotope fractionation (Foustoukos et al., 2004,
Teng et al., 2006, Wunder et al., 2007, Masukawa et al., 2013, Tomascak et al., 2016).
In the case of a minor effect of magmatic differentiation on Li isotope fractionation
(Teng et al., 2006, Barnes et al., 2012), fluid-rock interaction may be a more likely
mechanism for producing strong Li isotope fractionation in granite. As the most Li-rich
mineral in the studied samples (Table 3), mica was a major factor constraining Li
isotope fractionation in the Xihuashan and Yashan plutons. This hypothesis is
supported by the strong positive correlation between bulk-rock δ7Li values and δ7Li
values of mica (R2 = 0.88; Fig. 7a) but the very weak correlation of δ7Li values
between the bulk-rock and feldspars or quartz (Fig. 7b, c). It is further supported by
the positive correlation between the measured and calculated bulk-rock δ7Li values
(Fig. 7d).

Download high-res image (419KB) Download full-size image

Fig. 7. Plots of (a) whole-rock δ7Li versus mica δ7Li; (b) whole-rock δ7Li versus quartz δ7Li; (c)
whole-rock δ7Li versus feldspar δ7Li; and (d) whole-rock δ7Li versus calculated δ7Li based on
mineral models, Li concentrations and δ7Li values of major minerals. Abbreviation: whole rock
(WR), mica (mc), quartz (qt), feldspars (fs), calculated values (cv).

In addition, as mica is among the main carriers of Li in granitic rock, interactions

between mica and fluid were the principal reason for Li isotope fractionation during
fluid-rock interaction. In this case, heavier 7Li is preferentially leached from micas into
the fluid (Chan et al., 1993, Brenan et al., 1998, Wunder et al., 2007), elevating the
δ7Li value of the fluid and producing strong Li isotope fractionation (e.g., Chan et al.,
1993, Wunder et al., 2007, Wunder et al., 2011). Accordingly, the rock that is subject
to strong fluid-rock interaction will have a lighter Li isotope composition because the
fluids might disperse significant amounts of 7Li-rich material if the new phases cannot
preferentially incorporate the heavier 7Li.

The Xihuashan greisen samples have much lower δ7Li values (from −2.7‰ to −2.1‰;
Table 2) than those of the granitic samples (Fig. 5), which cannot be attributed to mica
accumulation because the greisen is typically generated through fluid metasomatism
(Moura et al., 2014). Nevertheless, the Xihuashan greisen samples have much higher
bulk-rock Li concentrations than those of the granitic samples (Table 2), corresponding
to a high modal mica (zinnwaldite + Li-mica) (Table 2), a mineral that prefers to
incorporate 6Li (Wunder et al., 2007, Magna et al., 2016). Subsolidus fluid-rock
interaction is widespread in the mining area of the Xihuashan pluton (e.g., Hu et al.,
2012), and it potentially resulted in significant Li isotope fractionation. The zoned
micas of the Xihuashan greisen samples all show a homogeneous core and rim with a
sharp compositional boundary (Fig. 4c, d). The rim contains higher Si and Al content
but lower Fe, F, Li, Rb and Cs content than those of the core (Table 4), indicating that
the fluid was most likely exotic and depleted in Li, F, Rb and Cs relative to that of the
magmatic minerals. In addition, the fluid-rock interaction lasted sufficiently long to
develop the compositional homogeneity of the wide reaction rims in the zoned micas
of the greisen samples (Fig. 3a). Because the fluid was depleted in Li relative to the
magmatic minerals, it is possible that the Li leached from the micas into the fluid
during fluid-rock interaction. Furthermore, the interacted rim of the mica had a
relatively lower δ7Li value than that of the core because 7Li was preferentially leached
from the micas into the fluid during the interaction. Therefore, the low δ7Li value in the
Xihuashan greisen was mostly because of Li isotope fractionation between fluid and
rock. It is noteworthy that the δ7Li values of the separated micas in the Xihuashan
greisen are overall higher than the bulk-rock values (Fig. 7a). This result is reasonable
because the central part of the zoned micas has a greater chance of being picked out
from an over-crushed rock for producing overall higher δ7Li values than those of the
rims. In addition, the preference of the central part of the micas will result in an
overestimation of the Li concentrations, which is supported by the calculated bulk-rock
Li concentrations of the greisen samples (1830–1910 μg/g; Table 3) that are much
higher than the measured bulk-rock Li concentrations (441–1160 μg/g; Table 2).

Similar to the Xihuashan greisen sample, the zoned mica of the Yashan Li-mica
granite shows a homogeneous core and rim with a sharp compositional boundary (Li
et al., 2015), which indicates extensive and sufficient fluid-rock interaction. The final
effect of the interaction is a lowering of the δ7Li value of the Yashan Li-mica granites.
However, it is of particular interest that the Yashan Li-mica granite did not show any
notable lithium isotope fractionation (Fig. 5), and its δ7Li value is similar to that of the
protolithionite granite, because of its much lower mica mode than the protolithionite
granite (Table 2). Micas in the Yashan topaz-lepidolite granite also exhibit
compositional zoning, suggesting slight fluid-rock interaction (Li et al., 2015).
However, the interaction in the Yashan topaz-lepidolite granite was weak, as
demonstrated by the very thin rims of zoned mica (Li et al., 2015), and was therefore
insufficient for producing a notable Li isotopic shift of the bulk rock.

5.4. Diffusion-driven lithium isotope fractionation

The muscovite granite samples in the Xihuashan pluton have distinctly higher δ7Li
values (+1.9‰ and +4.4‰) than those of the biotite granite and two-mica granite
samples (δ7Li = −0.2‰ − +0.7‰), which might be because of the fractional
crystallization of the predominant mica. However, fractional crystallization of the
predominant mica is unlikely in a high-viscosity granitic melt and is also contradicted
by the gradually elevated mica Li concentration during differentiation (Li et al., 2013a).

The micas in the Xihuashan muscovite granite all exhibit compositional zoning in the
BSE images (Fig. 3a, b), indicating extensive fluid-rock interaction. Clearly, Li isotope
fractionation between mica and a fluid phase cannot account for the higher δ7Li value
of the Xihuashan muscovite granite samples. It is interesting to note that the zoned
micas in the Xihuashan muscovite granite samples show compositional gradients from
the mantle to rim (Fig. 4a, b), which implies that the zinnwaldite had undergone a
diffusion process during the disequilibrium fluid-rock interaction.

Because of a significant mass difference between the Li isotopes, 6Li diffuses up to

3% more rapidly than 7Li does in melts, fluids, minerals and rocks (Richter et al., 2003,
Beck et al., 2006). For example, diffusion experiments by Lynton et al. (2005)
demonstrated that muscovite may undergo rapid, sizable, and distinct changes in its Li
isotope compositions by diffusion through interaction with a Li-bearing fluid, and
muscovite has a higher δ7Li value than that of a coexisting fluid (e.g., Δmuscovite-aqueous
of ∼+18 to +20‰; Lynton et al., 2005) because 6Li diffuses measurably faster than
does the 7Li from a mica into a fluid. Lithium concentrations in zoned mica of the
Xihuashan muscovite granite gradually decrease from mantle to rim according to
compositional gradients (Fig. 3b) and the much lower Li concentrations of the rims
relative to the cores (Table 4). This result suggests that Li diffused from the mica into a
fluid, due to the higher diffusivity of the light 6Li isotope, producing a higher δ7Li value
in the rock (Richter et al., 2003, Liu et al., 2010). Therefore, the different diffusion
rates of Li isotopes during disequilibrium fluid-rock interaction were partially
responsible for the elevated δ7Li values in the Xihuashan muscovite granite.

5.5. Implication for the diversity of mineralization in the rare-metal granitic rocks
Extreme magmatic fractionation is required for the saturation of rare-metal and Li-
bearing minerals in granitic melts (e.g., Linnen, 1998, Linnen and Cuney, 2005),
whereas hydrothermal processes play an important role in leaching, accumulation and
transportation of rare-metal elements (Zhao et al., 2005, Xie et al., 2010, Li et al.,
2015, Han et al., 2016). Different magmatic and hydrothermal processes may produce
a diversity of mineralization in rare-metal granites (Li and Huang, 2013, Li et al.,
2015). However, magmatic differentiation in rare-metal granites is in most cases
overprinted by hydrothermal processes (e.g., Huang et al., 2002, Wang et al., 2004).
Thus, it is difficult to evaluate the practical effects of these processes on the
mineralization in rare-metal granitic rocks.

The Yashan and Xihuashan granitic plutons, as typical Li-F rich rare-metal granites in
South China that contain niobium-tantalum and tungsten deposits, respectively
(Huang et al., 2002, Wang et al., 2004, Li et al., 2015), show contrasting Li isotope
fractionation. The Yashan pluton has extremely variable lithium concentrations with
wide ranges in Nb/Ta and Zr/Hf ratios but only slightly elevated δ7Li values in the
topaz-lepidolite granite samples, suggesting that strong magmatic differentiation can
only produce weak Li isotope fractionation. In contrast, the Xihuashan pluton has
lower Li, Rb and Cs concentrations and a narrower range of Nb/Ta and Zr/Hf ratios but
more variable Li isotope compositions than those of the Yashan pluton, suggesting
strong Li isotope fractionation but less magmatic differentiation (Fig. 5).

The strong Li isotope fractionation in the Xihuashan pluton was most likely caused by
extensive fluid-rock interaction. Two types of fluids have been identified in the
Xihuashan pluton according to fluid inclusions, i.e. meteoric fluid and the fluid
exsolved from the granitic magma (Giuliani, 1988, Hu et al., 2012, Wei et al., 2012).
The meteoric fluid is depleted in Li, F, Rb and Cs, while the fluid exsolved from a
highly evolved magma is characterized by Cs enrichment (Audétat and Pettke, 2003,
Wang et al., 2004, Li et al., 2015). The rims of the zoned micas in the Xihuashan
muscovite granite and greisen samples mostly contain much less Cs content than that
of the cores (Table 4), indicating an exotic aqueous fluid during hydrothermal
percolation. The widespread faults within the Xihuashan pluton (Fig. 1c) were effective
channels for fluid leaching Li during the fluid-rock interaction.

The fluid in the hydrothermal process of the Yashan topaz-lepidolite granite was likely
a supercritical fluid exsolved from a highly evolved magma based on its enrichment in
Cs and Rb (Huang et al., 2002, Wang et al., 2004, Li et al., 2015). The exsolution of a
supercritical fluid has a marginal effect on Li isotope composition unless a large
amount of water has been exsolved (Foustoukos et al., 2004, Teng et al., 2006). The
thin reaction rims of the zoned lepidolite in the Yashan topaz-lepidolite granite (Li et
al., 2015) indicate that the volume of the exsolved fluid during magmatic differentiation
was restricted and insufficient to produce significant Li isotope fractionation. In
addition, the supercritical fluid-rock interaction in a closed magma-hydrothermal
system might have no effect on Li isotopic fractionation.

In brief, the contrasting Li isotope fractionation between the Xihuashan and Yashan
plutons is attributable to distinct magmatic and hydrothermal processes, which were
also essential mechanisms for the diversity of W and Ta-Nb mineralizations
associated with the rare-metal granites. Ta-Nb mineralizations are closely related to
relatively closed magma-hydrothermal systems, corresponding to a relatively low
fractionation of Li isotopes. In contrast, W mineralization is likely associated with open
hydrothermal processes, producing notable Li isotope fractionation.

6. Conclusion
The single-step column separation method used in this study was successfully applied
to the investigation of Li isotope fractionation in rare-metal granitic rocks. The
following conclusions can be drawn regarding Li isotope fractionation in the Yashan
and Xihuashan rare-metal granitic plutons of South China.
(1) Magmatic differentiation can significantly elevate Li concentrations in residual
magma but only produce minor fractionation of Li isotopes.

(2) As an important phase for Li in the Yashan and Xihuashan rare-metal granitic
plutons, mica is the key mineral in Li isotope fractionation. Fluid-rock interaction
generally decreases δ7Li values in the greisen because the light Li isotope is
preferentially fractionated into mica relative to that of the fluid phase. Elevated
δ7Li values in the Xihuashan muscovite granite are likely a result of the high
diffusion rate of 6Li relative to that of 7Li during disequilibrium fluid-rock
interaction.

(3) Fluid-rock interaction has a much stronger effect on Li isotope fractionation

than does magmatic differentiation in a highly evolved magmatic system. The
exsolution of supercritical fluid during magmatic differentiation and fluid-rock
interaction in a closed magmatic-hydrothermal system is insufficient to produce
notable Li isotope fractionation.

Acknowledgments
We appreciate L. Zhang and X.L. Tu for analytical assistance. We acknowledge the
constructive comments of Prof. H.R. Marschall and five anonymous reviewers, which
helped considerably in improving the manuscript, and thank Dr. Marc Norman for
editorial handling. This study was financially supported by the National Key Research
and Development Program of China (No. 2016YFC0600204) and National Natural
Science Foundation of China (NSFC Projects 41625007, U1701641). This is
contribution No. IS-2574 from GIG-CAS.

Appendix A. Supplementary material

The following are the Supplementary data to this article:

Download Word document (144KB) Help with docx files

Supplementary data.

References

Aigner-Torres et al., 2007 M. Aigner-Torres, J. Blundy, P. Ulmer, T. Pettke

Laser ablation ICPMS study of trace element partitioning between plagioclase and basaltic
melts: an experimental approach
Contrib. Mineral. Petrol., 153 (2007), pp. 647-667
CrossRef View Record in Scopus

Audétat and Pettke, 2003 A. Audétat, T. Pettke

The magmatic-hydrothermal evolution of two barren granites: a melt and fluid inclusion
study of the Rito del Medio and Cañada Pinabete plutons in northern New Mexico (USA)
Geochim. Cosmochim. Acta, 67 (2003), pp. 97-121
Article Download PDF View Record in Scopus

Bai et al., 2013 X.J. Bai, M. Wang, Y.D. Jiang, H.N. Qiu
Direct dating of tin–tungsten mineralization of the Piaotang tungsten deposit, South China,
by 40Ar/39Ar progressive crushing
Geochim. Cosmochim. Acta, 114 (2013), pp. 1-12
Article Download PDF View Record in Scopus

Barnes et al., 2012 E.M. Barnes, D. Weis, L.A. Groat

Significant Li isotope fractionation in geochemically evolved rare element-bearing
pegmatites from the Little Nahanni Pegmatite Group, NWT, Canada
Lithos, 132–133 (2012), pp. 21-36
Article Download PDF View Record in Scopus

Bea et al., 1994 F. Bea, M.D. Pereira, A. Stroh

Mineral/leucosome trace-element partitioning in a peraluminous migmatite (a laser
ablation-ICP-MS study)
Chem. Geol., 117 (1994), pp. 291-312
Article Download PDF View Record in Scopus

Beck et al., 2006 P. Beck, M. Chaussidon, J.A. Barrat, P. Gillet, M. Bohn

Diffusion induced Li isotopic fractionation during the cooling of magmatic rocks: the case
of pyroxene phenocrysts from nakhlite meteorites
Geochim. Cosmochim. Acta, 70 (2006), pp. 4813-4825
Article Download PDF View Record in Scopus

Belkasmi et al., 2000 M. Belkasmi, M. Cuney, P. Pollard, A. Bastoul

Chemistry of the Ta-Nb-Sn-W oxide minerals from the Yichun rare metal granite (SE China):
genetic implications and comparison with Moroccan and French Hercynian examples
Mineral. Mag., 64 (2000), pp. 507-523
CrossRef View Record in Scopus

Bindeman et al., 1998 I.N. Bindeman, A.M. Davis, M.J. Drake

Ion microprobe study of plagioclase-basalt partition experiments at natural concentration
level of trace elements
Geochim. Cosmochim. Acta, 62 (1998), pp. 1175-1193
Article Download PDF View Record in Scopus

Bindeman and Davis, 2000 I.N. Bindeman, A.M. Davis

Trace element partitioning between plagioclase and melt: investigation of dopant influence
on partition behaviour
Geochim. Cosmochim. Acta, 64 (2000), pp. 2863-2878
Article Download PDF View Record in Scopus

Bouman et al., 2004 C. Bouman, T. Elliott, P.Z. Vroon

Lithium inputs to subduction zones
Chem. Geol., 212 (2004), pp. 59-79
Article Download PDF View Record in Scopus

Brenan et al., 1998 J.M. Brenan, F.J. Ryerson, H.F. Shaw

The role of aqueous fluids in the slab-to-mantle transfer of boron, beryllium, and lithium
during subduction: experiments and models
Geochim. Cosmochim. Acta, 62 (1998), pp. 3337-3347
Article Download PDF View Record in Scopus

Breiter et al., 2013 K. Breiter, L. Ackerman, M. Svojtka, A. Müller

Behavior of trace elements in quartz from plutons of different geochemical signature: a
case study from the Bohemian Massif, Czech Republic
Lithos, 175–176 (2013), pp. 54-67
Article Download PDF View Record in Scopus

Brigatti et al., 2000 M.F. Brigatti, C. Lugli, L. Poppi, E.E. Foord, D.E. Kile
Crystal chemical variations in Li- and Fe-rich micas from Pikes Peak batholith (central
Colorado)
Am. Mineral., 85 (2000), pp. 1275-1286
CrossRef View Record in Scopus

Brigatti et al., 2003 M.F. Brigatti, D.E. Kile, L. Poppi

Crystal structure and chemistry of lithium-bearing trioctahedral micas-3T
Eur. J. Mineral., 15 (2003), pp. 349-355
CrossRef View Record in Scopus

Chan et al., 1993 L.H. Chan, J.M. Edmond, G. Thompson

A lithium isotope study of hot springs and metabasalts from mid-ocean ridge hydrothermal
systems
J. Geophys. Res., 98 (B6) (1993), pp. 9653-9659
CrossRef

Choi et al., 2013 M.S. Choi, J.S. Ryu, H.Y. Park, K.S. Lee, Y. Kil, H.S. Shin
Precise determination of the lithium isotope ratio in geological samples using MC-ICP-MS
with cool plasma
J. Anal. At. Spectrom., 28 (2013), pp. 505-509
CrossRef View Record in Scopus

Deveaud et al., 2015 S. Deveaud, R. Millot, A. Villaros

The genesis of LCT-type granitic pegmatites, as illustrated by lithium isotopes in micas
Chem. Geol., 411 (2015), pp. 97-111
Article Download PDF View Record in Scopus

Dohmen and Blundy, 2014 R. Dohmen, J. Blundy

A predictive thermodynamic model for element partitioning between plagioclase and melt
as a function of pressure, temperature and composition
Am. J. Sci., 314 (2014), pp. 1319-1372
CrossRef View Record in Scopus

Foustoukos et al., 2004 D.I. Foustoukos, R.H. James, M.E. Berndt, W.E. Seyfried Jr
Lithium isotopic systematics of hydrothermal vent fluids at the Main Endeavour Field,
Northern Juan de Fuca Ridge
Chem. Geol., 212 (2004), pp. 17-26
Article Download PDF View Record in Scopus

Giuliani, 1988 G. Giuliani, Y.D. Li, T.F. Sheng

Fluid inclusion study of Xihuashan tungsten deposit in the southern Jiangxi province,
China
Miner. Deposita, 23 (1988), pp. 24-33
View Record in Scopus

Guo et al., 2012 C.L. Guo, Y.C. Chen, Z.L. Zeng, F.S. Lou
Petrogenesis of the Xihuashan granites in southeastern China: constraints from
geochemistry and in-situ analyses of zircon U-Pb-Hf-O isotopes
Lithos, 148 (2012), pp. 209-227
Article Download PDF View Record in Scopus

Han et al., 2016 L. Han, X.L. Huang, J. Li, P.L. He, J.M. Yao
Oxygen fugacity variation recorded in apatite of the granite in the Dahutang tungsten
deposit, Jiangxi Province, South China
Acta Petrol. Sinica, 32 (2016), pp. 746-758
(in Chinese with English abstract)
View Record in Scopus

Hu et al., 2012 R.Z. Hu, X.W. Bi, G.H. Jiang, H.W. Chen, J.T. Peng, Y.Q. Qi, L.Y. Wu, W.F. Wei
Mantle-derived noble gases in ore-forming fluids of the granite-related Yaogangxian
tungsten deposit, Southeastern China
Miner. Deposita, 47 (2012), pp. 623-632
CrossRef View Record in Scopus

Huang et al., 2002 X.L. Huang, R.C. Wang, X.M. Chen, H. Hu, C.S. Liu
Vertical variations in the mineralogy of the Yichun topaz–lepidolite granite, Jiangxi
Province, southern China
Can. Mineral., 40 (2002), pp. 1047-1068
CrossRef View Record in Scopus

Huang et al., 2010 K.F. Huang, C.F. You, Y.H. Liu, R.M. Wang, P.Y. Lin, C.H. Chung
Low-memory, small sample size, accurate and high-precision determinations of lithium
isotopic ratios in natural materials by MC-ICP-MS
J. Anal. At. Spectrom., 25 (2010), pp. 1019-1024
CrossRef View Record in Scopus

Icenhower and London, 1995 J. Icenhower, D. London

An experimental study of element partitioning among biotite, muscovite, and coexisting
peraluminous silicic melt at 200 MPa (H2O)
Am. Mineral., 80 (1995), pp. 1229-1251
View Record in Scopus

James and Palmer, 2000 R.H. James, M.R. Palmer

The lithium isotope composition of international rock standards
Chem. Geol., 166 (2000), pp. 319-326
Article Download PDF View Record in Scopus

Janoušek et al., 2010 V. Janoušek, V. Erban, F.V. Holub, T. Magna, H. Bellon, B. Mlčoch, U. Wiechert, V.
Rapprich
Geochemistry and genesis of behind-arc basaltic lavas from eastern Nicaragua
J. Volcanol. Geoth. Res., 192 (2010), pp. 232-256
Article Download PDF View Record in Scopus

Jeffcoate et al., 2004 A.B. Jeffcoate, T. Elliott, A. Thomas, C. Bouman

Precise/small sample size determinations of lithium isotopic compositions of geological
reference materials and modern seawater by MC-ICP-MS
Geostand. Geoanal. Res., 28 (2004), pp. 161-172
CrossRef View Record in Scopus

Jochum et al., 2005 K.P. Jochum, U. Nohl, K. Herwig, E. Lammel, B. Stoll, A.W. Hofmann
GeoReM: a new geochemical database for reference materials and isotopic standards
Geostand. Geoanal. Res., 29 (2005), pp. 333-338
CrossRef View Record in Scopus

Jochum et al., 2006 K.P. Jochum, B. Stoll, K. Herwig, M. Willbold, A.W. Hofmann, M. Amini, S. Aarburg,
W. Abouchami, E. Hellebrand, B. Mocek, I. Raczek, A. Stracke, O. Alard, C. Bouman, S. Becker,
M. Dücking, H. Brätz, R. Klemd, D. de Bruin, D. Canil, D. Cornell, C.J. de Hoog, C. Dalpé, L.
Danyushevsky, A. Eisenhauer, Y.J. Gao, J.E. Snow, N. Groschopf, D. Günther, C. Latkoczy, M.
Guillong, E.H. Hauri, H.E. Höfer, Y. Lahaye, K. Horz, D.E. Jacob, S.A. Kasemann, A.J.R. Kent, T.
Ludwig, T. Zack, P.R.D. Mason, A. Meixner, M. Rosner, K. Misawa, B.P. Nash, J. Pfänder, W.R.
Premo, W.D. Sun, M. Tiepolo, R. Vannucci, T. Vennemann, D. Wayne, J.D. Woodhead
MPI-DING reference glasses for in situ microanalysis: new reference values for element
concentrations and isotope ratios
Geochem. Geophys. Geosyst., 7 (2006), p. Q02008

Košler et al., 2009 J. Košler, T. Magna, B. Mlčoch, P. Mixa, D. Nývlt, F.V. Holub
Combined Sr, Nd, Pb and Li isotope geochemistry of alkaline lavas from northern James
Ross Island (Antarctic Peninsula) and implications for back-arc magma formation
Chem. Geol., 258 (2009), pp. 207-218
Article Download PDF View Record in Scopus

Li et al., 2012 X.H. Li, Z.X. Li, B. He, W.X. Li, Q.L. Li, Y.Y. Gao, X.C. Wang
The Early Permian active continental margin and crustal growth of the Cathaysia Block: in
situ U-Pb, Lu-Hf and O isotope analyses of detrital zircons
Chem. Geol., 328 (2012), pp. 195-207
Article Download PDF View Record in Scopus

Li et al., 2015 J. Li, X.L. Huang, P.L. He, W.X. Li, Y. Yu, L.L. Chen
In situ analyses of micas in the Yashan granite, South China: constraints on magmatic and
hydrothermal evolutions of W and Ta-Nb bearing granites
Ore Geol. Rev., 65 (2015), pp. 793-810
Article Download PDF View Record in Scopus

Li et al., 2013a J. Li, J.W. Zhong, Y. Yu, X.L. Huang

Insights on magmatism and mineralization from micas in the Xihuashan granite, Jiangxi
Province, South China
Geochimica, 42 (2013), pp. 393-404
(in Chinese with English abstract)
View Record in Scopus

Li and Huang, 2013 J. Li, X.L. Huang

Mechanism of Ta-Nb enrichment and magmatic evolution in the Yashan granites, Jiangxi
Province, South China
Acta Petrol. Sinica, 29 (2013), pp. 4311-4322
(in Chinese with English abstract)
CrossRef View Record in Scopus

Li et al., 2013b Q.L. Li, X.H. Li, Z.W. Lan, C.L. Guo, Y.N. Yang, Y. Liu, G.Q. Tang
Monazite and xenotime U-Th–Pb geochronology by ion microprobe: dating highly
fractionated granites at Xihuashan tungsten mine, SE China
Contrib. Mineral. Petrol., 166 (2013), pp. 65-80
CrossRef View Record in Scopus

Linnen, 1998 R.L. Linnen

The solubility of Nb-Ta-Zr-Hf-W in granitic melts with Li and Li+F; constraints for
mineralization in rare metal granites and pegmatites
Econ. Geol., 93 (1998), pp. 1013-1025
CrossRef View Record in Scopus

Linnen and Cuney, 2005 R.L. Linnen, M. Cuney

Granite-related rare-element deposits and experimental constraints on Ta-Nb-W-Sn-Zr-Hf
mineralization
R.L. Linnen, I.M. Samson (Eds.), Rare element geochemistry and mineral deposits, Geological
Association of Canada Short Course Notes (2005), pp. 45-68
View Record in Scopus

Liu et al., 2008 Y.S. Liu, Z.C. Hu, S. Gao, D. Gunther, J. Xu, C.G. Gao, H.H. Chen
In situ analysis of major and trace elements of anhydrous minerals by LA-ICP-MS without
applying an internal standard
Chem. Geol., 257 (2008), pp. 34-43
Article Download PDF View Record in Scopus

Liu et al., 2010 X.M. Liu, R.L. Rudnick, S. Hier-Majumder, M. Sirbescu

Processes controlling lithium isotopic distribution in contact aureoles: a case study of the
Florence County pegmatites, Wisconsin
Geochem. Geophys. Geosyst., 11 (8) (2010), p. Q08014

Lynton et al., 2005 S.J. Lynton, R.J. Walker, P.A. Candela

Lithium isotopes in the system Qz-Ms-fluid: an experimental study
Geochim. Cosmochim. Acta, 69 (2005), pp. 3337-3347
Article Download PDF View Record in Scopus

Magna et al., 2004 T. Magna, U.H. Wiechert, A.N. Halliday

Low-blank isotope ratio measurement of small samples of lithium using multiple-collector
ICPMS
Int. J. Mass Spectrom., 239 (2004), pp. 67-76
Article Download PDF View Record in Scopus

Magna et al., 2006 T. Magna, U. Wiechert, T.L. Grove, A.N. Halliday

Lithium isotope fractionation in the southern Cascadia subduction zone
Earth Planet. Sci. Lett., 250 (2006), pp. 428-443
Article Download PDF View Record in Scopus

Magna et al., 2010 T. Magna, V. Janoušek, M. Kohút, F. Oberli, U. Wiechert

Fingerprinting sources of orogenic plutonic rocks from Variscan belt with lithium isotopes
and possible link to subduction-related origin of some A-type granites
Chem. Geol., 274 (2010), pp. 94-107
Article Download PDF View Record in Scopus

Magna et al., 2016 T. Magna, M. Novák, J. Cempírek, V. Janoušek, C. Ullmann, U. Wiechert

Crystallographic control on lithium isotope fractionation in Archean to Cenozoic lithium-
cesium-tantalum pegmatites
Geology, 44 (2016), pp. 656-658

Maloney et al., 2008 J.S. Maloney, P.I. Nabelek, M.L.C. Sirbescu, R. Halama
Lithium and its isotopes in tourmaline as indicators of the crystallization process in the
San Diego County pegmatites, California, USA
Eur. J. Mineral., 20 (2008), pp. 905-916
CrossRef View Record in Scopus

Maruéjol et al., 1990 P. Maruéjol, M. Cuney, L. Turpin

Magmatic and hydrothermal R.E.E. fractionation in the Xihuashan granites (SE China)
Contrib. Mineral. Petrol., 104 (1990), pp. 668-680
View Record in Scopus

Masukawa et al., 2013 K. Masukawa, Y. Nishio, K. Hayashi

Lithium-strontium isotope and heavy metal content of fluid inclusions and origin of ore-
forming fluid responsible for tungsten mineralization at Takatori mine, Japan
Geochem. J., 47 (2013), pp. 309-319
CrossRef View Record in Scopus

Moura et al., 2014 M.A. Moura, N.F. Botelho, G.R. Olivo, K. Kyser, R.M. Pontes
Genesis of the Proterozoic Mangabeira tin–indium mineralization, Central Brazil: evidence
from geology, petrology, fluid inclusion and stable isotope data
Ore Geol. Rev., 60 (2014), pp. 36-49
Article Download PDF View Record in Scopus

Pei and Hong, 1995 F.R. Pei, D.W. Hong

New advances in the study of collision orogeny of granites in South China and their
metallogenic series
Min. Deposits, 14 (1995), pp. 189-194
(in Chinese)

Penniston-Dorland et al., 2012 S. Penniston-Dorland, G.E. Bebout, P.A.E. Pogge von Strandmann, T.
Elliott, S.S. Sorensen
Lithium and its isotopes as tracers of subduction zone fluids and metasomatic processes:
evidence from the Catalina Schist, California, USA
Geochim. Cosmochim. Acta, 77 (2012), pp. 530-545
Article Download PDF View Record in Scopus

Pistiner and Henderson, 2003 J.S. Pistiner, G.M. Henderson

Lithium-isotope fractionation during continental weathering processes
Earth Planet. Sci. Lett., 214 (2003), pp. 327-339
Article Download PDF View Record in Scopus

Richter et al., 2003 F.M. Richter, A.M. Davis, D.J. DePaolo, E.B. Watson
Isotope fractionation by chemical diffusion between molten basalt and rhyolite
Geochim. Cosmochim. Acta, 67 (2003), pp. 3905-3923
Article Download PDF View Record in Scopus

Rosner et al., 2007 M. Rosner, L. Ball, B. Peucker-Ehrenbrink, J. Blusztajn, W. Bach, J. Erzinger

A simplified, accurate and fast method for lithium isotope analysis of rocks and fluids, and
δ7Li values of seawater and rock reference materials
Geostand. Geoanal. Res., 31 (2007), pp. 77-88
CrossRef View Record in Scopus

Soltay and Henderson, 2005 L.G. Soltay, G.S. Henderson

The structure of lithium containing silicate and germanate glasses
Can. Mineral., 43 (2005), pp. 1643-1651
CrossRef View Record in Scopus

Teng et al., 2006 F.Z. Teng, W.F. McDonough, R.L. Rudnick, R.J. Walker, M.L.C. Sirbescu
Lithium isotopic systematics of granites and pegmatites from the Black Hills, South Dakota
Am. Mineral., 91 (2006), pp. 1488-1498
CrossRef View Record in Scopus

Teng et al., 2009 F.Z. Teng, R.L. Rudnick, W.F. McDonough, F.Y. Wu
Lithium isotopic systematics of A-type granites and their mafic enclaves: further
constraints on the Li isotopic composition of the continental crust
Chem. Geol., 262 (2009), pp. 370-379
Article Download PDF View Record in Scopus

Tischendorf et al., 1997 G. Tischendorf, B. Gottesmann, H.J. Foerster, R.B. Trumbull

On Li-bearing micas; estimating Li from electron microprobe analyses and an improved
diagram for graphical representation
Mineral. Mag., 61 (1997), pp. 809-834
View Record in Scopus

Tomascak et al., 2016 P.B. Tomascak, T. Magna, F. Dohemen

Advances in lithium isotope geochemistry
Springer International Publishing Switzerland (2016), pp. 5-112
CrossRef

Van Lichtervelde et al., 2010 M. Van Lichtervelde, F. Holtz, J.M. Hanchar

Solubility of manganotantalite, zircon and hafnon in highly fluxed peralkaline to
peraluminous pegmatitic melts
Contrib. Mineral. Petrol., 160 (2010), pp. 17-32
CrossRef View Record in Scopus

Virgier et al., 2008 N. Vigier, A. Decarreau, R. Millot, J. Carignan, S. Petit, C. France-Lanord

Quantifying Li isotope fractionation during smectite formation and implications for the Li
cycle
Geochim. Cosmochim. Acta, 72 (2008), pp. 780-792
Article Download PDF View Record in Scopus

Wang et al., 1982 L.K. Wang, W.F. Zhu, S.L. Zhang

On the evolution of two petrogenetic and mineralized series of granites in South China
Geochimica, 4 (1982), pp. 329-339
(in Chinese with English abstract)
View Record in Scopus

Wang et al., 2003 R.C. Wang, F. Fontan, X.M. Chen, H. Hu, C.S. Liu, S.J. Xu, P. de Parseval
Accessory minerals in the Xihuashan Y-enriched granitic complex, Southern China: a
record of magmatic and hydrothermal stages of evolution
Can. Mineral., 41 (2003), pp. 727-748
CrossRef View Record in Scopus

Wang et al., 2004 R.C. Wang, H. Hu, A.C. Zhang, X.L. Huang, P. Ni
Pollucite and the cesium-dominant analogue of polylithionite as expressions of extreme Cs
enrichment in the Yichun topaz–lepidolite granite, southern China
Can. Mineral., 42 (2004), pp. 883-896
CrossRef View Record in Scopus

Wang et al., 2011 F.Y. Wang, C.Y. Li, M.X. Ling, H. Zhang, Y.L. Sun, W.D. Sun
Geochronology of the Xihuashan Tungsten Deposit in Southeastern China: constraints
from Re–Os and U-Pb Dating
Resour. Geol., 61 (2011), pp. 414-423
CrossRef View Record in Scopus

Wenger and Armbruster, 1991 M. Wenger, T. Armbruster

Crystal chemistry of lithium: oxygen coordination and bonding
Eur. J. Mineral., 3 (1991), pp. 387-399
View Record in Scopus

Wei et al., 2012 W.F. Wei, Z.C. Hu, X.W. Bi, J.T. Peng, W.C. Su, S.Q. Song, S.H. Shi
Infrared microthermometric and stable isotopic study of fluid inclusions in wolframite at
the Xihuashan tungsten deposit, Jiangxi province, China
Mineral Deposita, 47 (2012), pp. 589-605
CrossRef View Record in Scopus

Wunder et al., 2006 B. Wunder, A. Meixner, R. Romer, W. Heinrich

Temperature-dependent isotopic fractionation of lithium between clinopyroxene and high-
pressure hydrous fluids
Contrib. Mineral. Petrol., 151 (2006), pp. 112-120
CrossRef View Record in Scopus

Wunder et al., 2007 B. Wunder, A. Meixner, R.L. Romer, A. Feenstra, G. Schettler, W. Heinrich
Lithium isotope fractionation between Li-bearing staurolite, Li-mica and aqueous fluids: an
experimental study
Chem. Geol., 238 (2007), pp. 277-290
Article Download PDF View Record in Scopus

Wunder et al., 2011 B. Wunder, A. Meixner, R.L. Romer, S. Jahn

Li-isotope fractionation between silicates and fluids: pressure dependence and influence
of the bonding environment
Eur. J. Mineral., 23 (2011), pp. 333-342
CrossRef View Record in Scopus

Xie et al., 2016 L. Xie, R.C. Wang, X.D. Che, F.C. Huang, S. Erdmann, W.L. Zhang
Tracking magmatic and hydrothermal Nb–Ta–W–Sn fractionation using mineral textures
and composition: a case study from the late Cretaceous Jiepailing ore district in the
Nanling Range in South China
Ore Geol. Rev., 78 (2016), pp. 300-321
Article Download PDF View Record in Scopus

Xie et al., 2010 L. Xie, R.C. Wang, J. Chen, J.C. Zhu

Mineralogical evidence for magmatic and hydrothermal processes in the Qitianling
oxidized tin-bearing granite (Hunan, South China): EMP and (MC)-LA-ICPMS investigations
of three types of titanite
Chem. Geol., 276 (2010), pp. 53-68
Article Download PDF CrossRef View Record in Scopus

Yin et al., 1995 L. Yin, P. Pollard, S.X. Hu, R. Taylor

Geologic and geochemical characteristics of the Yichun Ta-Nb-Li deposit, Jiangxi Province
South China. Economic Geology, 90 (3) (1995), pp. 577-585

Zhang et al., 2009 W.L. Zhang, R.M. Hua, R.C. Wang, H.M. Li, W.J. Qu, J.Q. Ji
New dating of the Piaotang granite and related tungsten mineralization in Southern Jiangxi
Acta Geol. Sinica, 83 (2009), pp. 659-670
(in Chinese with English abstract)
View Record in Scopus

Zhao et al., 2005 K.D. Zhao, S.Y. Jiang, Y.H. Jiang, R.C. Wang
Mineral chemistry of the Qitianling granitoid and the Furong tin ore deposit in Hunan
Province, South China: implication for the genesis of granite and related tin mineralization
Eur. J. Mineral., 17 (2005), pp. 635-648
CrossRef View Record in Scopus

Zhou et al., 2006 X.M. Zhou, T. Sun, W.Z. Shen, L.S. Shu, Y.L. Niu
Petrogenesis of Mesozoic granitoids and volcanic rocks in South China: a response to
tectonic evolution
Episodes, 29 (2006), pp. 26-33
View Record in Scopus

© 2018 Elsevier Ltd. All rights reserved.

About ScienceDirect Remote access Shopping cart Contact and support Terms and conditions Privacy policy

We use cookies to help provide and enhance our service and tailor content and ads. By continuing you agree to the use of cookies.
Copyright © 2018 Elsevier B.V. or its licensors or contributors. ScienceDirect ® is a registered trademark of Elsevier B.V.